A temperature-controlled photoelectrochemical cell for quantitative product analysis

Corson, Elizabeth R.; Creel, Erin B.; Kim, Young-Sang; Urban, Jeffrey J.; Kostecki, Robert; McCloskey, Bryan D.

doi:10.1063/1.5024802

Cited by 16 publications

(33 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We can exclude the possibility that increased CO 2 reduction selectivity arises solely due to plasmonic heating of the electrocatalytic surface, as it has previously been shown that increased electrolyte temperatures promote H 2 evolution while reducing the selectivity for CO 2 reduction. 73 Such heating-induced trends in reaction selectivity are clearly opposite to those observed here. The linear relationship observed between incident light power and photocurrent ( Figure S5) further indicates that the improved photoelectrochemical selectivity is not associated with a thermal process.…”

Section: Introductioncontrasting

confidence: 73%

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes

et al. 2020

View full text Add to dashboard Cite

We report the light-induced modification of catalytic selectivity for photoelectrochemical CO 2 reduction in aqueous media using copper (Cu) nanoparticles dispersed onto p-type nickel oxide (p-NiO) photocathodes. Optical excitation of Cu nanoparticles generates hot electrons available for driving CO 2 reduction on the Cu surface while charge separation is accomplished by hot hole injection from the Cu nanoparticles into the underlying p-NiO support. Photoelectrochemical studies demonstrate that optical excitation of plasmonic Cu/p-NiO photocathodes imparts

show abstract

Section: Introductioncontrasting

confidence: 73%

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Liquid product concentrations were determined by using phenol and DMSO as internal standards. 22 Complete details on the GC and NMR calibration and quantification methods are reported in Corson et al 21 The cathode fabrication method was optimized to synthesize a Ag thin film that both enhanced the SEIRAS signal while remaining stable and intact during (photo)electrochemical experiments. Preparation of Ag films for ATR-SEIRAS using vacuum evaporation, chemical deposition, and Ar sputtering have previously been reported.…”

Section: Product Measurementsmentioning

confidence: 99%

In Situ ATR–SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode

Corson

Kaş

Kostecki³

et al. 2020

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

Illumination of a voltage-biased plasmonic Ag cathode during CO 2 reduction results in a suppression of the H 2 evolution reaction while enhancing CO 2 reduction. This effect has been shown to be photonic rather than thermal, but the exact plasmonic mechanism is unknown. Here, we conduct an in situ ATR-SEIRAS study of a sputtered thin film Ag cathode on a Ge ATR crystal in CO 2-saturated 0.1 M KHCO 3 over a range of potentials 1 in both dark and illuminated (365 nm, 125 mW cm −2) conditions to elucidate the nature of this plasmonic enhancement. We find that the onset potential of CO 2 reduction to adsorbed CO on the Ag surface is-0.25 V RHE and is identical in the light and the dark. As the production of gaseous CO is detected in the light near this onset potential but is not observed in the dark until-0.5 V RHE we conclude that the light must be assisting the desorption of CO from the surface. Furthermore, the HCO − 3 wavenumber and peak area increase immediately upon illumination, precluding a thermal effect. We propose that the enhanced local electric field that results from the LSPR is strengthening the HCO − 3 bond, further increasing the local pH. This would account for the decrease of H 2 formation and increase of CO 2 reduction products in the light. Experimental Methods Cathode Fabrication To prepare the cathode, a 60°Ge ATR crystal (Pike Technologies, 013-3132) was polished three times with subsequently smaller diameter alumina suspensions of 1.0 µm, 0.3 µm, and 0.05 µm (Buehler, 40-10081, 40-10082, and 40-10083) using microcloth pads (BASi, MF-1040). The crystal surface was cleaned with water and acetone using lint-free wipes and dried with compressed nitrogen. The crystal was placed in a Faraday cage and subjected to air plasma for 8 minutes on high power (Harrick Plasma, PDC-002-CE). A 40 nm film of Ag was deposited on the crystal surface in a custom-built sputtering tool with an argon (Ar) pressure of 50 µbar, deposition rate of 0.01455 nm s −1 , and substrate rotation of 15°s −1. After deposition, the resistance across the surface of the cathode was typically 4-8 Ω, as measured by a multimeter. A schematic of the cathode is shown in Figure S2.

show abstract

“…All (photo)electrochemical measurements were performed in the temperature-controlled photoelectrochemical cell described by Corson et al [29] CO 2 was mixed with argon (Ar) using two mass flow controllers (Alicat, MC-10SCCM-D) to achieve the desired P CO2 at a total flow rate of 5 sccm and total pressure of 1 atm (the cell was not designed for high pressure experiments). This mixture was continuously bubbled through a glass frit into the electrolyte.…”

Section: (Photo)electrochemical Measurementsmentioning

confidence: 99%

Effect of pressure and temperature on carbon dioxide reduction at a plasmonically active silver cathode

Corson

Creel

Kostecki

et al. 2021

Electrochimica Acta

Self Cite

View full text Add to dashboard Cite

Carbon dioxide reduction at a plasmonically active silver cathode was investigated by varying the pressure and temperature at multiple applied potentials under both dark and illuminated conditions to understand the mechanism of selectivity changes driven by plasmon-enhanced electrochemical conversion. Carbon dioxide partial pressures (P CO2 ) from 0.2 to 1 atm were studied during linear sweep voltammetry and chronoamperometry at -0.7, -0.9, and -1.1 V RHE . At a given applied overpotential the total current density increased with increasing P CO2 in both the dark and the light, but there were significant differences in the Tafel behavior between dark and illuminated conditions. The reduction of CO 2 to carbon monoxide (CO) was found to have first-order behavior with respect to P CO2 at all applied potentials in both the dark and the light, likely indicating no change in the rate-determining step upon illumination. Activity for the hydrogen (H 2 ) evolution reaction decreased with increasing P CO2 at slightly different rates in the dark and the light at each applied potential, making it unclear if light is influencing CO or H 2 intermediate adsorbate coverage. Both formate and methanol production showed no dependence on P CO2 under any conditions, but the true reaction orders may be masked by the much higher activity for CO and H 2 at the silver cathode. The investigation of product distribution with temperature at 14, 22, and 32°C at -0.7, -0.9, and -1.1 V RHE in both the dark and the light demonstrated that the selectivity changes observed upon illumination are not caused by local heating of the cathode surface.

show abstract

A temperature-controlled photoelectrochemical cell for quantitative product analysis

Cited by 16 publications

References 28 publications

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes

In Situ ATR–SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode

Effect of pressure and temperature on carbon dioxide reduction at a plasmonically active silver cathode

Contact Info

Product

Resources

About

A temperature-controlled photoelectrochemical cell for quantitative product analysis

Cited by 16 publications

References 28 publications

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO2 Reduction in Aqueous Electrolytes

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO2 Reduction in Aqueous Electrolytes

In Situ ATR–SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode

Effect of pressure and temperature on carbon dioxide reduction at a plasmonically active silver cathode

Contact Info

Product

Resources

About

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes