New Insights Into the Role of Imidazolium-Based Promoters for the Electroreduction of CO<sub>2</sub> on a Silver Electrode

Lau, Genevieve P. S.; Schreier, M. M.; Vasilyev, Dmitry; Scopelliti, Rosario; Grätzel, Michaël; Dyson, Paul J.

doi:10.1021/jacs.6b03366

Cited by 198 publications

(248 citation statements)

References 26 publications

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“…At the same time, the current-carrying ions are unlikely to be OH − or H + since in the case of a cation exchange membrane, the positively charged electrolyte cation, present in large excess, will flow from the anode to the cathode compartment, building up a cation concentration gradient since these ions are not electroactive. A similar phenomenon would occur for anion exchange membranes, where HCO 3 − ions are to be expected to carry the current. Furthermore, passive exchange of ions will occur across the membrane as long as their concentration is different in the two compartments.…”

Section: Bifunctional Catalysismentioning

confidence: 63%

“…A number of products have been successfully synthesized by this process, most notably carbon monoxide (CO) [1][2][3] , formic acid (HCOOH), methane (CH 4 ) 4 , ethylene (C 2 H 4 ) 5 and ethanol (CH 3 CH 2 OH) 6 , as well as other compounds 7,8 . Due to the numerous possible reaction pathways, selectively targeting one specific product at high yield has remained a challenge, which, to the present day, has been achieved only for CO and formic acid in aqueous electrolytes.…”

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confidence: 99%

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Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO

et al. 2017

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The solar-driven electrochemical reduction of CO 2 to fuels and chemicals provides a promising way for closing the anthropogenic carbon cycle. However, the lack of selective and Earth-abundant catalysts able to achieve the desired transformation reactions in an aqueous matrix presents a substantial impediment as of today. Here we introduce atomic layer deposition of SnO 2 on CuO nanowires as a means for changing the wide product distribution of CuO-derived CO 2 reduction electrocatalysts to yield predominantly CO. The activity of this catalyst towards oxygen evolution enables us to use it both as the cathode and anode for complete CO 2 electrolysis. In the resulting device, the electrodes are separated by a bipolar membrane, allowing each half-reaction to run in its optimal electrolyte environment. Using a GaInP/GaInAs/Ge photovoltaic we achieve the solar-driven splitting of CO 2 into CO and oxygen with a bifunctional, sustainable and all Earth-abundant system at an e ciency of 13.4%.T he electrochemical reduction of CO 2 to fuels and chemicals has the promise to provide a versatile way of storing renewable electrical energy in chemical bonds while simultaneously closing the anthropogenic carbon cycle. A number of products have been successfully synthesized by this process, most notably carbon monoxide (CO) 1-3 , formic acid (HCOOH), methane (CH 4 ) 4 , ethylene (C 2 H 4 ) 5 and ethanol (CH 3 CH 2 OH) 6 , as well as other compounds 7,8 . Due to the numerous possible reaction pathways, selectively targeting one specific product at high yield has remained a challenge, which, to the present day, has been achieved only for CO and formic acid in aqueous electrolytes. Unfortunately, selective electroreduction of CO 2 to these products relies on the use of precious metals (Au, Ag, Pd) [9][10][11][12] , requires operation at considerable overpotentials 13 , or requires the use of electrolyte additives, such as ionic liquids 14 . Developing inexpensive, selective and stable catalysts operating at low overpotentials is therefore a crucial requirement.Recently, substantial progress toward decreasing the overpotential of copper-based electrodes was made by employing catalysts derived from copper oxides 15 . However, the insufficient selectivity remained an issue, with the catalyst producing CO, H 2 and formic acid at comparable selectivities. Following up on this work, it was demonstrated that by electrochemically reducing copper oxide in the presence of indium ions, the selectivity toward producing CO could be substantially enhanced 16,17 . More recently, the same group demonstrated tin to have a similar effect 18 . Although adding sources of metal ions during the catalyst reduction process is effective in tuning the selectivity, it is difficult to control and may not guarantee uniform coating.Here, we demonstrate the surface modification of CuO nanowire electrodes with SnO 2 using atomic layer deposition (ALD), leading to a highly selective catalyst for the electrochemical reduction of CO 2 to CO. By using SnO 2 -modified...

