Presented by M. G. PRAKASH National Centre for Catalysis Research

Nickel based bimetallic catalysts supported on titania for selective hydrogenation of

cinnamaldehyde

Presented by M. G. PRAKASH

National Centre for Catalysis Research Indian Institute of Technology, Madras

Introduction Bimetallic catalysts - composed of two metal elements in either alloy or intermetallic form often develop as materials of new category with catalytic properties different from monometallic catalysts.

Generally bimetallic alloys in particular , is an import subject for a number of technological reasons some of which are (1) Catalyst Chemistry (2) Electrochemistry (3) Metal-Metal Interfaces (4) MicroelectronicFabrication etc.

The following aspect of an alloy surface should be examined ,

1)The chemical composition of an alloy surface

2)The surface structure factor

3)The electronic structure and geometric factors

Fig A hypothetical situation of (100) surfaces of an alloy XY with the fcc structure (a) Pure X (b) 50 % X , 50 % Y , ordered (C) 50 % X, 50% Y with Clustering of Y (d)75% X,25 % Y

Nieuwenhuys, The chemical physics of Solid Surface Amsterdam 1993, 6 185-22

Schematic illustration of producing crown jewels structure

X.Liu, D. Wang and Y.Li Nano Today(2012) ,7 448-466

Objectives To prepare Nickel Nano particles by using green chemistry via glucose as reducing agent, supported on P25 .

Preparation of bi-metallic Ni-Cu/TiO2, Ni-Ag/TiO2 and Ni-Au/TiO2 catalysts. Optimization of the reduction conditions for the prepared catalysts.

Studying the Physico-chemical properties of the catalyst samples using various techniques like XRD, TPR, TEM etc.

Studying the catalytic activity of the reduced catalysts using model reactions, liquid phase hydrogenation of cinnamaldehyde.

Identifying the reaction products using GC.

Establishing correlations between the activity, stability and selectivity of the catalysts and their Physico-chemical properties .

6

Reaction scheme Carbonyl group

Olefinic group

Desired productundesired rex

Desired rex

undesired rex

G = 118 KJ/molG = 80.71KJ/mol

G = 37.79 KJ/molG = 0.49KJ/mol

CAL=cinnamaldehyde, COL=cinnamyl alcohol, HCAL= hydrocinnamaldehyde,HCOL=hydrocinnamyl alcohol

Aim and scope of the work

Experimental approach

To prepare, characterize and test performance of following catalysts

1)Influence of preparation Methods (Bimetallic catalysts) • Direct Impregnation Method • Urea Deposition method• Impregnation of stabilzed Ni Nano particles (a)hydrazine hydrate (b) glucose (green chemistry)

0.03 moles of Nickel acetate + 0.03 moles of Cu or Ag or Au + 40 ml of D-glucose solution (0.1 M)

Stirred for 30 min at RT 10ml of liq.ammonia solution

Refluxed for 5 h at 80 C⁰ The solution was changed black colour

1g of TiO2 ( P25) Stirred for 2 h at 80 C⁰

Cooled , centrifuged and dried at 60 C⁰

Preparation of Bimetallic Cataslyst

M .Vaseema,N.Tripathya G. Khangbandb Y.Hahn*aRSC Adv., 2013, 3, 9698–9704

Fig .1 shows the XRD patterns of (a) Ni/P25 (b) Ni-Cu/P25 (c)Ni-Ag/P25 (d)Ni-Au/P25

Fig .2 shows the TPR profile of (a) Ni/P25 (b)Ni-Cu/P25 (c)Ni-Ag/P25 (d)Ni-Au/P25

Fig .3 shows the TEM Images are (a) Ni/P25 (b)Ni-Cu/P25 (c)Ni-Ag/P25 (d)Ni-Au/P25

Fig.4Hydrogenation of cinnamaldehyde on Ni/P25 ,Ni-Cu/P25,Ni-Ag/P25and Ni-Au/P25 conversion and selectivity. Reaction temperature 373 K ,Time 1 h ,catalyst 150 mg, cinnamaldehyde 1.2 g reactant.

