PLATINUM METALS REVIEW · 2016. 1. 28. · I Fig. I The perjhnance losses seen in a typical DMFC MEA operuting with dilute MeOH and air at SOT, compared to those in a PEMFC. The PEMFC

UK ISSN 0032-1400

PLATINUM METALS REVIEW A Quarterly Survey of Research on the Platinum Metals and

of Developments in their Application in Industry www.matthey.com and www.platinurn,matthey.com

VOL. 46 OCTOBER 2002 NO. 4

Contents

Catalysis for Low Temperature Fuel Cells Ey M. P Hogarth and I R. Ralph

The Chemistry of the Platinum Group Metals By John Evans

Platinum Metals in Biological and Medicinal Chemistry By Matthew D. Hall

An Equilibrium in Catalyst Optimisation and Development? ByG. R. Owen

Structural Changes and Their Kinetics in Hydrogen-Containing Palladium Systems

By V: M. Avdjukhina, A. A. Katsnelson and G. t? Revkevich

Polymer-Supported Rhodmm Catalysts Soluble in sc-COz

9th International Platinum Symposium By R. G. Cawthorn

Recyclable Ruthenium-BINAP Catalysts

A C F Power Coatingsm By Paul Williams

Electrically Induced Phosphorescence

Abstracts

New Patents

Indexes to Volume 46

146

165

166

167

169

176

177

180

181

187

188

192

195

Communications should be addressed to: The Editor, Susan V. Ashton, Platinum Metals Review, [email protected] Johnson Matthey Public Limited Company, Hatton Garden, London EC1N 8EE

Catalysis for Low Temperature Fuel Cells PART 1 1 1 : CHALLENGES FOR THE DIRECT METHANOL FUEL CELL

By M. P. Hogarth and T. R. Ralph Johnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH, U.K.

The direct methanol fuel cell (DMFC) is a low temperature fitel cell operating ut temperutures of30 to 130°C. The DMFC i s powered by CI liquidfie1 (usually considered essentia1,for transport uses) and is therefore regarded by some as the idea1,fuel cell system. I I I this piper, the DMFC is cornpared to the hydrogen-fuelled proton exchange mentbrane firel cell (PEMFC) which was discussed in detail in the Jaiiuaty and July issues. While a typical DMFC is less eficient than a PEMFC, work to improve its performance with new electrocatulyst murerials j o r utilisation in the membrane electrode assemblies has proved successfiil. This work is described here and some possible commercial uses j o r the DMFC are also considered.

Two of the most advanced low temperature fuel cells are the proton exchange membrane fuel cell (PEMFC) and the direct methanol fuel cell (DMFC). The DMFC directly consumes liquid fuel (methanol), while the PEMFC is fuelled by hydrogen. Operating a fuel cell with liquid fuel is considered by some to be essential for transport applications - for compatibility with the existing petroleum distribution network. The DMFC also has some system-related advantages over the PEMFC, making it of interest to fuel cell developers. For instance, the DMFC has no need for a fuel processor (or reformer) to convert a liquid hydro- carbon fuel (gasoline) into a consumable source of hydrogen. This considerably reduces the complexity and cost of the system. The DMFC system does not require the complex humidification and heat management hardware modules used in the PEMFC system: the d u t e methanol-water mix- tures circulating around the DMFC provide the necessary humidification and heat management.

If it can meet the performance required of a commercially viable device, the DMFC system will be potentially more cost effective than the PEMFC. Performance has been a major problem for the DMFC: it typically produces only one third of the PEMFC's power density. Hence, the DMFC com- munity has made great efforts to bring the performance closer to that of the PEMFC, and particularly to extend the maximum operating temperature. The majority of the work has involved

developing materials, such as new anode and cathode electrocatalysts and new proton conducting polymers, to promote the efficiency of the membrane electrode assemblies (MEiAs) used in the DMFC stack. Advanced MEA designs have also been developed. Since most effort has been direct- ed towards increasing the efficiency of the MEA components, the DMFC system itself has remained relatively undeveloped compared to the PEMFC - particularly for transport use.

However, interest in producing low temperature (< 60°C) ambient-pressure portable DMFC systems has increased recently. This is because the power densities now accessible by state-of-the-art MEAs may be enough for these systems to become competitive with leading secondary battery technologies. This area could thus become a near-term market oppommity for the DMFC, with transport uses being a longer-term goal, if further performance gains can be achieved.

Comparison of PEMFCs and DMFCs The PEMFC and DMFC have much in com-

mon, in particular their MEAs. The MEA and its components were described in detail in Part I (1). The MEA of a DMFC usually consists of five layers which include gas and liquid diffusion layers, and electrocatalyst layers with a polymeric proton conducting acidic membrane in between (2). The proton conducting membrane acts as an electronic insulator between the electrodes, but allows protons

Phfimm Metals Rev., 2002,46, (4), 146164 146

I

Fig. I The perjhnance losses seen in a typical DMFC MEA operuting with dilute MeOH and air at SOT, compared to those in a PEMFC. The PEMFC is operating with pure hydrogen. A list of furtors affecting the eflciencies of both .fuel cells i s on the right in the Figure

to migrate efficiently from the anode to the cathode. The membrane also functions as a physical barrier to prevent mixing of the reactants. In ad&- tion, a soluble form of the membrane m a t e d is used to impregnate the electrocatalyst layers to extend the membrane interface. This provides a proton conducting pathway.

While the structures of the MEAs used in the PEMFC and DMFC are similar, the performance of each is very different. A comparison of the performance of the two fuel cells and the factors which limit their efficiencies is shown in Figure 1.

The DMFC has a maximum thermodynamic voltage of 1.1 8 V at 25”C, dehned by its anode and cathode half-cell reactions:

Anode reaction: CH30H + H20 = COz + 6H’ + 6e- E , = 0.046 v (i)

Cathode reaction: 3/202 + 6H’ + 6e- = 3H20 E”, = 1.23 V (ii)

Cell reaction: CH3OH + HzO + 3/202 = COZ + 3H20 Encd = 1.18 V (ii)

In comparison, the PEMFC has a maximum thermodynamic voltage of 1.23 V at 25°C. In prac-

tice, the cell voltage in both fuel cells is much less than this, see Figure 1. For example, at a current density of 500 mA cm”, the cell voltage is typically around 0.75 V for the PEMFC (1) and 0.4 V for the DMFC (3). Therefore, the power density and efficiency are considerably hgher in the PEMFC (61 per cent) than in the DMFC (34 per cent).

The Effect of Poor Kinetics Both types of fuel cell are limited by the poor

electrochemical activiy of their cutbode-r, for reasons described in Part I (1). This reduces the cell voltage of both by up to 0.4 V at 500 mA

However, unlike the PEMFC (when operated with pure hydrogen), the DMFC anode is also h- ited by poor electrochemical activity (kinetic loss [8] in Figure 1). This can account for a further loss in cell voltage of more than 0.3 V at 500 mA cm-’ (at

To increase both the anode and cathode activities in the DMFC, the electrocatalysts employed are usually unsupported (with high Pt loadmgs of typically 5 to 10 mg Pt cm-’ for each electrode) rather than the carbon-supported electrocatalysts used in the PEMFC. This Pt loading is too high

900C).

Phtinnm MefaLr h., 2002,46, (4) 147

for commercial exploitation of the DMFC (but it does of course dramatically increase the power densities attainable by the MEA). By contrast, typical PEMFC electrodes are carbon-supported electrocatalysts, loaded at 0.2 to 0.5 mg Pt cm”.

Fuel Crossover Another critical effect, which reduces the effi-

ciency of the DMFC, is fuel crossover (methanol ~ J J O V W [4] in Figure 1). Methanol and water readily diffuse through all the commercially available polymeric membrane electrolytes (such as Nafion), and significant quantities of methanol and particularly water pass from the anode to the cathode. This reduces the cathode efficiency in two ways.

First, any methanol that comes into contact with the cathode electrocatalyst will reduce the efficiency of the oxygen reduction reaction by a compet- ing electrochemical process - known as the mixed potential effect. Second, the cathode structure becomes waterlogged or flooded, and is no longer an efficient structure for gas diffusion (mars transport loss, [3] in Figure 1). Both these effects can reduce the cell voltage by a further 0.2 to 0.3 V, particularly when practical air flows are used.

In practice, the effects of methanol crossover can be reduced to a large extent by careful design of the MEA structure or by the application of novel membrane materials (4) or cathode electrocatalyst materials ( 5 , 6). The use of thick membrane materials, such as Nafion 117 (- 180 pn), in preference to those used in the PEMFC, such as Nafion 112 (50 q), is often a sensible choice. Using a thick membrane does increase the cell resistance (ehchu&e ndJtance [5] in Figure 1). but it is usually easily outweighed by an improved performance as a result of reduced crossover.

A further consequence of the high methanol crossover rates in commercially available materials is that to reduce it, the DMFC anode must be supplied with dilute methanol fuel, typically 0.5 to 1.0 molar concentration. This presents problems for system design because, in addition to the methanol fuel, large quantities of water must be stored, adding to the size and complexity of the system. It is particularly awkward for applications where space is limited, such as portable devices. As the

methanol concentrations used in the DMFC are low, the anode structure has to be designed to allow both efficient diffusion of the liquid fuel into the electrocatalyst layer and effective removal of the product carbon dioxide (COz). Correct design of the anode electrode spucture is very important for limiting anode mass iransportlosses ([GI in Figure 1).

Anode Electrocatalyst Limitations Although the electrooxidation of methanol is

thermodynamically driven (by the negative Gibbs free energy change, AG, in the fuel cell), in practice, the rate of methanol electrooxidation is severely limited by poor reaction kinetics. To increase the efficiency of the anode reaction, it is necessary to understand the reaction mechanism. Indeed, there are now probably over 100 published papers that deal with identifying the nature and rate limiting steps of this reaction (7).

