Surface-Immobilized Conjugated Polymers Incorporating

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Supporting Information

Surface-Immobilized Conjugated Polymers Incorporating

Rhenium Bipyridine Motifs for Electrocatalytic and

Photocatalytic CO2 Reduction

Nicholas M. Orchanian, Lorena E. Hong, John A. Skrainka, Jacques A. Esterhuizen, Damir A.

Popov, and Smaranda C. Marinescu*

Department of Chemistry, University of Southern California, Los Angeles, California 90089,

United States

*email: [email protected]

Experimental Methods

Materials and Synthesis

All manipulations of air- and moisture-sensitive materials were conducted under nitrogen

atmosphere in a Vacuum Atmospheres glovebox or on a dual manifold Schlenk line with oven-

dried glassware. Water was deionized with the Millipore Synergy system (18.2 MΩ·cm). All

other solvents used were degassed with nitrogen, passed through activated alumina columns, and

stored over 4Å Linde-type molecular sieves. Proton NMR spectra were acquired using a Varian

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400-MR 2-Channel spectrometer at room temperature and referenced to the residual 1H

resonances of the deuterated solvent (1H: CD3CN, δ 1.95 ppm). The [2,2'-bipyridine]-5,5'-

diamine ligand was synthesized according to reported literature procedures.1 Complex 1 was

synthesized according to our previous report.2 All other chemical reagents were purchased from

commercial vendors and used without further purification.

Synthesis of 2

Complex 1 was recrystallized by slow diffusion of ether into a concentrated DMF

solution. Recrystallized complex 1 (45 mg) was suspended in acetonitrile (1.9 mL) and briefly

sonicated for 5 minutes. Separately, a solution of nitrosonium tetrafluoroborate (24 mg) was

dissolved in a minimal amount of acetonitrile (0.9 mL). Both solutions were cooled to -40 °C.

Once cooled, the suspension of 1 was added dropwise to the NOBF4 solution, leading to an

immediate color change from pale-yellow to dark blue. Addition of diethyl ether (6 mL) resulted

in the formation of a dark blue precipitate, which was collected by filtration, and stored in the

dark at -27 °C (1H in CD3CN: δ 10.10, 9.29 and 9.02 ppm).

Electrochemistry

Cyclic Voltammetry

Electrochemistry experiments were carried out in acetonitrile solution with 0.1 M

TBAPF6 electrolyte using a Pine potentiostat. The pseudo-reference electrode used was a Ag

wire purchased from VWR. The platinum wire used as a counter electrode was purchased from

Alfa Aesar. Ohmic drop was compensated using the positive feedback compensation

implemented in the instrument. All experiments in this paper were referenced relative to

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ferrocene (Fc) with the Fe3+/2+ couple at 0.0 V. Electrochemical experiments were carried out in

a three electrode configuration electrochemical cell under a nitrogen or CO2 atmosphere using

glassy carbon, graphite rod, carbon nanotubes, FTO, TiO2, or gold as the working electrode. The

reference and counter electrodes were isolated in glass capillaries with Vycor frits.

Estimation of Electrochemically-Active Coverage

The electrochemically-active catalyst loading was estimated by cyclic voltammetry. A

cathodic scan sweeping from Pi = -0.6 V to Pi = -2.25 V was performed for the modified

electrode under a nitrogen atmosphere. The resulting current-time plot was integrated for the film

redox feature at -1.95 V, which was used to determine and estimated catalyst loading based on

Equation S1 below. Q represents the total charge passed at the electrode for the cathodic wave

(C), F represents the Faraday constant (96,485 C mol-1), n represents the number of electrons for

the reduction event (2), and A represents the area of the electrode (cm2).