Table.1. Hydrogenation of cinnamaldehyde on Ni and Ni based bimetallic catalysts on TiO2 supports at different temperatures

No Catalysts CAL Conv. % Selectivity (%)

HCAL COL HCOL others

1Ni/ P25-100º C Ni/ P25-120º CNi/ P25-140º C

60.091.098.0

63.031.029.0

31.061.027.3

5.06.943.6

1.01.10.1

2

Ni-Cu/P25-60ºCNi-Cu/P25-80ºCNi-Cu/P25-100ºCNi-Cu/P25-120ºC

62.076.389.298.0

14.313.612.511.0

64.546.035.119.0

2038.552.370

1.20.90.11.5

3

Ni-Ag/P25-60ºCNi-Ag/P25-80ºCNi-Ag/P25-100ºCNi-Ag/P25-120ºC

64.076.090.598.0

14.512.710.99.0

60.944.435.918.0

17.540.242.576.0

7.13.70.71.0

4

Ni-Au/P25-60ºCNi-Au/P25-80ºCNi-Au/P25-100ºCNi-Au/P25-120ºC

60.077.092.6598.0

14.113.112.711.0

70.8647.3727.312.2

13.136.349.679.0

1.943.230.40.8

15

Mixture of reactant and products

Reactant

Calibration of GC

COLHCAL

HCOL

C=O bond activation by electropositive Fe on Pt surface

Concept of Lewis sites

Ref: Richard, J. Ockelford, A. Giroir-Fendler, and P. Gallezot, Catal.Lett., 3,53 (1989).

Conculsion

oNi-Au/P25,Ni-Cu/P25 & Ni-Ag/P25 bimetallic systems are showing more activity and selectivity, but when compared to monometallic Ni/P25.

oThe strong interaction between Ni and Cu or Ag or Au was demonstrated to the main reason for the enhanced catalytic activity of catalysts.

oThe Electronic structure of the surface Ni atoms was modified upon the addition of Cu or Ag or Au ,so reducibility of nickel increased.

oImproved the activity can be also ascribed to the high dispersion of Cu or Ag or Au on nickel nanoparticles of the bimetallic catalysts.

Summary

HYDRGENOLYSIS OF BIO-MASS DERIVED POLYOLS TO VALUE

ADDED CHEMICALS

R.Vijaya Shanthi,S.SivasankerNational Centre for Catalysis Research,

I I T – M, Chennai.

One of the most attractive routes of biomass utilization is its direct conversion to valuable organic compounds which gets more and more attention an ever .

An effective process for the biomass utilization is hydrogenolysis of polyalcohols derived from biomass.

Hydrogenolysis has a great potential in the conversion of biomass-derived polyols, such as sugars or sugar alcohols.

Introduction

We had earlier reported studies on Ni, Pt and Ru supported on the basic support, NaY for sorbitol hydrogenolysis. (Topics in Catalysis (2012) 55:897–907.)

As a part of our investigations on the influence of the support on the performance of supported metal catalysts we have now carried out hydrogenolysis of glucose & glycerol over unconventional support, viz.

Present work

Hydroxyapatite

Materials based on Ca10(PO4)6(OH)2 (hydroxyapatite, HAP) have attracted tremendous interest because of high stability at high temperatures and least soluble in aqueous medium which will be very useful for reactions involving aqueous medium .

Taking into account environmental and economical considerations, the handling of hydroxyapatite used as a catalyst presents many advantages such as to easier separation,recovery from the reaction mixture and thus, enhanced recycling possibilities, which are now well established in fine organic synthesis.

HAP has recently received much attention in view of its potential usefulness as adsorbent and most importantly as catalyst in solid/gas reactions.

The various products obtainable by hydrogenolysis of glucose

Crystalline structure of hydroxyapatite

stirred at room temperature

Filtered, dried for 12 h at 120 °C

Calcined in air at 600 °C for 4 h

Reduced in H2 for 4 h at 400 °C (prior to use)

6%Ni/HAP;1%Pt/HAP;1%Ru/HAP

refluxed for 4 h

7.927g of (NH4)2HPO4 in 250ml solution( at a pH>12 (60–70 ml NH4OH) )+ 23.63 g of Ca(NO3)2 .4H2O

in 150ml solution

Impregnation method-(Ni -6 wt.%;Pt-1 wt.%;Ru-1 wt.%)

HAP

dried for 12 h at 120 °C

Calcined in air at 600 °C for 4 h

Synthesis of HAP & preparation of catalysts

Support

Catalyst

Characterization of HAP & the catalysts

XRD patterns Physicochemical property

TEM images - The crystals are rod-like in shape & the particles are ofapproximately 20–40 nm in diameter with 40–60 nm in length.