The most likely reaction scheme to describe the methanol electrooxidation process is shown in Figure 2 (Steps i to viii). Only Pt-based electrocatalysts display the necessary reactivity and stability in the acidic environment of the DMFC. Spectroscopic studies on polycrystalline Pt have shown that methanol is electrosorbed in a complex process analogous to dehydrogenation. Sequential stripping of protons and electrons is believed to take place (Steps i to iv), leading to the formation of carbon-containing intermediates, such as linear- ly bonded - c o , d , and -CHO,d, (8, 9).

Although the vast majority of these studies have been carried out on bulk polycrystalline or single crystal metallic Pt surfaces, it is possible to study the methanol electrosorption process on finely divided electrocatalysts in a single cell. Methanol electrosorption appears to occur spontaneously when the anode and cathode of an MEA are connected externally by an electrical circuit. Hence, when methanol comes into contact with the electrocatalyst, an electric current flows between the two electrodes. This occurs for only a brief period of time until the electrocatalyst becomes poisoned with surface-bound intermediates, such as -CO,d,.

The results of an experiment in which three different anode electrocatalysts were exposed to a dilute methanol/water mixture are shown in

P h f h m Met& Rev., 2002, 46, (4) 148

Fig. 2 A reaction .scheme ilescribing the probable methntiol electrooxidutiorr process (Steps i to vii i) )tithin ( i D M F C titiode. Only Pt-bciscd electrocatalyst.~ show /he necessary reactivity rind sicrbility in the acidic environment of the DMFC to be ofprclcticnl use

Pt

Figure 3. The electrocatalysts were 40 wt.% Pt/Vulcan XC72R carbon black, 20 wt.% Pt, 10 wt.% Ru/Vulcan XC72R and PtRu black alloy. The loadings on each electrode were: 1 mg Pt cm-* and 0.5 mg Ru cm-2 (ruthenium). Experiments were carried out at 90°C in a 50 cm2 in-house designed single cell using Nafion 112 membrane- based MEAs with Pt black cathodes (4 mg cm-*). The half-cell behaviour of the anode was studied by supplying pure hydrogen to the cathode, which then functioned as a reversible hydrogen electrode @HE) and also as a counter electrode.

Electrosorption was carried out under poten- tiostatic control at 75 mV (vs. WE) with a 2 M methanol solution for a period of 20 minutes. This potential was chosen because it is below the threshold potential at which the electrosorbed methanol would be electrooxidised to C02. The cell was then flushed with pure water for a further 20 minutes to remove any unreacted methanol.

As Figure 3 shows, a charge was produced by each electrocatalyst when it came into contact with

methanol (at - 400 s). The charge levelled out after a few minutes, suggesting that the electrocatalyst surface became poisoned and was unable to

Fig. 3 Three anode electroccitulysts (locrdings: I mg Pt em-', 0.5 nig Ru cni') in u single cell. with Nqfiorl 112 membrctne-based MEAs. exposed to dilute methanoUwter ( i t 90°C. The ccithodes are Pt bkrck (4 mg Pt en-'). At - 400 s after methanol contac/, the electroccrtcr1v.st.s produce charge which levels out rrs the su~cice becomes poisoned mid stops reacting. Cyclic voltammetry cmjirmed tin intermediate species was present

PLdnntn Metah b., 2002, 46, (4) 149

I Table I I Surface Areas of Electrocatalyst Materials Pt and PtRu Determined with Gas-Phase CO and Electrochemically with CO and Methanol, and the Resulting Stripping Peak Potentials

Electrocatalyst surface area, m2 g" Pt or m2 g-' PtRu

Stripping peak potential, I Electrocatalyst

40 wt.% PtiXC72R 20 wt.% Pt, 10 Wt.% Ru/XC72R PtRu alloy black

co, gas-p hase

67 139 83

co, electrochemical

( E PSAco)

40 80 46

Methanol, electrochemical

(EPSAM~OH)

37 78 39

co, electrochemical

538 305 302

Methanol, electrochemical

react further with methanol. It was not possible to quantify the rate of t h i s reaction since a few sec- onds were required to pass the methanol solution through the flow field and across the entire area of the electrode. The presence of an intermediate species was confinned by ramping the anode potential up to 0.9 V (vs. RHE) at a scan rate of 10 mV s-'. This resulted in an electrooxidation peak (stripping peak) for each electrocatalyst, shown in Figure 4 (corresponding to Steps vi to viii in Figure

2). Water electrosorption is believed to occur leading to the formation of -OHdd, species which then react with the intermediate species to form COz (10,ll). This process results in the saipping peaks.

As the nature of the surface-bound intermediate was unknown but was believed to be 40- l ike , the experiments were repeated but with CO gas passing through the fuel cell instead of methanol. A CO,d,-stripping peak was recorded for each electrocatalyst, see Figure 4. In addition to the elec-

Fig. 4 Stripping peaks (electrosorbed methanol intermediates and electrosorbed carbon monoxide (CO(,'IJ) .for three mode electrocatalysts. The peaks probably correspond to Steps vi to viii in the reaction scheme of Figure 2

Phrinum Metab b., 2002,46, (4) 150

438 292 292

mv (vs. (RHE)

trochemical measurements, the gas-phase CO chemisorption areas of the electrocatalysts were determined. The data are summarised in Table I, and show the CO gas-phase and CO electrochemical surface areas for each electrocatalyst. The CO gas-phase surface areas correspond to the absolute maximum metal surface area. The electrochemically determined CO values, however, correspond to the electrode platinum surface area (EPSACO), which is the total metal area in contact with the proton conducting polymer in the electrode. For each electrocatalyst the EPS&O was less than the gas-phase value, indicating that not all the electrocatalyst in the electrodes was utilised.

Table I also summarises the EPSAMeoH values of each anode electrocatalyst, determined using the methanol electrosorption (or electrosorbate) stripping peak. (7%. dominant surface-bound intermediate was assumed to be Co&) These were found to agree well with the CO-stripping values (EPS&O) for the 40 wt.% Pt/XC72R and 20 wt.% Pt, 10 wt.% Ru/XC72R electrocatalysts. However, the values for the PtRu alloy black were somewhat different. A further difference was observed in the stripping-peak positions of each electrocatalyst, see Figure 4 and Table I. The Ru- containing electrocatalysts produced stripping peaks at much lower potentials than the pure Pt electrocatalyst, showing that the removal of the surface-bound intermediates was promoted by Ru. This is believed to occur more readily for PtRu alloys since Ru is more easily electrooxidised than pure Pt, and forms Ru-OHds at lower potentials (12). The -Had, species are then believed to spill over onto neighbouring Pt sites where they react with -Cods. This occurs at lower potentials than with pure Pt.

Another interesting observation was made con- cerning the relative positions of the methanol and -Codd, stripping peaks. For 40 wt.% Pt/XC72R the methanol stripping peak was observed at a lower potential (438 mv) than the CO stripping peak (538 mv). This could be an indication that the pure Pt electrocatalyst was not completely poisoned by the methanol, although the similar EPSA values from the methanol (EPSAM,,H) and CO (EPSAco) experiments make this debatable.

Further, the presence of a shoulder on both the methanol and CO Stripping peaks also suggests that the electrocatalyst contains either two types of reaction site or crystallites with differing activities that were resolvable by both techniques.

One final point to consider is the relevance of the EPSA values determined by each technique. Although the values in Table I are normalised for the Pt and Ru content of the electrocatalysts, it is not clear how the Ru components interact with CO in the gas-phase and in the electrochemical experiments. For example, the Ru (or Ru oxides) may not be covered with a complete monolayer of CO during the electrochemical measurements. This process is also probably strongly dependent on time, temperature and the partide size of the electrocatalyst. Similarly, the significance of the EPSA values determined with methanol are open to debate. Although methanol is believed to pref- erentially electrosorb on Pt sites, the process probably requires an ensemble of Pt atoms. Therefore, for complete poisoning, the methanol fragments must be mobile enough to release the Pt ensembles so further reaction with methanol can occur.

Nevertheless, the use of methanol stripping voltammetry appears to give an excellent indication of the available electrocatalyst surface area for methanol electrooxidation. This strongly comple- ments the measurements that are routinely carried out with co.

Better Anode Electrocatalyst Materials The search undertaken for more active anode

electrocatalyst materials for methanol electrooxidation in acid electrolyte is illustrated by studies similar to the one above. The electrocatalyst needs to provide both an efficient mechanism for methanol dehydrogenation and an efficient mechanism to electrooxidise - c o , d , to COZ.

Of great importance are materials that might combine with Pt to promote Steps iv to viii in Figure 2, and Ru in particular significantly increases the activity of Pt for methanol electrooxidation. Other studies have looked at elements that form binary alloys with Pt (Ru, Sn, Re, Au, Mo, W, Pd, R h (13-20)), and ternary (PtRuSn (21)) and

Phtinwm Metals Rev., 2002,46, (4) 151

-0- P t tXC72R -X- Pt lr lXC72R +- PtPdlXC72R + PtOstXC72R -A- PtRh IXC72R t PtRulXC72R -Xr PtWIXC72R +PtRuRhIXC72R 4 PtGalXC72R -.A.-PtRuSn/XC72R

0 0.1 0.2 0.3 0.4 0.5 0 6 0.7 0.6 SPECIFIC ACTIVITY, mA cfn-’ Pt

Fig. 5 Half-cell specific uctirity plots,fur Pt cilloy tnaterials in I M sulfuric acidR M methanol at 80°C shoning that Ru-conraining electrocutulysts ure the most cicrive. A lower mode potential corresponds to a more active electrocatalvst for methanol electrooxidution

quaternary alloys (P tRu I rOs (22)). At the Johnson Matthey Technology Centre,

the focus of DMFC anode development has been on using carbon-supported high surface area electrocatalysts. Figure 5 presents anode half-cell polarisation data for a series of Vulcan XC72R- supported Pt materials. These include pure Pt, and alloys of Pt with iridium (Par), palladium (PtPd), osmium (Ptos), rhodium (PtRh),. tungsten (PtW), gaUium (PtGa), ruthenium (PtRu), ruthenium- rhodium (PtRuRh) and ruthenium-tin (PtRuSn).