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Controlled Potential Electrolysis and Gas Chromatography

CPE measurements were conducted in a two-chambered H cell. In the first chamber, the

working and reference electrodes were immersed in 40 mL of 0.1 M tetrabutylammonium

hexafluorophosphate (TBAPF6) in acetonitrile. The counter electrode (graphite rod) was placed

in the second chamber in 20 mL of 0.1 M TBAPF6 in acetonitrile. The two chambers were

separated by a fine porosity glass frit and the reference electrode was placed in a separate

compartment connected by a Vycor tip. Graphite rod electrodes (0.8 cm diameter; NAC Carbon

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Products, Inc.) were used as the working and auxiliary electrodes. For gas chromatography

experiments, 2 mL of gas were withdrawn from the headspace of the H cell with a gas-tight

syringe. This was injected into a gas chromatography instrument (Shimadzu GC-2010-Plus)

equipped with a BID detector and a Restek ShinCarbon ST Micropacked column. Faradaic

efficiencies were determined by dividing the amount of CO produced as measured by gas

chromatography by the amount of CO expected based on the total charge measured during

controlled potential electrolysis. For each experiment, the controlled-potential electrolysis

measurements were performed at least twice (with two electrodes prepared under identical

conditions), leading to similar behavior. The reported Faradaic efficiencies, TON, TOF, and

µmol of CO produced are average values.

Physical Methods

X-Ray Photoelectron Spectroscopy

XPS data were collected using a Kratos AXIS Ultra instrument. The monochromatic X-

ray source was the Al K α line at 1486.6 eV. Low-resolution survey spectra were acquired

between binding energies of 1–1200 eV. Higher-resolution detailed scans, with a resolution of

~0.1 eV, were collected on individual XPS lines of interest. The sample chamber was maintained

at < 2 × 10–9 Torr. The XPS data were analyzed using the CasaXPS software.

FT-IR

FT-IR spectra were acquired using a Bruker Vertex 80v spectrometer. Reflectance

spectra were collected using a VeeMAX III specular reflectance accessory from Pike

Instruments. Samples were positioned face-down over an aperture (3/8” diameter). All IRRAS

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measurements were collected with a 56° angle of incidence under vacuum pressure with 1 cm-1

resolution. Polarization studies were performed with a ZnSe polarizing lens purchased from Pike

Instruments. The spectra measured for unmodified substrates under identical experimental

parameters (angle, polarization, and resolution) were subtracted as background. Studies were

performed at 1 cm-1 resolution with 128 scans. ATR-FTIR measurements for complex 2 were

performed using a Bruker Optics Alpha FTIR spectrometer in the ATR mode.

UV-Vis

UV-Vis spectra were collected using a UV-1800 Shimadzu UV spectrophotometer. FTO

samples were studied in transmittance mode and the spectrum measured for an unmodified FTO

substrate was subtracted as background.

SEM

Scanning electron microscopy (SEM) was performed on a JEOL JSM 7001F scanning

electron microscope using an accelerating voltage of 15 kV.

AFM

Atomic force microscopy (AFM) topography images were collected in tapping mode

using an Agilent 5420 SPM instrument S3. The probe tips were Tap300-G Silicon AFM probes

(resonant frequency 300 kHz, force constant 40 N/m) purchased from Budgetsensors.com and

aligned prior to use. Images were collected with a scan rate of 0.25 lines per second and over an

area of 20 µm2. All samples were imaged under one atmosphere of air at room temperature. For

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each sample, three measurements were conducted and averaged to determine the root-mean-

square surface roughness.

ICP-OES

Inductively coupled plasma optical emission spectroscopy (ICP-OES) measurements

were performed using a Thermo Scientific iCAP 7000 ICP-OES.

Photocatalytic Studies

Mesoporous TiO2 (m-TiO2) electrodes were prepared by spin-coating a suspension of 20

mg TiO2 nanoparticles (anatase, ~20 nm) in 10 mL ethanol onto fluorine-doped tin oxide (FTO)

electrodes, which were then annealed at 450 °C for 30 minutes. All photocatalysis experiments

were conducted using a ThorLabs HPLS-30-03 solid state light source with a wavelength range

of 350 to 700 nm. For studies conducted with a filter, a 399 nm cutoff filter (purchased from

Schott Glass) was introduced. Using a gastight syringe, 2 mL of gas were withdrawn from the

headspace of the photocatalysis cell and injected into a gas chromatography instrument

(Shimadzu GC-2010-Plus) equipped with a BID detector and a Restek ShinCarbon ST

Micropacked column. TONs were determined by dividing the measured CO produced by the

catalyst loading determined by ICP-OES or CV analysis. All studies were conducted in 5:1

mixtures of DMF:TEOA (10 mL).