Catalyst SBET

(m2/g)

Pvtot

(cm3/g)

Av. pore

dia.(Å)

Metal dispersion (%) [crystallite

size, nm]

HAP (Ca:P-1.58) 45 0.42 374

Ru(1%)-HAP - - - 26 [2.2]

Pt(1%)-HAP - - - 15 [11.4]

Ni(6%)-HAP - - - 2.5 10.4]

6%Ni- H

AP

12%Ni- H

AP

6%Cu- HAP

12%Cu- HAP

1%Pt- H

AP

1%Ru- HAP

0

10

20

30

40

50

60

70

80

90

100 CONV. SEL. (PD+EG)

Wt

(%)

180 190 200 210 2200

10

20

30

40

50

60

70

80

90

100

Temperature C

Con

vers

ion

/sel

ecti

vity

(W

t%)

Conversion 1,2-PD EG

Conditions: 15% glycerol in water; press.: 60 bar; time: 6 h; stirring speed: 300rpm; G= glycerol; PD = 1,2-propanediol & EG = ethylene glycol; A-absence of base; B-presence of base

Effect of temperature – 12%Ni/HAPEffect of catalysts

Fresh I Cycle II Cycle III Cycle0

10

20

30

40

50

60

70

80

90

100

Con

vers

ion

/sel

ecti

vity

(W

t%)

CONV. SEL. (PD+EG)A


10

20

30

40

50

60

70

80

90

100

B

Con

vers

ion

/sel

ecti

vity

(W

t%)

CONV. SEL. (PD+EG)

A

Recyclability – 12%Ni/HAP

0

10

20

30

40

50

60

70

80

90

100

0

10

20

30

40

50

60

70

80

90

100

CONV. SEL. (PD+EG)

Wt

(%)

A

0

10

20

30

40

50

60

70

80

90

100

B CONV. SEL. (PD+EG)

Wt

(%)

Effect of solvent– 12%Ni/HAP

The presence of base enhances the conversion & selectivity

Catalyst Glucose Conv.

(%)

Product Selectivity (wt%)

S Dihydric alcohols

G Others

1,2 PD EG

Ru/Hap 80 26 20 18 16

Ru/Hap+ Ca(OH)2 86 22 22 20 14

Pt(1%)-HAP 74 34 18 20 12

Pt/Hap+ Ca(OH)2 80 31 21 20 14

Ni/Hap 96 18 18 24 26

Ni/Hap+ Ca(OH)2 98 10 16 26 28Conditions: 15% glucose in water; cat.: 0.2 g; temp.: 140 °C; press.: 60 bar; time: 6 h; stirring

speed: 1000 rpm; S = Sorbitol; G= glycerol; PD = 1,2-propanediol & EG = ethylene glycol; trihydric(except glycerol) and higher alcohols; monohydric alcohols and :others

(methanol,ethanol&butanol); Ca(OH)2 , 0.25g.

Order of activity: (A) Ni/Hap > Ru/Hap > Pt/Hap (in absence of Ca(OH2). (B) Ni/Hap > Ru/Hap > Pt/Hap (in presence of Ca(OH2).

Effect of reaction parameters – 6%Ni/HAP

120 130 140 150 1600

10

20

30

40

50

60

70

80

90

100

Temperature C

Con

vers

ion/

sele

ctiv

ity

(Wt%

)

Conversion Glycerol 1,2-PD EG

Temperature

0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.450

10

20

30

40

50

60

70

80

90

100

Conversion Glycerol 1,2-PD EG HA

Catalyst amount (g)

Con

vers

ion

/sel

ecti

vity

(W

t%)

Catalyst amount

Effect of run duration – 6%Ni/HAP

0

10

20

30

40

50

60

70

80

90

100

6%Ni- H

AP

1%Pt- H

AP

1%Ru- HAP

0

10

20

30

40

50

60

70

80

90

100 CONV. SEL. (PD+EG)

Wt

(%)

Yield (PD+EG)

Temp - 140 °C; Catalyst - 0.2g Run duration – 6 h

Optimum conditions

Effect of catalysts

0 1 2 3 4 5 6 7 8 9 10 11 120

10

20

30

40

50

60

70

80

90

100


Con

vers

ion

/sel

ecti

vity

(W

t%)