Steady-state measurements were performed at 80°C in 1 M sulfuric acid electrolyte containing 2 M methanol. Prior to the methanol electrooxidation studies, the in situ electrochemical metal area (ECA, m2 g-’ Pt) of each electrode was determined using CO stripping voltammetry. Unlike the EPSAco measurement, this value corresponds to the maximum available Pt surface area in the electrode. The sulfuric acid can make effective contact with the entire electrocatalyst surface because it floods the electrodes, as it also does in the gas- phase CO chemisoiption experiment. Thus, the performance of each electrocatalyst is not limited by electrode structure or by the EPSA effects that are seen in the MEAs. Using the ECA value for

each electrode, the half-cell polatisation data were corrected to give the intrinsic activity of the electrocatalysts (specific activity, mA cm-’ Pt). Hence, the activity of each anode electrocatalyst could be compared, independent of its surface area.

The half-cell data in Figure 5 show that the activities of the materials fall into two distinct bands. The most active electrocatalyst materials - those having the lowest potentials - all contain Ru. The elements Rh, 0 s and Ga appear to show pro- motional effects, but much smaller than that of Ru. Tungsten did not promote methanol electrooxidation on Pt, and Pd and Ir appeared to inhibit it.

The methanol electrooxidation activity of the PtRu was found to be the highest of the binary Pt- based alloys. A number of groups have claimed to have developed ternary or even quaternary materials with activities higher than PtRu alloy (23, 24). The rationale behind some of these materials is sometimes unclear and quite often their new materials are compared with what could be considered a poor PtRu alloy baseline. Figure 5 also compares the methanol electrooxidation data of two ternary materials, PtRuRh and PtRuSn. Both Rh and Sn have been shown to promote the activity of Pt for methanol electrooxidation, but neither were found

PIatinrrm Met& Rm, 2002.46, (4) 152

to co-promote PtRu. This observation led to the conclusion that only modest improvements in the PtRu activity can be attained by addmg co-promoting elements. Indeed, quite often, adding ternary or even quaternary electrocatalyst components can reduce the production friendliness of the material and dramatically increase its cost. Hence, at Johnson Matthey, the electrocatalyst development work has focused on optimising the PtRu alloy.

An Optimum P1atinum:Ruthenium Ratio There are a number of published papers which

describe work to determine the optimum PtRu alloy composition for the DMFC anode (25, 26). For this type of study to be carried out successful- ly, the composition of the electrocatalyst must be controlled so that the surface structure is repre- sentative of the bulk alloy composition. (This can be challenging for carbon-supported electrocatalysts.) The composition of the electrocatalyst surface is determined by the chemical deposition process used to deposit the particles and/or by any post-treatment it receives, such as thermal annealing. The wide range of methods reported in the literature for preparing PtRu electrocatalysts therefore probably results in a range of materials with different surface compositions. This makes it difficult to assess which composition is most active for methanol electrooxidation. There is also evi- dence that different alloy compositions are favoured at high and low temperatures (27). Hence, it is probably only possible to select the most active PtRu alloy phase from a range of compositions prepared using the same deposition process and post-treatment conditions.

In order to determine the most active alloy composition for methanol electrooxidation, a range of PtRu/Vulcan XC72R electrocatalysts was prepared by an aqueous-based slurry route. Each electrocatalyst contained a 6xed Pt loadmg (20 wt.Yo); the Ru loadmg was varied to give a range of atomic compositions from PtlM to PtJtu,,. The preparation involved codeposition of highly-dispersed mixed oxide particles onto the carbon, followed by drying and heat treatment. Characterisation by X-ray difhction (XRD) was

used to estimate the bulk alloy composition (from the Pt lattice parameter) and the average crystallite size (using Scherrer’s equation (28)).

From Figure 6 (which shows some early work that used an experimental deposition technique) the bulk alloy composition and average crystallite size (as a function of alloy composition) can be seen. The XRD-determined bulk alloy compositions shown here are a reasonable match to the theoretical compositions. Alloys PtwRulo and Pt&uzo had bulk alloy compositions identical to the theoretical compositions, but alloys from Pt7oRu~ to Pt&u,O appeared to be Pt-rich. Thus, part of the Ru was not being incorporated into the predominant crystalline face centred cubic (f.c.c.) PtRu phase but was present either in an amorphous Ru oxide phase or in an amorphous Ru-rich PtRu phase - but neither of these phases could be detected with XRD. X-ray photoelectron spectroscopy (XF’S) measurements suggested that the electrocatalyst surface was indeed Ru-rich.

The XRD crystallite size data showed an interesting effect: the crystallite size of P t l m was very large (- 12 nm) but fell dramatically as the Ru content was increased to 30 at.% and above. The crystallite size of alloys with theoretical compositions between Pt70Ru~ and P ~ ~ O R U ~ ~ was found to be between 2 to 3 nm. This suggests that Ru promotes the dispersion of the electrocatalyst. The effect was most noticeable for materials having

Fig. 6 XRD dutu j b r a range af’PtRdYC72R electrocutu1y.st.s. showing cilloy composition cmd uverage ctystallite size. The diagonal dushed line represents the theoreticul cornpodion. These mciteriuls were used to assess the suitahilir?. of a new laboratary-.sccile chemicul deposition process

Pkadnwm Metah Rey., 2002,46, (4) 153

compositions (Pt&uW to Pt&u7,,) which deviated most from the theoretical composition. Therefore, the unalloyed amorphous material that may reside on or near the surface of the PtRu alloy particles may help prevent sintering during the deposition or thermal reduction processes. For alloys Pt&ulo and PtsoRuzo this effect was less prominent because all the Ru was incorporated into the bulk alloy.

To investigate the surface electrochemical behaviour of the PtRu alloy electrocatalysts and their activities for methanol electrooxidation, all the electrocatalysts were used to prepare electrodes suitable for testing in sulfuric acid electrolyte. Aqueous-based Nafion ionomer inks were prepared and carbon-fibre paper electrodes were manufactured using a coating process.

Figure 7 shows the half-cell methanol electrooxidation activity and the ECA (mz g-' PtRu, determined with CO-stripping voltammetry) for each PtRu material. The methanol electrooxidation activities were determined in 1 M sulfuric acid and 2 M methanol at 80°C. The electrodes contained 0.35 mg Pt cm-'. The methanol electrooxidation activity is compared at a mass activity of 100 mA me-' Pt; electrocatalysts with lower anode potentials were the most active. (The mass activity corresponds to the current density corrected for the electrode Pt loading.) As expected, pure Pt was

Fig. 7 Electrochemical dutu recorded in u hulfcell for PtRu ullovs in I M suljirric acid. The effect of the PtRu ulloy compohition is shown on: ( i ) methunol electrooxidotion uctivit?, at 100 mA mg-' Pt und 80°C in 2 M MeOH; (ii) the ECA (m' g ' PtRu) determined with CO stripping voltummetry ut u sweep rute .f I0 mV s I : (iii) the 1-ulculuted totul electrochemicul nietul ureu (m' g ' PtRu) from the XRD cnwullite size

the least active material, requiring an anode potential of - 0.500 V (vs. RHE). However, its activity increased dramatically as the Ru content was increased to Pt70Ru,o, but at higher Ru contents the activity became constant at - 0.340 V (vs. RHE).

Figure 7 also shows the theoretical (calculated from XRD data assuming spherical particles) and electrochemical (from CO-stripping voltammetry) metal surface areas as a function of alloy composition. The two sets of values compare well; the ECA values of Pt3oRu70 to Pt&uN are the hghest.

An examination of the data suggests that two effects may control the activity of the electrocatalysts. First, as the level of Ru was increased in the alloy to 30 at.% and above, the ECA of the electrocatalyst increased. The XRD data also suggest that part of the Ru was not incorporated into the Pt lattice but may have remained segregated on the surface of the particles, perhaps as an oxide. Further addition of Ru beyond Pt~Rum did not lead to a relative increase in the amount incorporated into the Pt lattice. Instead, the amount of unalloyed Ru remained essentially the same (as shown by the constant deviation of the XRD alloy composition versus the theoretical composition in Figure 6). Thus, the methanol electrooxidation activity of all these materials is roughly similar. It appears that good alloying of Ru into the Pt lattice

Plalinwm Met& Rev., 2002,46, (4) 154

I Table I I

Composition

20 Wt.% Pt, 10 Wt.% RU 40 Wt.% Pt, 20 Wt.% RU PtRu black Pt black

I Some Physical and Electrochemical Parameters for Pt Black and Various PtsoRuso Alloy Electrocatalyst I ComDositions XRD crystallite XRD lattice Calculated surface CO chernisorption metal

size, nm parameter, 8, area, rn2 g-' Pt(Ru) area, ECA, m2 g-' Pt(Ru)

1.9 3.877 174 139 2.5 3.883 132' 104 2.9 3.882 114 83 6.5 3.926 43 24

is required to produce an active electrocatalyst, but that the process of 'tilling the Pt lattice' may also enable a stable surface Ru component to be built up - most likely essential for promoting methanol electrooxidation (1 2).

This contrasts with the proposed mechanism by which PtRu alloy promotes CO tolerance in the PEMFC at practical anode potentials. The CO tolerance (in PEMFCs) of PtRu is believed to occur because the incorporation of Ru in the Pt lattice decreases the Pt-COd, bond strength, reducing the -Codd, coverage (28). Surface Ru only comes into play at hgher potentials where it promotes -co& electrooxidation. as in the DMFC.