Computational Methods

All calculations were run using the Q-CHEM program package.7 Geometry optimizations

were run with unrestricted DFT calculations at the M06 level of theory with a composite basis

set.8 The Pople 6-31G* basis set was used for H, C, N, and O atoms and the Hay–Wadt VDZ

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(n+1) effective core potentials and basis sets (LANL2DZ) were used for Cl and Re atoms.9,10,11,12

All optimized geometries were verified as stable minima with frequency calculations at the same

level of theory. The M06 functional was used throughout this study, as it provides reduced

Hartree-Fock exchange contributions and includes empirical fitting for accuracy in

organometallic systems. Single point energy calculations were run with a larger 6-311G** basis

for H, C, N, and O atoms. Kohn-Sham orbital images are presented with isovalues of 0.05 for

clarity.

Figure S1. 1H NMR spectrum of 1 in acetonitrile-d3.

Figure S2. 1H NMR spectrum of 2 in acetonitrile-d3.

Figure S3. 19F NMR spectrum of 2 in acetonitrile-d3.

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Figure S4. ATR FTIR spectrum of complex 2.

Figure S5. Calculated vibrational spectrum of 2 at the LANL2DZ/M06 level of theory. Only stretching modes with

calculated intensity > 200 are included for clarity.

Figure S6. UV-Vis spectrum of 2 in an acetonitrile solution (0.5 mM 2).

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Figure S7. XPS survey scan for complex 2.

Figure S8. High-resolution XPS of the Re 4f region for complex 2.

Figure S9. High-resolution XPS of the Cl 2p region for complex 2.

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Figure S10. High-resolution XPS of the N 1s region for complex 2.

Figure S11. High-resolution XPS of the B 1s region for complex 2.

Figure S12. High-resolution XPS of the F 1s region for complex 2.

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Figure S13. Cyclic voltammetry of a glassy carbon electrode in 0.5 mM 2 in acetonitrile with 0.1 M TBAPF6

supporting electrolyte (ν = 100 mV/s).

Figure S14. Cyclic voltammetry of a FTO electrode in 0.5 mM 2 in acetonitrile with 0.1 M TBAPF6 supporting

electrolyte (ν = 100 mV/s).

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Figure S15. Cyclic voltammetry of a FTO electrode in 0.5 mM 2 in acetonitrile with 0.1 M TBAPF6 supporting

electrolyte (ν = 100 mV/s).

Figure S16. Estimated electroactive coverage as determined by cyclic voltammetry for FTO electrodes modified

with varying potential windows and scan rates. Initial potential (Pi), switching potential (Ps), and scan rate (ν) are

shown with the corresponding plots.

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Figure S17. XPS survey scan for FTO electrodes modified with a) n=1 b) n=5 c) n=10 and d) n=20.

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Figure S18. High resolution XPS of the Re 4f region for FTO electrodes modified with a) n=1 b) n=5 c) n=10 and

d) n=20.

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Figure S19. High resolution XPS of the Sn 2p region for FTO electrodes modified with a) n=1 b) n=5 c) n=10 and

d) n=20.

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Figure S20. High resolution XPS of the Cl 2p region for FTO electrodes modified with a) n=1 b) n=5 c) n=10 and

d) n=20.

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Figure S21. High resolution XPS of the P 2p region for FTO electrodes modified with a) n=1 b) n=5 c) n=10 and d)

n=20.

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Figure S22. High resolution XPS of the F 1s region for FTO electrodes modified with a) n=1 b) n=5 c) n=10 and d)

n=20.

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Figure S23. High resolution XPS of the C 1s region for FTO electrodes modified with a) n=1 b) n=5 c) n=10 and d)

n=20.

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Figure S24. SEM images of FTO films with varying thickness.

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Figure S25. SEM images of interfacial regions for FTO films.

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Figure S26. AFM data collected for FTO films with varying thickness.

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Figure S27. 3D projections of AFM data.

Table S1. RMS surface roughness of modified FTO electrodes.

n Sq (nm)

1 11.25±0.56

5 10.46±0.52

10 10.32±0.51

20 9.88±0.49

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Figure S28. PM-IRRAS of a modified FTO electrode (n = 20) with s- (red) and p- (black) polarization.