Time (h)

B

0 1 2 3 4 5 6 7 8 9 10 11 12 130

10

20

30

40

50

60

70

80

90

100


Con

vers

ion

/sel

ecti

vity

(W

t%)

Time (h)

A

Recyclability – 6%Ni/HAP


10

20

30

40

50

60

70

80

90

100

C

on

ver

sio

n/s

elec

tivit

y (

Wt%

)

Conversion Glycerol 1,2-PD+EG

A


10

20

30

40

50

60

70

80

90

100

C

on

ver

sion

/sel

ecti

vit

y (

Wt%

)

Conversion Glycerol 1,2-PD+EG

B

(A) in the absence of Ca (OH)2and (B) in the presence of Ca(OH)2

Conditions: Temp., 140 °C; pressure, 60 bars; run duration, 6 h; catalyst, 0.2g; sorbitol, 15 g; water, 85 g; Ca(OH)2 , 0.25g.

The presence of base enhances the conversion & selectivity marginally

The influences of temperature, catalyst loading and reusability on sorbitol conversion and selectivity were investigated with 6%Ni/HAP catalyst. The influence of the addition of the base Ca(OH)2 on conversion and product yields is also influenced the conversion and selectivity of both glycerol & glucose.

The influence of the support on Hydrogenolysis of glycerol & glucose was investigated over HAP metal supported catalysts.

The loading of the metals was: Ni, 6%; Cu, 6 %; Ru 1 %; and Pt, 1 %. Ni/HAP & Ni/Hap were found to be the most active and selective (for glycols) amongst all the catalysts.

Conclusion

Mechanism of the hydrogenolysis of sorbitol in the presence of a base

A general observation is that the reaction proceeds better in a basic medium, typically, in the presence of Ca(OH)2.

Photocatalytic reduction of Carbon dioxidePhotocatalytic reduction of Carbon dioxide over Strontium titanate surfacesover Strontium titanate surfaces

V. Jeyalakshmi, K. R. Krishnamurthy & B. ViswanathanNCCR, IIT Madras

Utilization of COUtilization of CO2 2 - A global endeavor- A global endeavor

Global demand for energy to set to increase by 50 % by 2030

Fossil fuels continue to be the major source of energy

Increase in CO2 emission levels- a matter of concern

Increase in earth’s average surface temp. - 0.6K in the last century

Green house effect, changes in weather patterns

COCO22 management - A challenging task management - A challenging task

Utilization of COUtilization of CO2 2 - A global endeavor- A global endeavor

Processes for COProcesses for CO22 conversion conversion

Chemical

Photo-chemical

Bio-chemical

Photo bio-chemical

Radio-chemical

Electro-chemical

Photo electro-chemical

Photo bio-electrochemical (MA Scibioh & B.ViswanathanProc.Ind.Natl. Sci.Acad.70A,407,2004)

.

Photo catalytic reduction that utilizes solar energy which has

tremendous potential

Photo catalytic reduction of COPhoto catalytic reduction of CO22 with H with H22OO

Process & catalyst Splitting of water to yield hydrogen Reductive conversion of CO2 to hydrocarbonsBoth steps proceeding via photo catalysis. Bi-functional catalyst design to include components that are

active for both functionalities suitable for activation with the most abundant visible light

Challenges for practical applicationChallenges for practical applicationMaximization of hydrocarbons formation Maximization of hydrocarbons formation Selectivity towards narrow range hydrocarbons

Choice of catalysts- Guiding principlesChoice of catalysts- Guiding principles

Valence band top energy level to be suitable for splitting of water Conduction band bottom energy level to be more negative with

respect to reduction potential of CO2

VB & CB potentials for selected semi-conductors relative to the energy levels for CO2 redox couples in water(T.Inoue, A.Fujishima,S.Konishi & K.Honda, Nature,277,637,1979)

38

SrTiO3, Sr3Ti2O7 & Sr4Ti3O10

Kudo et al. Chem. Soc. Rev., 38(2009) 253

SrTiO3, as one of the most promising photocatalysts, is now used in various practical applications.

In these materials , slabs of SrTiO3 are cut parallel to

the idealised cubic perovskite (100) planes and stacked

together , each slab being slightly displaced from the process.