Anode Electrocatalyst Structure Unsupported PtRu alloy blacks are the most

widely used electrocatalysts employed at the DMFC anode, primarily because they provide very high Pt loadings (210 mg Pt cm") to maximise the EPSA in the electrode. Such electrodes are very active for methanol electrooxidation but are too expensive for most commercial applications.

To investigate whether the metal h d n g could be reduced to a more economical level and find the effects on performance, a series of PtRu alloy electrocatalysts of composition Pt&uw was prepared. The materials were PtRu black (HiSPEC" 6000), and two Vulcan XC72R-supported electrocatalysts of composition 20 wt.% Pt, 10 wt.% Ru (HtSPECm 5000) and 40 wt.% Pt, 20 wt.% Ru. The crystallite sizes and lattice parameters were determined by XRD, see Table 11. The smallest crystallite size was 1.9 nm for the 20 wt.% Pt, 10 wt.% Ru electrocatalyst. The 40 wt.?? Pt, 20 wt.%

Ru electrocatalyst had a slightly larger crystallite size (2.5 nm), while the PtRu black had the largest (2.9 nm). These are excellent dispersions, especia- ly for the latter two, and this is very apparent when their crystaJlite sizes are compared to that of unsupported Pt black (6.5 nm) (HLSPECTM 1000).

The improved dispersions found for PtRu electrocatalysts compared with a pure Pt electrocatalyst at a similar loading on carbon was described in Part I1 (29). The presence of Ru again appears to promote the dispersion, most probably through small amounts of surface-segregated Ru oxides (or surface enrichment with Ru) which prevent sintering. The XRD lattice parameter values for each PtRu electrocatalyst also show a shift from the value for pure Pt black. This is not indicative of exactly PtsoRuso alloy but of slightly Pt-rich alloy (compared to the theoretical composition).

The CO chemisorption metal areas c o n k e d the trend seen in the XRD crystallite size data. The CO gas-phase area of 20 wt.% Pt, 10 wt.% Ru was the highest (139 mz g-' PtRu); slightly lower (104 mz g-' PtRu) for 40 wt.% Pt, 20 wt.% Ru; and lowest (83 mz g-' PtRu) for PtRu black alloy, although this last value is much higher than that of the Pt black (24 m2 g-' Pt). The difference between the calculated and CO gas-phase areas is probably due to obscuring of the metal crystallites, and was very evident for the Pt black sample.

Specific Activity for Methanol Elcctrooxidation To find the methanol electrooxidation activity

of the electrocatalysts, flooded steady-state half- cell experiments were performed in 1 M sulfuric acid and 2 M methanol at 80°C. Electrodes were

Phfinnm Metals h., 2002,46, (4) 155

Fig. 8 Flooded anode half-cell polarisation dafu ut 80°C in I M sulfuric a c i d n M methuno1,for three PtRu materials with a Pt loading of - I mg Pt cm '. The intrinsic activity of each material was cornparable under these conditions

prepared using electrocatalyst-containing aqueous Nafion inks, with a loacllng of - 1 mg Pt cm-'. Figure 8 shows the specific activities of the three PtRu electrocatalyst materials; under the reaction conditions, the methanol electrooxidation activities were comparable. That is, the intrinsic kinetic activity of the electrocatalysts was unaffected by the electrocatalyst structure and no significant electrode structure effects were observed. The lack of electrocatalyst structure effects is probably due to the sulfuric acid electrolyte penetranng the entire electrode structure, and utilising all the electrocatalyst.

MEA Anode Performancc To study the effect of the anode electrode

structure on the MEA performance, a series of experiments was carried in a 3 cmz micro-fuel c d .

The electrodes described above (with 1 mg Pt cn-3 were used to prepare MEAs using Nafion 112 membrane and Pt black cathodes (4 mg Pt cm-2).

Figure 9 shows the results of pseudo anode half-cell (or half MEA) experiments at 90°C. In these experiments, the anode of the MEA was supplied with 2 M methanol fuel and the counter electrode with pure hydrogen. The fuel cell was then driven by a potentiostat and the anode potential (vs. RHE) was measured as a function of the current density. The resistance of the MEA was determined using current-interrupt techniques.

Although the intrinsic activities of the electrocatalysts had been identical in sulfuric acid electrolyte (Figure 8) this was not the case when these electrocatalysts were employed in the anode of an MEA. Within the MEA, their anode performance appears to be linked to a number of factors

Fig. 9 Pseudo anode halfcell (or half MEA) experiments at 90°C. The anode potential (w. RHE) is measured as afunction qj'current densip,for the three PtRu muterials. 2 M Methanol was supplied to the anode and pure hydrogen to the cathode. The 40 wt. % Pt, 20 wt. % Ru electrocatalyst had the highesr performance, shown b?j its lower potential

Ph%imm Me& Rev., 2002,46, (4) 156

Fig. 10 Single cell polurisation curves showing the effect of the anode structure on the MEA performance. The highest anode perforniance is given by 40 wt.% Pt, 20 wt.% Ru. The anode loading is I m g Pt c t d . The operating temperature is 90°C, and Najion I I7 membrane is used. The fuel is 0.75 M MeOH

The cuthodes are bused on Pi black (4 m g Pt ern-’ ) ond the oxidant is pressurised air (30 p i g , L,,w = 5)

( A h f < O H = 4.5).

including electrocatalyst udisation (the extent of the electrocatalyst/ionomer interface), the thickness of the electrocatalyst layer and its porosity.

The anode containing the 20 wt.% Pt, 10 wt.% Ru electrocatalyst had the lowest performance of the three anode electrocatalysts, see Figure 9. This anode had the highest EPSA (EiPSAMdH = 78 mz g-’ PtRu) but corresponded to the thickest electrode layer (at 1 mg Pt crn-’)). Its performance suggests it was suffering from mass transport limitations at current densities > 200 mA cm-’. It seems that methanol could not enter the entire structure and COZ could not escape. At current densities > 1000 mA cm-’ th is was particularly severe.

This observation suggested that the PtRu black should have the best performance of the three materials as it produced the thinnest electrocatalyst layer, but this is not the case. The PtRu black anode has a significantly better performance only at high current densities (> 1000 mA cm-’). At low current densities, when kinetic control is attained, the performances of the PtRu black and 20 wt.% Pt, 10 wt.% Ru anodes were almost identical. (Kinetic control is attained when mass transport does not occur and only electocatalyst kinetics limit performance.)

In fact, the 40 wt.% Pt, 20 wt.% Ru electrocatalyst had the hlghest performance of the three over the complete range of current densities. This electrocatalyst seems to produce the best compro- mise between available electrocatalyst surface area

(when operating in the MEA) and electrocatalyst layer thickness (to minimise mass transport losses). At a current density of 500 mA cm-’ (corresponding to an anode potential of 0.35 V (vs. M E ) ) its potential was about 30 mV lower than that of the PtRu black electrocatalyst and more than 50 mV lower than that of the 20 wt.% Pt, 10 wt.% Ru electrocatalyst. This is an excellent performance with none of the mass transport limitations shown by the 20 wt.% Pt, 10 wt.% Ru electrocatalyst. The reason for its superior performance over PtRu black is not easy to explain.

One aspect is the EPSA; the 40 wt.% Pt, 20 wt.% Ru electrocatalyst has a higher available EPSA (EPSAM,oH = 59 m’ g-’ PtRu) than the PtRu black (EPSAM,oH = 39 m2 g-’ PtRu). However, EPSA values should only at best be considered as corresponding to the maximum accessible electrocatalyst surface area. In operation the actual active surface area of the anode may be lower than the EPSA value or may change dynamically with CUT- rent. The real udisation of the 40 wt.% Pt, 20 wt.% Ru electrocatalyst may therefore be significantly %her than that of the PtRu black.

Following the micro-fuel cell experiments, MEAs of area 50 cmz were prepared with the same anode and cathode electrodes as before but th is time with Nafion 117 membrane (instead of Nafion 112), see Figure 10. The resulting MEAs were tested in a DMFC single cell at 90°C. Methanol fuel (0.75 M) was supplied to the anode of the MEA at ambient

Piatinurn Metah REV., 2002,46, (4) 157

pressure and at a flow 4.5 times in excess of stoichiometry = 4.5) (a stoichiometry of 1 is the amount needed to sustain the current). The cathode was supplied with unhumidified air at a pressure of 30 psig at a flow 5 times stoichiometry

The data in Figure 10 show the same clear trend as the pseudo anode half-cell data in Figure 9. The MEA containing the 40 wt.%, Pt, 20 wt.% Ru electrocatalyst gave the highest performance (0.5 V at 228 mA cm-’) compared with 20 wt.% Pt, 10 wt.% Ru (0.5 V at 170 mA ern-') and PtRu black (0.5 V at 187 mA cm-’); all had the same Pt loading of 1 mg Pt cm-’. Figure 10 also gives current-interrupt resistance data for the same series of MEAs, also showing that the structure of the anode did not influence the resistance of the MEA. That is, the performance difference was entirely due to the change in anode structure.

Therefore it appears that 40 wt.% Pt, 20 wt.% Ru gives an MEA performance superior to those of 20 wt.% Pt, 10 wt.% Ru and PtRu black. Excellent single cell performance have been attained with MEAs containing only 1 mg Pt cm-’ with power densities exceeding 100 mW cm-’. This shows that careful choice of the anode structure is important to maximise DMFC MEA performance and that the levels of PtRu electrocatalyst can be reduced significantly fiom the 2-10 mg Pt cm” levels that are traditionally employed.

The Effect of Membrane Thickness

(L = 5).