Figure S29. a) IRRAS of modified FTO electrodes with p polarization b) IRRAS peak height for the high-energy

carbonyl stretching mode as a function of the number of grafting scans applied.

Figure S30. UV-Vis spectra of FTO films with varying thickness.

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Figure S31. Cyclic voltammetry of a modified glassy carbon electrode (n = 5) in acetonitrile with 0.1 M TBAPF6

supporting electrolyte.



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Figure S35. Four sequential cyclic voltammetry scans of a modified FTO electrode (n=5) from -0.6 V to -2.4 V.

The third and fourth scans begin with an anodic sweep to +0.6 V and lead to the stabilization of the current density

at the reduction event. The purple trace represents the same electrode after 24 hours of air exposure. All scans in

acetonitrile with 0.1 M TBAPF6 (ν = 100 mV/s).

Figure S36. A) Modified glassy carbon stick electrodes (n = 1, 5, 10, and 20) prepared with varying catalyst

loadings. b) Unmodified glassy carbon electrode (n = 0) and modified glassy carbon electrodes (n = 5) immediately

after grafting with CV scans to Ps = -2.60 V (blue coloration) and an identically-modified electrode after 5 minutes

of air exposure (orange coloration). c) A modified Au electrode (n = 10) with a portion of the electrode not modified

for visual comparison (n = 0).

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Table S2. Catalyst loading for FTO electrodes as determined by cyclic voltammetry (CV) and ICP-OES.

CV Loading ICP Bulk Loading

n C nmol/cm2 ppm nmol/cm2

1 0.00009 3.4±0.3 0.018 5.0±0.5

5 0.00037 13.7±1.4 0.026 6.9±0.7

10 0.00036 18.7±2.0 0.036 9.8±1.0

20 0.00065 26.8±2.7 0.040 10.8±1.1

Figure S37. Double-layer charging current density (ΔJ = Janodic - Jcathodic) at the open-circuit potential for a modified

glassy carbon electrode (n = 1) as a function of scan rate.

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Figure S42. Catalyst loading for modified graphite rod electrodes (n = 1, 5, 10, and 20) as determined by cyclic

voltammetry (red) and ICP (blue).

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Table S3. Summary of controlled potential electrolysis studies for modified graphite rod electrodes. TON and TOF

are calculated based on cyclic voltammetry (CV) estimated loading and ICP estimates. All experiments performed in

acetonitrile with 0.1 M TBAPF6 supporting electrolyte for 2 hours at -2.25 V. Modified graphite rod electrodes

served as the working electrodes, with a Ag wire reference and graphite rod counter electrode.

n

CV

ICP

C

CO

(µmol)

FE

(%)

Loading

(nmol) TON TOF (s-1)

Loading

(nmol) TON TOF (s-1)

1 1.33±0.1 3.32±0.3 48±5 4.1±0.4 806±80 0.112±0.01 2.9±0.3 1149±110 0.319±0.3

5 3.64±0.4 18.82±1.9 99±7 11.7±1.2 1606±160 0.223±0.02 5.3±0.5 3583±360 0.498±0.5

10 5.99±0.6 27.20±2.7 88±8 18.0±1.8 1508±150 0.210±0.02 7.5±0.8 3606±360 0.501±0.5

20 4.17±0.4 13.81±1.4 64±6 34.7±3.5 398±40 0.055±0.006 22.2±0.2 623±60 0.086±0.09

Figure S43. Catalyst loading for modified TiO2 electrodes (n = 1, 5, 10, and 20) as determined by cyclic


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Table S4. Summary of photocatalytic studies for modified TiO2 electrodes. TON and TOF are calculated based on

cyclic voltammetry (CV) estimated loading and ICP estimates. All studies performed in 10 mL 5:1 DMF:TEOA

under illumination for 5 hours. *399 nm cut-on filter was introduced for this measurement.

n

CV

ICP

t (hr) CO (µmol)

Loading

(nmol)

TON

TOF

(hr-1)

Loading

(nmol)

TON

TOF (hr-

1)