COCO2 2 Photo reduction on Strontium titanate surfacePhoto reduction on Strontium titanate surface

The large band gap sizes of early transition-metal oxides (>3.0eV) restrict The large band gap sizes of early transition-metal oxides (>3.0eV) restrict their photocatalytic activities to ultraviolet wavelengths.their photocatalytic activities to ultraviolet wavelengths.

Non metal doping (N doping) Metal doping (Fe doping) (a) the charge carrier recombination time is largely influenced by the presence of iron cations, (b) presence of iron induces a batho-chromic effect, and (c) iron doped photocatalyst is efficient in several important photocatalytic reduction and oxidation reaction

STO:N, Fe. Will exhibit high photocatalytic activities under vis illumination, which is due to the decrease in the oxygen vacancies

because co doping maintains the charge balance.

Modified Strontium titanate catalystsModified Strontium titanate catalysts

Synthesis of SrTiO3 Polymerized complex method gives fine and well-crystalline powders with

a high surface area at relatively low calcination temperature and short

calcination time compared with a conventional solid state method.

Kudo et al. Chem. Soc. Rev., 38(2009) 253–278

Ethylene glycol : Methanol(1:2).

0.5mole of Citric acid + 3mole of Sr(NO3)2 + 2mole of Urea/Thiourea or 3% Fe2O3 added to the mixture .

The solution was stirred at 130°C for 20 hrs.

The resulting polymerized complex gel was pyrolyzed at 350 °C

N,S/Sr3Ti2O7 or Fe2O3/Sr3Ti2O7

2 mole of C16H36O4Ti was added.

Precursor was calcined at 900°C for 2 h.

Methanol, Ethylene glycol , citric acid should be in the molar ratio of 1:2:0.5.

H.Jeong et al. International Journal of Hydrogen Energy 31 (2006)1142 – 1146

Preparation of Strontium titanate

XRD pattern for SrTiOXRD pattern for SrTiO33

The shift indicates that a part of Iron at least is homogeneously doped into the SrTiO3 lattice. Ionic radii of six-coordinated Fe3+ (0.62A˚) are almost the same

as Ti4+ ion (0.61A˚).

XRD pattern for SrXRD pattern for Sr33TiTi22OO77

The shift indicates that a part of Iron at least is homogeneously doped into the Sr3Ti2O7 lattice. Ionic radii of six-coordinated Fe3+ (0.62A˚) are almost the same

as Ti4+ ion (0.61A˚).

XRD pattern for SrXRD pattern for Sr44TiTi33OO1010

The shift indicates that a part of Iron at least is homogeneously doped into the Sr4Ti3O10 lattice. Ionic radii of six-coordinated Fe3+ (0.62A˚) are almost the same

as Ti4+ ion (0.61A˚).

Catalyst Crystalline size (nm)

Band gap (nm)

SrTiO3 28.9 3.05

Fe/NS/SrTiO3 33 3

Sr3Ti2O7 46 3.14

Fe/NS/Sr3Ti2O7 39 2.4

Sr4Ti3O10 52.7 3.12

Fe/NS/Sr4Ti3O10 46.7 2.9

DR spectra for the catalystsDR spectra for the catalysts

Photo luminescence spectraPhoto luminescence spectra of the catalystsof the catalysts

Co doping increases exciton life time.

SEM ImageSEM Image

SrTiO3 Sr3Ti2O7 Sr4Ti3O10

Fe NS SrTiO3 Fe NS Sr3Ti2O7Fe NS Sr4Ti3O10

Reactor volume - 650 mlReaction medium - 400 ml of 0.2 N aqueous NaOH.Temperature- 298KCatalyst loaded - 0.4g. Dispersed in the medium with continuous agitation-400 rpmCO2 was bubbled for 30 min.

pH of the medium- Reduced to 8.0 after saturation with CO2 from the initial value 13.0 Reaction medium was irradiated through a 5cm dia. quartz window.Light source-High pressure Hg lamp-UV-Vis radiation -300-700 nm

77W powerThe products were analyzed using Perkin Elmer Clarus 500 Gas chromatograph - Poroplot Q, 30 m, at 150ºC with FID for analysis of hydrocarbons and Mol.Sieve 5A column for H2 & O2 analysisGas (0.2 ml) and liquid (1 µl) phase samples were withdrawn every two hours from the reactor and injected into the GC.

Reaction & AnalysisReaction & Analysis

• Reactor volume - 650 ml, Reaction medium - 400 ml of 0.2 N NaOH .• Catalyst loaded - 0.4g . CO2 was bubbled for 30 min.






Catalyst Products formed after 20hrs of irradiation (μmol/g) Conversion (%)CH4 C2H4 C2H6 CH3OH C2H4

OC2H5

OHC3H6

OC3H6 Total CO2

consumed

SrTiO3 0.42 0.3 0.14 212 0 89.2 0 0 391.8 0.55

Fe/NS/SrTiO3 0.5 0.6 0 498.9 0 66.4 0 0.2 567.8 0.79

Sr3Ti2O7 0.5 0.2 0.2 248.8 7.6 53.4 0 0.2 373 0.5

Fe/N,S/Sr3Ti2O7 0.1 5.4 0.2 561 1.6 284 25 0.9 1221.7 1.7

Sr4Ti3O10 0.22 0.8 0.2 222.3 0 129. 0 0.8 485.4 0.68

Fe/NS/Sr4Ti3O10 0.28 0 0.2 409.6 1.8 123.6 0 0 661.1 0.93

Photo reduction of COPhoto reduction of CO22- Cumulative - Cumulative

conversionconversion

Activity pattern for COActivity pattern for CO22 photo photo reductionreduction

SrTiO3, Sr3Ti2O7 ,Sr4Ti3O10 & modified samples were prepared by polymerised complex method.

Layered strutured shows impured photocatalytic activity compared to neat perovskite SrTiO3, which is probably due to separation of active site and increased the exciton life time.

SrTiO3 codoped with nitrogen and Iron exhibited the high photocatalytic activity due to the decrease of the oxygen vacancies, which may act as electron-hole pair recombination centers, because codoping with Fe3+ and N3- ions maintained the charge balance.

SummarySummary

Thank you!Thank you!

pH dependent carbonate ions in solution

After bubbling carbon dioxide the most likely species present in the reaction medium is HCO3

-

OH- ions act as hole scavengers, form OH radicals, and reduce the electron-hole recombination rate. Increase in lifetime of photo electrons would facilitate the reduction of CO2.(I-H

Tseng et al.,Appl.Catal.B Env.37,37,2002)

Alkaline medium increases the solubility of CO2.

Role of alkaline (NaOH) reaction Role of alkaline (NaOH) reaction mediummedium

Criteria for selection of SC photo-catalysts1. The SC should have narrow band gap to absorb as much light as possible.2. The bottom of the conduction band must be more negative than the

reduction potential of water to produce hydrogen and the top of the valence band must be more positive than the oxidation potential of water to evolve oxygen.

3. Efficient charge separation and fast charge transport simultaneously avoiding the bulk and surface recombination are essential to migrate the photo-generated charge carriers to the surface reaction sites.

4. Kinetically feasible surface chemical reactions must take place between the charge carriers and water or other molecules and the backward chemical reaction should be capable being suppressed.

Outcome Develop SC specific bulk and surface propeties and energy band structures to satisfy these demands

Xinchen Wang, Kazuhiko Maeda, Arne Thomas, Kazuhiro Takanabe, Gang Xin, Johan M. Carlsson, Kazunari Domen & Markus Antoniett : A metal-free polymeric photocatalyst for hydrogen production from water under visible light, Nature Materials 8, 76 - 80 (2009)

a, Schematic diagram of a perfect graphitic carbon nitride sheet constructed from melem units. b, Experimental XRD pattern of the polymeric carbon nitride, revealing a graphitic structure with an inter planar stacking distance of aromatic units of 0.326 nm. c, Ultraviolet–visible diffuse reflectance spectrum of the polymeric carbon nitride. Inset: Photograph of the photo-catalyst.

a, Density-functional-theory band structure for polymeric melon calculated along the chain (Gamma–X direction) and perpendicular to the chain (Y–Gamma direction). The position of the reduction level for H+ to H2 is indicated by the dashed blue line and the oxidation potential of H2O to O2 is indicated by the red dashed line just above the valence band. b, The Kohn–Sham orbitals for the valence band of polymeric melon. c, The corresponding conduction band. The carbon atoms are grey, nitrogen atoms are blue and the hydrogen atoms are white. The isodensity surfaces are drawn for a charge density of 0.01qe Å-3.