Nafion 117 membrane is the preferred electrolyte for the DMFC. It is the thickest (- 180 p) available commercial fuel cell membrane. The rate of methanol crossover through Nafion 117 is low compared to, for instance, the thinner Nafion 112 membrane (50 p). New membrane materials to help reduce the methanol crossover rate are being developed, but it is unlikely that any of the current candidates will completely eliminate it as all low-temperature proton conducting polymer materials only function efficiendy in a fully hydrated state. Methanol, being completely miscible with water, is carried by the water as it diffuses through the membranes.

In the PEMFC, thinner membrane materials (such as 30 p) are preferred as they offer reduced

ionic resistance and thus increased MEA performance. They also help to reduce the MEA cost. For the DMFC, it would be advantageous to use thinner membrane materials to reduce the ionic resistance of the MEA. However, there is a sensible lower thickness limit beyond which the rate of methanol crossover becomes too hgh and/or the membrane is no longer strong enough to maintain the large pressure differentials often needed.

Cathode Improvements With careful design of the cathode, it has been

possible to use Nafion 112 membrane as an alternative to Nafion 117, without significant loss in performance. Data from a 50 cmz single cell containing MEAs with Nafion 117 and Nafion 112 membranes is shown in Figure 11. Both MEAs contained a 40 wt% Pt, 20 wt% Ru (1 mg Pt ad) anode and a Pt black (4 mg Pt cm-’) cathode. Cell voltage data were recorded at 90°C with 0.75 M methanol ( 1 ~ 4 ~ = 4.5) and pressurised air (30 psig, h, = 5). In a second (pseudo half-cell diag- nostic) experiment, the anode potential was determined by passing pure hydrogen across the cathode (instead of air) and the fuel cell was driven by an electric load. Hence, the anode and cathode potentials could be decoupled from the cell voltage. Current-interrupt measurements were used to determine the MEA resistance.

Under these conditions, the MEA with Nafion 112 had the better performance than with Nafion 117, especially at lugher current densities. This was shown to be mainly a resistance effect - the resistance-corrected data for both MEAs were comparable (except that the cell voltage of the Nafion 112 MEA was about 10 mV lower at low current densities, probably due to enhanced methanol crossover). This observation was con- firmed by the anode and cathode half-cell data for the MEAS. As expected, the anode half-cell potentials of both MEAs were very similar. In the Nafion 112 MEA the cathode potential was only about 10 to 20 mV lower than in the Nafion 11 7 MEA due to the enhanced crossover rate through the thinner membrane.

Figure 11 also shows the cathode potential for the same Nafion 112 MEA when it was operating

Phfinum Met& Rcv., 2002,46, (4) 158

Fig. I I A comparison of Najion 117 and Najion 112 membranes in MEAT. Both MEAs hove (I 40 wt.% Pt, 20 wr.% Ru anode ( I mg PI cni ') and a Pt black cathode (4 mg Pt cm-'). The data were recorded in a 50 cm2 single cell at the operating temperature of 90°C with 0.75 M methanol,fuel (LOU = 4.5) and pressurised air (30 p i g . A,,, = 5). hi a pseudo halj-cell experiment, pure hydrogen was pussed across the cathode to help determine the mode potential. The Nujiori 112-bused MEA had the higher performance (especially at higher current densities) due to reduced membrane resistance

as a PEMFC. Instead of methanol and dry air, it was supplied with humidified hydrogen and humidified air, respectively, (both at 30 psig). The cathode potential in PEMFC-mode is only slightly higher (10 mv) than in DMFC-mode (but is slightly lower than the cathode potential for the Nafion 117 MEA in DMFC-mode). This suggests that the Pt black-based cathode structure used in these MEAS has good methanol tolerance and indicates that the cathode structure can be optimised to make it essentially methanol tolerant. However, these experiments were carried out with relatively high air flows (hk = 5) and at high pressures which reduce the effects of crossover to some extent.

Reducing the Cathode Air Flow

The air flow rate in the single cell shown in Figure 11 is too high for most practical fuel cell applications (large volumes of air require energy to

pressurise them). The cathode exhaust gas from the fuel cell stack must also be cooled efficiently to remove any methanol (from crossover) and water vapour. This places a high energy demand on the fuel cell system. A lower air flow, preferably equiv- dent to a stoichiometry of 2 (A- = 2) or less, is thus desirable.

Figure 12 shows the performance of a Nafion 117-based MEA, of similar construction to that in Figure 11. Single cell measurements were carried out at 30°C with 0.75 M methanol fuel ( ~ M , O H = 4.5) and pressurised air (30 PSI&, but at the lower air flow rate, h, = 2. Under these conditions, the MEA performance w a s very similar to that of the MEA in Figure 1 1 which was operating with a hgh

Pseudo half-cell experiments were carried out to decouple the anode and cathode half-cell potentials in the MEA. The cathode potential was found

air flow (L = 5).

Phtimm M e f d b., 2002,46, (4) 159

Fig. 12 Data recorded at low airflows to the cathode.

cell with a Nafion I1 7 MEA. The anode is 40 wt.% Pt, 20 wt.% Ru ( 1 mg Pt cm-') and the cathode is platinuni bkrck (4 mg PI cnii'). The operating temperuture is 90°C und the,fuel supplied to the anode is 0.75 M methanol (LOH = 4.5); the nir is pressurised (30 psig). The cell perjhnance under the low airflow conditions is compunible to that at higher air,flows. This demon.strutes the good methanoWwuter tolerance of the cathode

= 2, in n 50 cm' single

to be only 5 1 0 mV lower under the low air flow conditions, showing the excellent water and methanol tolerance of the cathode. The cathode potentials were also compared in DMFC- and PEMFC-modes, and were found to be identical under the low air flow condition. Thus, the effects of methanol crossover can be significantly reduced by careful design of the cathode and the performance can be maintained at low air flows. Indeed, methanol-tolerant materials (6) may not be required under these conditions, especially with Nafion 11 7 membrane.

Reducing Cathode Electrocatalyst Loading The DMFC anode electrocatalyst developments

described so far have been aimed at reducing the Pt loading to 1 mg Pt ern-', while maintaining performance. This has been achieved with 40 m.% Pt, 20 wt. YO Ru/Vulcan XC72R. By comparison, in the PEMFC the typical Pt electrocatalysts used in the cathodes are also supported on Vulcan XC72R, but the loading is only 0.2 to 0.7 mg Pt cm-2 which gives an excellent MEA performance (1). AU the DMFC single cell data described here

have used MEAs containing high loaded cathodes

(Pt black, 4 mg Pt cm-2). To reduce this loading, work was undertaken to develop carbon-supported Pt electrocatalysts of much hgher surface area than Pt black electrocatalyst (24 mz g-' Pt) (1). A reduction in Pt loading from 4 to 1 mg Pt cm-2 was investigated, and providmg that the methanol tolerance is comparable to that of Pt black, no impact on performance was expected. The new materials must also be able to cope with the high levels of water and methanol found at the DMFC cathode.

In Figure 13, data from a 25 cm2 single cell measured at 90°C for three MEAs is shown, one is based on Pt black (4 mg Pt cm-') and two are based on carbon-supported Pt cathodes (1 mg Pt cm-'). Methanol (0.5 M) was supplied to the anode

= 3) and pressurised air to the cathode (30 psig, h, = 10). Cathode A was based on 40 wt.% Pt on carbon @CA 60 m2 g-' Pt) of similar construction to that used in the PEMFC. Cathode B was based on a 60 wt.% Pt on carbon (ECA 45 m2 g-' Pt) and was optimised for DMFC operation. The performance of the MEA with cathode A was slightly lower than the Pt black cathode. The MEA with cathode B performed comparably to the Pt black cathode, showing that the cathode Pt loadmg

Platinnm Metalr Rev., 2002,46, (4) 160

Fig. 13 Cell voltage data recorded in u 25 cm' single cell of the performances of three MEA cathodes at u 90°C operating temperature. The Pt black cathode is loaded at 4 mg Pt cm-'. Cathode A (40 wt.% Pt/ carbon) and Cuthode B (60 wt.% Pt/carbon) are loaded at I mg Pt cm '. Methanol fuel (0.5 M ) was supplied to the anode (b,.,~ = 3). und pressurised uir (30 p i g ) to the cathode at high flows (A",, = 10). The anode was 40 wt. % PI, 20 wt.% RulXC72R (1 rng f t cm ')

can be reduced significantly without performance loss. Further optimisation is expected to bring the Pt loading to the levels used in the PEMFC.

Portable DMFC Applications Recently, the tremendous advances attained in

power densities by the DMFC have prompted companies, such as Smart Fuel Cell (Germany); Manhattan Scientific, MTI and Motorola (U.S.A.); and Toshiba gapan) to establish ambient micro- DMFC programmes to target the 1-100 W power range. While the power densities offered by the DMFC are considerably less than those from the PEMFC, the DMFC can still generate sufficiently high energy densities to make it an attractive alternative to secondary batteries for a wide range of applications. Miniaturisation of the DMFC system is also simpler. With liquid fuel, the main advantage is the convenience of almost instant recharging, by replacing a spent fuel cartridge - an advantage over rechargeable batteries. The DMFC is therefore being targeted at applications such as mobile phones, notebook computers and video cameras where rapid recharging is advantageous.

To date, the most efficient DMFC systems are almost all exclusively designed to operate at hgher temperatures and pressures where the power densities are the hghest. Most MEA development has focused on increasing the performance in the temperature range 80 to 130°C and little work has

been done to increase the MEA performance at lower temperatures and pressure (20 to 60"C, ambient air pressure). Often, the MEAs used in portable ambient DMFC systems have been optimised for higher operating temperatures and pressures, which may not be the best option to maximise power density. Tailoring the MEA components, including the electrocatalysts, substrate and membrane, may improve the performance further and is a hgh priority for device developers, as improvements in the stack power/size ratio will allow more straightforward miniaturisation.