1 5 0.41±0.04 4.0±0.4 103±10 20.6±2.1 5.8±0.6 70±7 14.0±1.4

5 5 0.31±0.03 7.9±0.8 39±4 7.8±0.8 10.9±1.1 28±3 5.6±0.6

5* 5 0.40±0.04 8.3±0.8 48±5 9.6±1.0 13.0±1.3 31±3 6.1±0.6

10 5 0.39±0.04 15.8±1.6 25±2 4.9±0.5 15.1±1.5 26±3 5.2±0.5

20 5 0.40±0.04 31.6±3.2 13±1 2.5±0.2 18.4±1.8 22±2 4.4±0.4

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Figure S44. High-resolution XPS of the Re 4f region for a modified FTO substrate (n = 20) before (blue) and after

(red) a 1 hour controlled potential electrolysis experiment at -2.25 V in acetonitrile solution with 0.1 M TBAPF6

supporting electrolyte under saturated CO2 atmosphere.

Figure S45. IRRAS studies of a modified FTO substrate (n = 20) before (black) and after (red) a 1 hour controlled

potential electrolysis experiment at -2.25 V in acetonitrile solution with 0.1 M TBAPF6 supporting electrolyte under

saturated CO2 atmosphere.

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Figure S46. UV-Vis studies of a modified FTO substrate (n = 20) before (blue) and after (red) a 1 hour controlled

potential electrolysis experiment at -2.25 V in acetonitrile solution with 0.1 M TBAPF6 supporting electrolyte under

saturated CO2 atmosphere.

Figure S47. Post-catalysis IRRAS results for a) a modified TiO2 device (n = 20) and b) a modified graphite rod

electrode (n = 20). After 5 hours of irradiation under photocatalytic conditions, the catalyst loading of the TiO2 film

has decreased by 66% as determined from the decrease in IRRAS intensity, while the loading on the graphite rod

electrode has decreased only by 5%.

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Figure S48. Electropolymerization scans in 0.5 mM 2 in acetonitrile with 0.1 M TBAPF6 supporting electrolyte (ν =

1 V/s, Pi = -0.6, Ps = -1.6) for a) glassy carbon, b) FTO, and c) graphite rod, d) TiO2, and e) gold working electrodes.

Only the first four grafting scans are shown for the gold electrode, as further scans exhibit sharp features indicating

scratching of the gold at the contact. Despite this behavior, continuous film growth is evident by visual coloration of

the films and growth of IRRAS signal.

Figure S49. XPS results for a bare FTO electrode. a) XPS survey scan b) High-resolution Re 4f region

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Figure S50. IRRAS characterization of modified TiO2 films with a) polarization-dependence studies of a modified

TiO2 film (n = 20) and b) IRRAS results from films of various catalyst loadings under s-polarization.

Figure S51. Catalyst loading for modified FTO electrodes (n = 1, 5, 10, and 20) as determined by cyclic


Figure S52. Controlled potential electrolysis results for modified (n = 1, 5, 10, and 20) and bare graphite rod

electrodes in acetonitrile (with 0.1 M TBAPF6 supporting electrolyte) at -2.25 V.

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Figure S53. IRRAS results for modified gold electrodes prepared with varying numbers of grafting scans. All

exhibit enhanced carbonyl stretching modes under s-polarization relative to p-polarization.

Figure S54. IRRAS results for a modified graphite rod electrode (n = 10) indicating the presence of carbonyl

stretching modes, absence of diazonium stretches, and polarization dependence.

Figure S55. Side-on SEM image acquired for a modified FTO electrode (n = 20). The FTO + film layer is estimated

at 420 nm thickness. Based on the reported thickness of FTO (250 nm) by the manufacturer (MTI Corp.), the film

thickness is estimated as ~170 nm.

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Figure S56. Cyclic voltammograms of a modified graphite rod electrode (n = 10) in acetonitrile solution with 0.1 M

TBAPF6 supporting electrolyte under CO2 atmosphere before (red) and after (green) a two hour controlled potential

electrolysis experiment. The bare electrode under CO2 atmosphere is shown in black.

Figure S57. Cyclic voltammograms of modified graphite rod electrodes (n = 1, 5, 10, and 20) in acetonitrile solution

with 0.1 M TBAPF6 supporting electrolyte a) under CO2 atmosphere and b) under CO2 atmosphere with the addition

of 0.5 M TFE.

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Surface-Immobilized Conjugated Polymers Incorporating