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Section: Bifunctional Catalysismentioning

confidence: 63%

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confidence: 99%

Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO

et al. 2017

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“…Therefore, the intermediates of CO 2 reduction must be adsorbed on the Ag surface37. It has been reported that Ag surfaces could stabilize anion radicals at certain negative potential depending on the experimental conditions, electrolyte and pH (standard redox potential for is −1.9 V)12363742. BDD can produce the anion radical in 0.1 M Na 2 SO 4 and this radical can be stabilized as an intermediate product under suitable experimental conditions (high pressure)30.…”

Section: Discussionmentioning

confidence: 99%

Boron-doped diamond semiconductor electrodes: Efficient photoelectrochemical CO2 reduction through surface modification

Roy

Hirano

Kuriyama³

et al. 2016

Sci Rep

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Competitive hydrogen evolution and multiple proton-coupled electron transfer reactions limit photoelectrochemical CO2 reduction in aqueous electrolyte. Here, oxygen-terminated lightly boron-doped diamond (BDDL) thin films were synthesized as a semiconductor electron source to accelerate CO2 reduction. However, BDDL alone could not stabilize the intermediates of CO2 reduction, yielding a negligible amount of reduction products. Silver nanoparticles were then deposited on BDDL because of their selective electrochemical CO2 reduction ability. Excellent selectivity (estimated CO:H2 mass ratio of 318:1) and recyclability (stable for five cycles of 3 h each) for photoelectrochemical CO2 reduction were obtained for the optimum silver nanoparticle-modified BDDL electrode at −1.1 V vs. RHE under 222-nm irradiation. The high efficiency and stability of this catalyst are ascribed to the in situ photoactivation of the BDDL surface during the photoelectrochemical reaction. The present work reveals the potential of BDDL as a high-energy electron source for use with co-catalysts in photochemical conversion.

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“…An understanding of the interactions between the RTIL and the CO 2 ‐reducing catalyst can have a significant impact on the reduction product. Lau et al . examined the role of an imidazolium based RTIL on the reduction of CO 2 at a silver electrode.…”

Section: Introductionmentioning

confidence: 99%

Altering the Coordination of Iron Porphyrins by Ionic Liquid Nanodomains in Mixed Solvent Systems

Atifi

2017

Chemistry A European J

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The solvent environment around iron porphyrin complexes was examined using mixed molecular/RTIL (room temperature ionic liquid) solutions. The formation of nanodomains in these solutions provides different solvation environments for substrates that could have significant impact on their chemical reactivity. Iron porphyrins (Fe(P)), whose properties are sensitive to solvent and ligation changes, were used to probe the molecular/RTIL environment. The addition of RTILs to molecular solvents shifted the redox potentials to more positive values. When there was no ligation change upon reduction, the shift in the E° values were correlated to the Gutmann acceptor number, as was observed for other porphyrins with similar charge changes. As %RTIL approached 100 %, there was insufficient THF to maintain coordination and the E° values were much more dependent upon the %RTIL. In the case of Fe (P)(Cl), the shifts in the E° values were driven by the release of the chloride ion and its strong attraction to the ionic liquid environment. The spectroscopic properties and distribution of the Fe and Fe species into the RTIL nanodomains were monitored with visible spectroelectrochemistry, F NMR and EPR spectroscopy. This investigation shows that coordination and charge delocalization (metal versus ligand) in the metalloporphyrins redox products can be altered by the RTIL fraction in the solvent system, allowing an easy tuning of their chemical reactivity.

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New Insights Into the Role of Imidazolium-Based Promoters for the Electroreduction of CO₂ on a Silver Electrode

Cited by 198 publications

References 26 publications

Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO

Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO

Boron-doped diamond semiconductor electrodes: Efficient photoelectrochemical CO2 reduction through surface modification

Altering the Coordination of Iron Porphyrins by Ionic Liquid Nanodomains in Mixed Solvent Systems

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New Insights Into the Role of Imidazolium-Based Promoters for the Electroreduction of CO2 on a Silver Electrode

Cited by 198 publications

References 26 publications

Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO

Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO

Boron-doped diamond semiconductor electrodes: Efficient photoelectrochemical CO2 reduction through surface modification

Altering the Coordination of Iron Porphyrins by Ionic Liquid Nanodomains in Mixed Solvent Systems

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New Insights Into the Role of Imidazolium-Based Promoters for the Electroreduction of CO₂ on a Silver Electrode