Miniaturising the Fuel Cell Stack

Figure 14 presents 50 cmz single cell data for an MEA based on Nafion 117 membrane, a 40 WL% Pt, 20 wt.% Ru/XC72R anode (1 mg Pt cm-') and a Pt black cathode (4 mg Pt cd). The data were measured at 40,60 and 80°C with 0.5 M methanol (flow rate 6 ml mid) and ambient air (< 0.3 psig inlet pressure) at low flows (L = 2). Although this MEA was optimised for hqgher temperatures and pressures, its performance under low pressure conditions was good. The data is summarised in Table In together with projected fuel cell stack volumes (cm') for a range of devices.

The fuel cell stack volumes were calculated based on a 3 mm cell pitch (the thickness of one bipolar flow field plate and one MEA), 10 mm thick stack end plates and an MEA membrane

Platinum Metah Rev., 2002, 46, (4) 161

Fig. 14 Single cell data for an MEA based on Nufion 117 with an anode of 40 wt.% Pt, 20 wt.% RdXC72R ( I mg Pt cm") and a Pt black cathode (4 mg PtT The temperatures were 40, 60 and 80°C with 0.5 M methanol fuel supplied to the anode (flow rate 6 ml mini') and ambient air (< 0.3 p i g inlet pressure) at flows (a,,,= 2 ) to the cathode. At 40°C the cell voltage was 0.409 V and power density 21 mW cm-2; at 60°C the cell voltage was 0.419 V and power density 42 m W crn-'; and at 80°C the cell voltage was 0.440 V and power density 66 m W cm

border of dimensions 5 mm x 5 mm x 5 mm x 10 mm for edge sealing (the 10 mm dimension includes provision for porting - the holes cut into the membrane to allow the gases and liquids to flow). The calculation does not include the volume of the fuel pump, the air blower or the fuel tank. The projected stack volumes are based on the power density of the MEA increasing by a factor of two.

The htst example in Table I11 shows, that to generate 1 W of power at a stack voltage of 3.6 V (typical cell phone requirements) when operating at N"C, 9 MEAs of active area 5.4 cm2 are required, giving a projected stack volume - 63 cm3 - far too large to fit a modern cell phone. Doubhg the power density produced by the MEA would only modestly reduce the stack volume to - 42 cm3 because the end plates and MEA edge seals are responsible for a large proportion of the stack volume. This demonstrates that miniaturisation of the DMFC to fit a cell phone will be challenging.

The other examples shown in Table III correspond to larger 30 W 10 V devices operating at 40, 60 and 80°C. The larger devices utilise volume more effectively, primarily because the end plates and edge seals represent a much smaller propor-

tion of the overall volume of the stack. When operating at 4O"C, the projected stack volume based on current MEA technology is 823 cm3 (requiring 24 MEAs of active area 61 cm'). If the temperature of the fuel cell stack is increased to 60 and 80"C, the volume of the stack decreases to 430 and 334 cm3, respectively. Temperature thus has a large effect on stack volume. When the temperature is increased from 40 to 60°C the stack volume almost halves. The stack volumes are very attractive; when operating at 60"C, the approximate dimensions of a 30 W 10 V stack would be 5.5 cm x 5.5 cm x 14 cm. When operating at 40"C, with a doubled MEA power density, the projected stack volume is again significantly reduced from 823 to 441 cm3. At 60 and 80"C, the impact on the stack volume is less marked, decreasing from 430 to 261 cm3 and from 334 to 191 cm3, respectively. Again, these are very attractive stack volumes and show why the DMFC is being rigorously developed as a secondary battery replacement device.

Extending Upper Temperature Limit While the power densities produced by low

temperature ambient pressure DMFC stacks have become attractive enough to drive its near term

PUnum Metals h., 2002,46, (4) 162

em-2

Table Ill Ambient Pressure DMFC MEA Performances and Fuel Cell Stack Dimensions*

Stack power, W

1

30

30

30

Stack voltage,

V

3.6

10

10

10

MEA active area,

cmz

5.4 (2.8)**

61 (31 )

30 (1 6)

20 (11)

* Data r im u 50 cm' single cell for an MEA based on Na&m 117 memhmne with on anode of 40 wt.% PI, 20 wt.% Ru/XC72R ( 1 m g Pt cn- j and a PI block ruthode (4 mg Pt em-')). Methanol fuel 0.5 M (flow rate 6 ml m i d ) is supplied to the anode and ambient air (< 0.3 psig inlet pressure) orflow (&,,, = 2 ) is supplied to the cuthode. "This value and 011 other volues in brackets are projections based on increasing the power density of the MEAs by a,fucror of two

f

Cell Power Stack voltage, density, volume,

V m W c m 2 cm3

0.409 20.5 63 (0.409) (40) (42)

0.409 20.5 823 (0.409) (40) (441 1

(0.419) (80) (261)

(0.440) (1 20) (191)

0.41 9 42 430

0.440 66 334

commercialisation, some argue that longer term transport applications should be targeted. The DMFC system, and the reformer-PEMFC system, are considered to be good options for transport uses, but the DMFC efficiency is poor compared to the PEMFC. On the other hand, the PEMFC stack must be humidified so the hydrogen (refor- mate) and air are saturated with water vapour. Without humidification the MEA will dry out and eventually fail due to resistive heating and pin-hol- ing of the membrane. In addition, the large

amounts of low grade heat must also be removed from the stack and radiated to the surroundmgs. However, the size resmctions, for example, of an automobile make this difficult to achieve effectively, and has led some to believe that the fuel cell stack operating temperature must be increased beyond 100°C. Heat management would then be less critical.

This presents an ideal opportunity for the DMFC, with its dilute methanol fuel solution providmg it with the necessary humidification. The

Fig. 15 The effects of operating temperatures 90 und 130°C on u DMFC single cell with a Narfion II 7-based MEA. The anode is 40 nit. % Pt. 20 wt. % Ru ( I mg Pt cmn ')); the cathode is Pt black (4 mg Pt ern-'). Pressui-ised air (30 p i g ) jlows (L = 2 ) to the cathode and 0.75 M methanol = 4.5) is supplied to the anode. At 90°C the MEA perfortnunre is - 330 mA c111i~ at 0.5 V A! 130°C the MEA performance is - 530 mA mi2 at 0.5 V (or 500 mA cn-' ut 0.510 V ) I

PIatinum Metals b., 2002,46, (4) 163

Stack temp.,

O C

40

40

60

80

Current density, mA cm-'

50

50

100

150

Number of MEAs in stack

9

24

24

23

MEA active area,

cmz

5.4 (2.8) **

61 (31 )

(1 6)

20 (11)

30

large volumes of water circulated around the stack help to keep the membrane humidified at temperatures where the PEMFC membrane could not operate.

Figure 15 presents DMFC single cell data for a Nafion 117-based M E A employing 40 wt.% Pt, 20 wt.% Ru anode (1 mg Pt cm-’) and a Pt black catt- ode (4 mg Pt cm-’). The design of the MEA is more advanced than previously presented. It is supplied with 0.75 M methanol @,McOH = 4.5) and pressurised air at low flows &,, = 2). At 9O”C, the h E A performance is - 330 m A cm-2 at a cell voltage of 0.5 V, which is significantly higher than presented earlier. Due to the advanced design of the MEA, its performance increases dramatically at hgher temperature. Hence, at 130°C the performance was about 530 mA m-’ at 0.5 V (or 500 mA cm-’ at 0.510 V). The current-interrupt resistance was found to be unchanged at 130°C showing that the MEA was well humidified.

This level of performance brings the DMFC much closer to that of the PEMFC and strongly suggests that with further modest improvement in power density, the DMFC system could success- fully compete with the reformer/PEMFC system.

Acknowledgements The financial assistance of the EU is acknowledged, under

the framework of the Non-Nuclear Energy Programme Joule III Contract, JOE3-ClY5-0025. The contributions of past and present members of the Johnson Matthey fuel cell research group are acknowledged: S. Ball, N. Collis, S. Cooper, J. Denton, D. Fongalland, M. Gascoyne, K Goodman, H. G. C. Hamilton, G. A. Hards, K L. Hogarth, G. Hoogers, J. Keatmg, D. Lonergan, D. Peat, E. Smith, B. Theobald, D. Thompsett and N. Walsby.

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28 P. W. Atkins, “Physical Chemistry“, 4th Edn., Oxford University Press, 1990, p. 622

29 R Ralph and M. P. Hogarth, Pkdnnm Metah Rm, 2002, 46, (3), 117

The Authors Martin Hogarth is a Senior Scientist at the Johnson Matthey Technology Centre and has worked in the area of DMFCs since 1992. His main interests are the development of new electrocatalyst materials and high-performance MEAs for DMFCs. He is also interested in novel high-temperature and methanol- impermeable membranes for the PEMFC and DMFC, respectively.

Tom Ralph is the Head of Electrochemical Engineering at the Johnson Matthey MEA manufacturing facility based at Swindon. His main interests are the development of MEAs for PEMFC and DMFCs.

Platinwm Metah Ray., 2002,46, (4) 164

The Chemistry of the Platinum Group Metals A REPORT OF THE EIGHTH INTERNATIONAL CONFERENCE

By John Evans Department of Chemistry, university of Southampton, Southampton SO17 1 BJ, U.K.

The themes of the Eighth International Conference of the Chemistry of the Platinum Group Metals (PGM8), held at the University of Southampton, from 7th to 12th July 2002, covered a broad spectrum from the chemistry of these fascinating elements, ranging through

Organometallic chemistry Coordination and supramolecular chemistry Biological and medicinal chemistry Surfaces, materials and crystal engineering Photochemistry and electrochemistry

9 Catalysis and organic syntheses, to Theoretical chemistry and physical methods. The attendees also found time to cruise down

Southampton Water (in mist and rain), visit Stonehenge and Salisbury (only a little rain), walk through in the New Forest (totally dry!), and dine under Kmg Arthur’s Round Table in the Great Hall in Winchester.