A typical time course of H2 production from water containing 10 vol% triethanolamine as an electron donor under visible light (of wavelength longer than 420 nm) by (i) unmodified g-C3N4 and (ii) 3.0 wt% Pt-deposited g-C3N4 photocatalyst. The reaction was continued for 72 h, with evacuation every 24 h (dashed line). Unmodified g-C3N4 also photocatalysed steady H2 production from aqueous methanol solution (10 vol %)

Steady rate of H2 production from water containing 10 vol% methanol as an electron donor by 0.5 wt% Pt-deposited g-C3N4 photo-catalyst as a function of wavelength of the incident light. Ultraviolet–visible absorption spectrum of the g-C3N4 catalyst is also shown for comparison.

Time courses of O2 production from water containing 0.01 M silver nitrate as an electron acceptor under visible light (of wavelength longer than 420 nm) by 3.0 wt% RuO2-loaded g-C3N4. La2O3 (0.2 g) was used as a buffer (pH 8–9).

Thermal stability 873 K chemical stability acid base and organic solvents, Eg ~ 2.7 eV band positions suitable for water reduction and oxidation. Shining star of photo-catalysis

Synthesis of C3N4

Thermal condensation of nitrogen rich precursors such as cyanamide, dicyandiamide, melamineTexture modification, elemental doping, copolymerization

To: Viswanathan B

Perspectives and outlook1. Amenable for modification

2. Medium band gap with HOMO and LUMO positions for electron transfer with powerful chemical potential

3. Artificial photosynthesis, oxygenation, reduction, base catalysis, aromatic, double and triple bond activation.

4. Metal free, thermal, chemical stability, tunable electronic structure, abundant, cheap

5. Rates are still low role of covalence in reversible bonds formed or split

6. Enzyme like functionality possible

7. Structure and catalytic activity correlation?

8. Increasing the domain size and improvement of electrochemical properties due to incomplete poly condensation

9. Only a few reactions have been addressed - substrate specific reactions will be the future challenge

8

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27th July 2014

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employing DFT and other modern theories for condensed matter applications.

Research programmes in frontier areas

NCCR has successfully achieved NCCR has successfully achieved the goal/ mandates the goal/ mandates

Research Scholars Orientation programs-14Research Scholars Orientation programs-14M Tech Degree Course in Catalysis Technology-4M Tech Degree Course in Catalysis Technology-4Ph. D Degree Course- 5/25Ph. D Degree Course- 5/25Advanced research facilities in CatalysisAdvanced research facilities in CatalysisResearch programmes in frontier areasResearch programmes in frontier areasCollaborations with International and National Collaborations with International and National Universities/Institutes Universities/Institutes Establishing vibrant academia-industry Establishing vibrant academia-industry partnership- 12 industry sponsored research partnership- 12 industry sponsored research projectsprojectsCharting out a road map for futureCharting out a road map for future

NCCR-Research Contributions

Publications in journalsPublications in journals 228228

Presentations in Seminars/SymposiaPresentations in Seminars/Symposia 248248

PatentsPatents 18 18

Books/ChaptersBooks/Chapters 29 29

CatalysisCatalysisNearly two centuries old; continues to be an ever-green

branch of science, exciting & vibrantTremendous impact on society & science

Four Nobel prizes in Catalysis in the last decade-Asymmetric catalysis, Olefins MetathesisSurface chemistry, Pd catalyzed Cross-couplings

> 30 journals explicitly devoted to Catalysis besides

ACS & RSC journals New journals started in 2011-ACS- Catalysis ; RSC-Catalysis –Science & Technology

Undergoing a renaissance-science & technologyShift in focus- from chemical processes to Energy & Environment- major concerns of modern society

Set to emerge as a source for sustainable Set to emerge as a source for sustainable solutionssolutions

The approach ……..The approach ……..Basic functionalities to be built in : Activity, Selectivity,

Life, Regenerability, Thermal & Mechanical stabilitySelection of catalytic components that generate the

functionalities for a specific process- Empirical → Rational

Architectural approach in effective integration of the components.