But the open and challenging atmosphere was the most apparent hallmark of PGM8. Scientists with a breadth of approaches shared their differing experience and targets around common chemical foci, and these can be exemplified by an overview of the reports of the invited speakers.

The wel-established antitumour activity of cisplatin and carboplatin, and the onset of tumour resistance to them, was discussed by Lloyd Kelland (St. George’s Hospital Medical School, London, U.K.); and here there siill remain many important targets. Phase I trials of a ruthenium(I1I) complex were reported by Gianni Sava (University of Trieste, Italy), and these show promise for a selective effect on lung metastases. Indeed, ruthenium complexes occupied a significantly important posi- tion in the biological and medicinal chemistry theme, with Jackie Barton (Caltech, U.S.A.) using them to monitor electron transfer ranges and iden- tify the effect of oxidative damage on the conductivity of DNA. Peter Sader (University of

Edinburgh, U.K) described how his work on coordination spheres interacted with DNA bases is being extended to organometallic centres.

Control and exploitation of coordination spheres was preeminent in the programme. Many examples were elegant, such as the helicate complexes of open chain tetra- and hexa-dentate phosphines (Bruce Wild, Australian National University, Canberra) and osmabenzenes and fused osma-aromatics (Warren Roper, University of Auckland, New Zealand), while others chal- lenged conventional thinking, such as the careful design of complexes with monodentate phosphines acting as bridgmg ligands (Helmut Werner, University of Wiirzburg, Germany). Probably the ‘simplest’ hgand sets were presented by Gary Schrobdgen (McMaster University, Canada) who compared the htgh oxidation states of osmium and xenon (these elements have the widest +8 oxidation state chemistry). The simplicity of the formulae belied the technical challenges of unrav- elling this chemical frontier.

For the most part, ligand sets were chosen to engender attractive physicochemical properties. These included the luminescent properties of ter- pyridyl complexes of iridium and ruthenium (Gareth Williams, University of Durham, U.K), and the non-linear optical materials based upon dendrimeric oligomers of rutheniumQI) bipyridyls (Hubert Le Bozec, Universitt de Rennes 1, France). Dendrimers and other polymeric architec- tures (rings, chains and helices) have been synthesised with impressive control by Shgetoshi Takahashi (Osaka University, Japan), and Ian Manners (University of Toronto, Canada) described his control over the synthesis of different types of ferrocenyl polymers.

Catalysis was one of the recurring reasons for ligand design, with Duncan b Bruce (Univertsity of Exeter, U.K) demonstrating that metallorganic

Phtinnm Metalr Rm, 2002,46, (4), 165-168 165

Platinum Metals in Biological and Medicinal Chemistry By Matthew D. Hall, Centre for Heavy Metals Research, School of Chemistry, University of Sydney, NSW 2006, Australia

The Eighth International Conference on the Chemistry of the Platinum Group Metals provided an ideal opportunity for researchers to report their latest results on research and development in the field of biological and medicinal chemistry with respect to the platinum metals. A number of exciting new directions have emerged in this field, and these are summarised below.

Professor J. K. Barton (Caltech, U.S.A.) opened the proceedings, describing the elegant use of met- allointercalators to probe charge migration through DNA. DNA base mismatches and drug lesions (including those from cisplatin) on DNA can be characterised using this method. Her research group is currently embarlung on exciting in yitro cell studies using these novel probes.

The current status of several platinum drugs in clinical studies was reviewed by L. R. Kelland (St. George’s Hospital Medical School, London, U.K.) who described the challenge of drug resistance that needs to be faced in future drug development. While cisplatin and oxaliplatin remain successful in the clinic, novel drugs such as JM216 and BBR3464 are currently under evaluation. Professor T. G. Appleton (University of Queensland, Australia) described the complex reactions with endogenous thiols that contribute to tumour resistance, and their examination using NMR techniques.

While platinum drugs are the major research

thrust of platinum metals in medicinal chemistry, the emergence of several promising ruthenium complexes with antimetastatic and antitumour activity was described by Professors G. Sava (University of Trieste, Italy) and P. J. Sadler (University of Edinburgh, U.K.), respectively. Complexes trialled by Sava have been shown to localise in the lung basement membranes, not in DNA like many platinum drugs, thus preventing lung cancer metastasis. Sadler described the development of RuQI) arene complexes with reduced toxicity, non-cross-resistance and a different spectrum of activity to platinum compounds. Structure-activity relationships have been developed and highly selective DNA binding has been demonstrated. While it is clear that the development of further platinum chemotherapeutics is an ongoing endeavour, the emergence of active ruthenium compounds with the potential to enter clinical trials demonstrates that the medicinal chemistry of the platinum metals now has even wider potential.

The Author Matt Hall is a Ph.D. student at the Centre for Heavy Metals Research, University of Sydney, working on the biological fate of Pt(lV) antitumour complexes under the supervision of Professor Trevor W. Hambley. His interests are in bioinorganic chemistry, the biological fate of metals in medicine, and spectroscopy in cellular and biological systems.

Matt Hall is the joint winner of the Platinum Metals Review PGM8 conference student article competition.

liquid crystals could act as templates for the synthesis of heterogeneous metal catalysts based on mesoporous silicas. Jan Backvall (University of Stockholm, Sweden) demonstrated the use of allenes as nucleophiles in palladium-catalysed couplmg reactions, and the emphasis of palladium mediated C-C coupling reactions was continued by Hans de Vries (DSM Research, Geleen, The Netherlands) who presented thoughtful developments of Heck reactions. An alternative approach to C-C couplmg, namely hydroformlyation, was also stressed, with Kyoko Nozaki (University of

Tokyo, Japan) describing very effective asymmetric hydroformylation catalyst systems, and Eric Hope (University of Leicester, U.K.) showing how fluo- roorganic groups can be exploited in green chemistry: to enhance the solubility of rhodium and ruthenium complexes in supercritical COZ, and also utilising fluorous phases themselves as supercritical solvents.

More detailed fundamental studies relating to homogeneous catalytic processes were a feature of the programme. The elegant and penetrating studies of Bob Bergman (University of California,

Phtinmn Metah b., 2002,46, (4) 166

U.S.A.) provided great insight into C-H bond activation processes, and Zhenyang Lin (Hong Kong University of Science and Technology) showed how theoretical studies can add to the insight in an incisive way. Sylviane Sabo-Etienne (Laboratoire de Chimie de Coordination, Toulouse, France) described the activation of boranes and silanes, demonstrating the main group elements to hydro-

gen bonds as q2-ligands. Richard Eisenberg (University of Rochester, U.S.A.) reported the power of parahydrogen-induced polarisation to track through the mechanistic pathways of Hz through a catalytic cycle, while Jon Iggo (University of Liverpool, U.K.) reported on impressive technical developments with a flow cell to allow in situ NMR under h g h pressures, without

An Equilibrium in Catalyst Optimisation and Development? By G. R. Owen, Department of Chemistry, Imperial College, South Kensington, London SW7 2AY, U.K.

A number of the presentations at the Eighth International Conference on the Chemistry of the Platinum Group Metals focused on catalysis. One of the major issues addressed was the cost involved in the design, synthesis and optimisation of new catalysts. Why spend so much money and time on the preparation of expensive ligands and complicat- ed techniques when mphenylphosphine with PdC12, under standard conditions, works well?

As the conference progressed through imagina- tive and stimulating presentations it became cleat that the search for more efficient catalytic processes requires the involvement of both academia and industry. While the optimisation of the processes can be left to the industrialist, academics should dedicate their time to design and enhancement of novel systems that might involve unprecedented chemistry.

There were a number of fascinating and inspii- ing presentations. Professor B. R James (University of British Columbia, Canada) provided an amusing advertisement for the paper industry, describing the requirements for new strategies in the hydrogena- tion of lignul found in wood pulp, particularly one using a RuCl~3H20 and trioctylamine catalyst. This was a call to academia for some fresh ideas.

There were also some examples of novel routes for the overall dwelopment of catalytic systems. Two interesting presentations on the use of den- drimer catalysts by the van Koten group (G. P. M. van Klink and R J. M. Klein Gebbmk, Utrecht University, The Netherlands) were given. Organic products could be separated from the reaction

mixture by recently developed nanotiltration techniques. Careful choice of catalyst, the strong chelation of the pincer llgaflds in these cases, pre- vented catalyst leaching.

An important puzzle was also highlighted by Professor P. S. Pregosin PTHZ, Switzerland) in his talk on the ‘meta-&&yl fleet’. This interesting contribution showed that greatly improved enan- tiomeric excesses are obtained when meta-dialkyl substituted ligands are used. The reasons for this dramatic effect were discussed and studies have shown that in Pd-phospho-oxazoline ally1 complexes, the observed Cram-influence of both the N and P donors were the same. This remarkable ‘heL /i.g fleet’ dearly needs further investigation and may have many implications for reactivity.

The conference has shown that there is a great deal of chemistry which is available for study, and in partidar platinum group metals can be used to study a wide range of reactions. Pure curiosity and application-driven research will continue to be essential for the development of exciting and novel chemistry. In both cases, real investment will be required to achiwe the challenging a i m s ahead.

The Author Gareth Owen is working towards a Ph.D. in organometallic chemistry at Imperial College, under the supervision of Dr Rambn Vilar. His thesis will concentrate on the palladium-mediated reactivity and insertion chemistry of carbon-heteroatom multiple bonds, such as isocyanides, imines and heterocumulenes. His research interests include the design of novel supramolecular ligands and their uses in the control of selectivity in catalysis.

Gareth Owen is the joint winner of the Platinum Metals Review PGM8 conference student article competition.