Scientific basis for selection & integration-theoretical & experimental validation - - Significant progress

Concept of active centreConcept of active centre

The basis for catalyst designThe basis for catalyst design

Design of Design of CatalystsCatalysts

Supported metal catalysts-guiding principles Pt metal-Bulk Crystal-Crystal planes- Surface structure--active sites

Bonding/Reactivity of reactants on terrace/step/kink sites is determined by the co-ordination numbers/co-ordinative unsaturation

For cyclic hydrocarbon reactant C-H bond activation – step sites- Dehydrogenated product C-C- bond activation - kink sites- Ring opening

Active phase composition-Structure-Size-ShapeActive phase composition-Structure-Size-ShapeSurface structure-SelectivitySurface structure-Selectivity

Active sites on the Active sites on the surfacesurface

Topics in Catalysis (2010) 53:832–847

The resurgenceAdvent of nano science & technologyRole of size and shape of nano particles

Size-Activity ; Shape –SelectivityRange of catalyst preparation techniques

Colloidal synthesis, self-assembly, use of dendrimersSynthesis & characterization of New materials

Ordered mesoporous materials, MOF, CNT, GraphenesAdvanced theoretical-computational methodsSurface sensitive analytical techniques-molecular/atomic

levelCombinatorial catalysis

High throughput catalyst evaluation & preparation

Rational approach to design of catalystsRational approach to design of catalysts

Novel catalyst architecturesNovel catalyst architectures

Enabling techniques & Enabling techniques & toolstools

Design of active Design of active centrescentres

Well defined morphology Size & Shape control Exposure of specific planes Analytical techniques

AdsorptionActivationSurface reactionsDesorption

Activity Selectivity Stability

Process

Surface reactivity Performance

Mechanistic pathways

Surface structure

Preparation methods

Theoretical studies

Energetics of Reactant-surface

interactions

Modern approachesModern approaches

Sustainable processes and products Sustainable processes and products through Catalysis- Challengesthrough Catalysis- Challenges

Energy-Environment-Renewable feed-stocks-Energy-Environment-Renewable feed-stocks-Design, Synthesis and Application of New materialsDesign, Synthesis and Application of New materials

NCCR- Future activitiesNCCR- Future activities

Emphasis on•Educational activities•Training and manpower development•New areas of research-basic & applied•Strengthen research facilities•Expand research collaborations

NCCR-Plan for Next 5 YearsNCCR-Plan for Next 5 Years

Road aheadTo spread its wings over several emerging and new frontiers in the science of catalysis. To carve out its own place within IIT Madras as a vibrant entity with significant contributions in contemporary topics in Catalysis.

Focus for the next five years Intensifying Academic Research leading to publications in high impact journals.Aggressively pursuing Industry supported or industry oriented projects that would lead to Patent Disclosures covering cutting-edge product development/process technologies. Strengthening Academic activities related to: • Research for imparting knowledge and training to young researchers.• Resource generation in terms books, e-books and databases.

Expanding and strengthening international collaboration with other Catalysis Research Centres across the globe and provide a platform for Indian Scientists a uniform play ground to compete internationally.

To tread along the growth path & strive for recognition at global level

NCCR on Global HorizonNCCR on Global Horizon

Catalysis has emerged as a leading branch of science in the last two decades and expected to grow further Amply reflected with the initiation of specialized journals by RSC, ACS Catalysis will continue to flourish and blossom into a branch of science attracting fundamental knowledge creation and helping to achieve sustainable living in this universe.

Energy-Environment- Life style & EconomyEnergy-Environment- Life style & Economy The economic and environmental benefits of Catalysis have been established beyond doubt and will continue to be the centre stage of knowledge generation in the decades to come. India has in the past evolved path-breaking methodologies for a sustainable society in this world, could take lead and become one of the torch bearers in modern science. NCCR would play a major role in the realization of India’s potential in this branch of science and emerges as the knowledge centre.

NCCR on a Growth Path

NCCR has the potential to emerge as a:

• Knowledge storehouse not only for this country but to the entire world

• International centre for creation of skilled and competent human resources

• Centre where not only research in cutting edge technologies will be developed but also a nucleus for generating newer directions for research and practice in industry.

Above all, a Centre of excellence in an academic and applied area like Catalysis will be directly reflecting in the economy of the country.The Centre will have a leading role and contribute towards the advancement of science & technology in the years to come

On this day, 27th July 2014, let us all re-dedicate ourselves to the task of building a strong and vibrant NCCR

Thank you !

Documents

Presented by M. G. PRAKASH National Centre for Catalysis Research