Pkztinum Metah Rev., 2002,46, (4) 167

the attendant problems of slow gas dissolution due to poor mixing. This direct observation of homogeneous catalysis, such as hydroformylation and carbonylation, can be achieved under representa- tive conditions.

Although many of the complexes and materials describes above were ohgomeric and polymeric, few had direct metal-metal interactions. However, these were evident in the heterogeneous catalysts described by Stan Golunski (Johnson Matthey, U.K). He emphasised the ability of metals, especially palladium, to mediate the transfer of oxide ions from an oxide surface to a catalysis substrate.

Two talks, though, demonstrated differing but fascinating properties of nanoscopic metal structures; Phil Bartlett (University of Southampton, U.K.) described how liquid crystals and solid microspheres (of polystyrene and silica) could be used as templates for the chemical and electrochemical formation on mesoporous metals. These materials provide large surface areas, like those of the nanoparticles in heterogeneous catalysts, but the area within is a concave, rather than a convex, surface and generates different types of metal surface sites. It might also be expected that the large arrays that comprise mesoporous metals may be less prone to sintering than the clusters within a hgh dispersion metal catalyst. So novel chemical applications of these materials in catalysis, electro- catalysis and sensors can be anticipated.

The other approach was that of Giinter Schmid (University of Essen, Germany). His ligand-sta- bilised clusters lie at the boundary of molecular complexes and colloids. The Au55 type of duster with PPhs and the predominant protecang ltgand was reported to form 2-dimensional monolayers at a water-CHzClz boundary, and I-dimensional structures with different templates. A supramolecular chemistry was established between these hgh nuclearity cluster materials. The electrical conductivity across a single cluster molecule was also measured. In the junction to the nanoelectcodes, the ligand sheath acted as an insulating layer. The metal core itself behaved as a coulomb well with properties attributable to quantum size effects, rather than being merely a segment of an extended metal array.

It is unfair to the excellent contributed papers and to the poster presenters that I have concen- trated on the contributions of the invited speakers. In many ways they accentuated the perception that platinum metals chemistry is a mature, but still youthful science, with new vistas opening. Indeed, that view was expressed by Helmut Werner in his thanks to Giinter Schmid. The boundaries of platinum metals chemistry are still there to be probed in a fundamental way, aided by the great array of structural, spectroscopic, imaging and analytical techniques now available to us.

Indeed, the platinum group metals themselves are now part of the array of analytical techniques, used for example in understanding the effects of damage within DNA, and the capability for effective functioning is continually being extended. Ligand design and synthesis are developing apace, and can be used to construct clefts at single metal atoms, helicate grooves in oligomers, and complex surfaces in dendrimers and polymers. As yet we do not understand these new structures well enough to predict the applications in molecular electronics, optoelectronics and catalysis. However, we can see extended arrays of metal nanostructures that have a totally untapped potential. Perhaps even less do we understand how such complexes interact with living tissue. That they can do so to therapeutic benefit is a major impetus to research. The conference demonstrated that the range of complexes and materials that could be tested comprise a vast array of types. And, as always, development of the underlying theory of all of these interactions is essential to orient further synthetic developments.

We are grateful for the organisation provided by the Royal Society of Chemistry, and also to our sponsors: Johnson Matthey, Synetix, BP Chemicals and Nycomed Amersham. On behalf of the National and Local Organising Committees, we would like to thanks all of the attendees for a memorable scientific meeting.

The Author John Evans is a Professor of Chemistry at the University of Southampton. His main interests are in surface organometallic chemistry and heterogeneous catalysis, mechanisms of homogeneous catalysis reactions and X-ray absorption spectroscopy. Professor Evans was awarded the Royal Society of Chemistry Tilden Medal in 1994.

168 pLATINUMmETALS rEV., 2002, 46, (4)

Structural Changes and Their Ianetics in Hydrogen-Containing Palladium Systems By V. M. Avdjukhina, A. A. Katsnelson and G. P. Revkevich Department of Solid State Physics, Moscow State University, 117234 Moscow, Russia

Non-trivial structural changes and phase transformation kinetics have been found to occur in palladium-hydrogen and palladium-metal-hydrogen systems during relaxation processes as hydrogen is released. In the palladium-hydrogen system these changes take place in stages: an incubation period, a period of fast degassing, a period of stabilisation, and a post-stabilisation period. In palladium-metal-hydrogen systems the structural changes and phase transformations are non-monotonous (oscillating or stochastic). Time dependent kinetics have been observed over periods of up to tens of thousands of hours. An hypothesis based upon non-equilibrium thermodynamics and hydrogen interaction factors between matrix defects and atoms in the palladium systems is proposed to explain the phenomena.

The unique ability of palladium (Pd) to absorb large quantities of hydrogen (H) was discovered about 130 years ago by Thomas Graham (1). The solution of H in Pd has a considerable effect on the physical properties of the Pd (2,3); for example, the Pd-H alloy is diamagnetic and super- conducting, although Pd itself is strongly paramag- netic. These differences are connected with the atomic and electronic structural changes which occur when H dissolves in Pd. Only atomic structural characteristics will be considered here.

Solid solutions of H in Pd correspond to 01- phase regions if the atomic ratio of HPd, nH/npd, is less than 0.024.03, and to P-phase regions if the nH/npd ratio is greater than - 0.60. When the ratio lies between these values, a mixture of both phases is present. In both the 01- and P-phases, the Pd atoms form a f.c.c. structure, with H atoms occu- pying octahedral interstitial sites. The distance between Pd atoms in the P-phase is - 3 per cent greater than in the a-phase, which is why the a H P phase transition process is accompanied by defect generation. The structural changes talung place in Pd-H during saturation with hydrogen and during degassing have become the subject of sys- tematic research. The changes occurring in the lattice and in the defect structure during the 01 + P phase transition up to P saturation, and during courses of P + degassing are of particular inter-

est. These processes and their kinetics have been examined in our research (4-12).

Stnkmg data obtained during our work show the important roles that the formation of defect structure (at saturation) and its transformation (during degassmg) play. Thus the nature of the hydrogen effects on the structural changes in Pd-H solutions and on the kinetics is significant. The mutual disorder in the distribution of Pd and other metal atoms is an additional source of defect structure formation. The most striking effects may be expected in solutions where the metal is very different to Pd - in terms of its affinity to hydrogen. Some new characteristics of the structural changes that appear when Pd systems are saturated with hydrogen can also be expected. Our results confirm that these structural changes are non-

Characteristics of the structural changes in Pd and some Pd-M alloys at saturation and during degassing will be considered here. X-ray techniques described elsewhere were used (1621).

trivial (13-21).

Samples and Methods of Investigation Samples of Pd alloys were prepared by arc melt-

ing from highly pure (99.98Yo) elements in an argon atmosphere using a titanium getter, followed by annealing (for 24 h) at 900°C at a pressure of lo* mm Hg to reach a homogenised

P/azinwm Metah h., 2002,46, (4), 169-176 169

n - 1 5 - ;; 00.

-054

I TIME, minutes

1

3

I .

Fig. I The logarithmic dependence of the Pphase concentration ( p ) in Pd on the hydrogen saturation time. The lines relate to regions or ‘blocks’ (hkl blocks) of coherent scattering with crystallographic planes. The initial incubation periods for the three blocks can be seen before the lines begin. Line 1 is for ( 1 0 0 ) blocks Line 2 is for (311) blocks Line 3 is for ( I 10) blocks

state. After homogenisation, the samples were cut (using an electric spark method) into discs, 16-18 mm in diameter and 0.2-5 mm thick. These were then ground and polished with diamond paste to a mirror-like condition. The X-ray diffraction maxi- ma of these samples were wider than for non-deformed samples. The grinding and polish- ing had created a deformed surface layer to a depth of > 10 pm (greater than the X-ray penetration depth (4 to 5 pm)). Samples were hydrogenated electrolytically ( 7 4 0 minutes at a current density of 2 5 8 0 mA cm-’) in a bath of aqueous NaF solution (~?J’o) at room temperature. The sample under investigation was made into an cathode, the anode was a Pt plate. Degassing was performed in air at room temperature. In some samples annealing removed the effects of the deformation. Hydrogen saturation was attained after one sequence or after repeated cycles of ‘saturation- degassing’ (cycling).

Peculiarities of Phase Transformations in Pd-H

Plots of the dependence of the P-phase concentration p(t) in Pd on saturation times at low current density (2.5 mA cm”) show a logarithmic dependence between the In(1 - p) function and the

time, see Figure 1 (7). Lines 1, 2 and 3 relate to regions or ‘blocks’ of coherent scattering ((hh’) blocks) which have crystallographic planes with (loo), (311) and (110) indices, respectively, parallel to the external surfaces of the sample.

The experimental points lie on straight lines that do not pass through the coordinates (0,O). The dependence of the P-phase concentration on time is:

P(4 = ’ - *[- rtt- fdl where y represents the logarithmic rate of P-phase growth and to represents the duration of the incubation period. Both y and t o depend on the crystallographic orientation of the ‘block‘ planes with respect to the external surface. The factor is a maximum for the (100) blocks and a minimum for the (110) blocks, while to is a minimum for (100) blocks and a maximum for (110) blocks. The dependence on orientation is considered to be greater for y than for to.

In addition, to and y depend upon the current density,j. A s j increases up to 25 mA cm-’, the incubation period to decreases almost 40 times for the (100) block while y increases by one order of magnitude. These findings can be explained by the kinetic theory of first-order phase transformation (7). According to this theory, the P + a phase transformation can take place when the decrease in internal energy (due to a-phase formation) is greater than the amount of energy needed to make boundaries between the new phase and the o

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PLATINUM METALS REVIEW · 2016. 1. 28. · I Fig. I The perjhnance losses seen in a typical DMFC MEA operuting with dilute MeOH and air at SOT, compared to those in a PEMFC. The PEMFC