Selective and Efficient Reduction of Carbon Dioxide to Carbon Monoxide on Oxide‐Derived Nanostructured Silver Electrocatalysts

Abstract

In this work, the selective electrocatalytic reduction of carbon dioxide to carbon monoxide on oxide-derived silver electrocatalysts is presented. By a simple synthesis technique, the overall high faradaic efficiency for CO production on the oxide-derived Ag was shifted by more than 400 mV towards a lower overpotential compared to that of untreated Ag. Notably, the Ag resulting from Ag oxide is capable of electrochemically reducing CO2 to CO with approximately 80 % catalytic selectivity at a moderate overpotential of 0.49 V, which is much higher than that (ca. 4 %) of untreated Ag under identical conditions. Electrokinetic studies show that the improved catalytic activity is ascribed to the enhanced stabilization of COOH(.) intermediate. Furthermore, highly nanostructured Ag is likely able to create a high local pH near the catalyst surface, which may also facilitate the catalytic activity for the reduction of CO2 with suppressed H2 evolution.

Investigation of Electrocatalysts for Selective Reduction of CO2 to CO: Monitoring the Reaction Products by on line Mass Spectrometry and Gas Chromatography

“…However, it depends on several different experimental conditions such as applied potential, concentration of the reactants, electrolyte composition, temperature and electrocatalyst. 12 Metallic electrocatalysts have been commonly investigated in aqueous electrolyte such as gold, [13][14][15] copper, [16][17][18][19] tin, 20 silver 21,22 and nickel, 23 and they are classified according to their hydrogen evolution overpotentials and CO adsorption strength: 24 (i) metals such as Pb, Hg, In, Sn, Cd and Bi have high hydrogen overvoltages, negligible CO adsorption strength, high overpotentials for CO 2 to CO 2…”

Activation of Ni Particles into Single Ni–N Atoms for Efficient Electrochemical Reduction of CO2

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within acceptable limits are needed. [3] From these scenarios, robust catalysts that can selectively reduce CO 2 in lieu of protons at high turnover frequency (TOF) and faradaic efficiency (FE) for CO 2 reduction are desired.Since Hori's pioneering study on electroreduction of CO 2 in the 1980s, [4] Cu, [5] Au, [6] Ag, [7] Zn, [8] Sn, [9] and Bi [10] among others, have been widely investigated for electrocatalysis of CO 2 reduction, due to their promising capability to convert CO 2 into valuable chemicals and fuels while the HER is largely suppressed. [2] Unfortunately, the CO chemical bond in CO 2 (≈806 kJ mol −1 ) is thermodynamically very stable and its conversion is an uphill energy process with a high activation barrier.

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“…Since Hori's pioneering study on electroreduction of CO 2 in the 1980s, [4] Cu, [5] Au, [6] Ag, [7] Zn, [8] Sn, [9] and Bi [10] among others, have been widely investigated for electrocatalysis of CO 2 reduction, due to their promising capability to convert CO 2 into valuable chemicals and fuels while the HER is largely suppressed. Earth-abundant first-row transition metals such as Fe, Co, and Ni, however, are highly active for HER and also easily Electrochemical reduction of carbon dioxide (CO 2 ) to fuels and value-added industrial chemicals is a promising strategy for keeping a healthy balance between energy supply and net carbon emissions.…”

Tuning of Silver Catalyst Mesostructure Promotes Selective Carbon Dioxide Conversion into Fuels

“…[11] As aresult, the local pH environment at the electrode surface is expected to be significantly more alkaline than the bulk environment. Indeed, recent reports of highly efficient, selective CO-evolving catalysts feature high surface area metal films prepared by methods such as nanoparticle deposition, [12,13] de-alloying, [14] or reduction of an oxide [6,[15][16][17][18] or chloride precursor phase. Indeed, recent reports of highly efficient, selective CO-evolving catalysts feature high surface area metal films prepared by methods such as nanoparticle deposition, [12,13] de-alloying, [14] or reduction of an oxide [6,[15][16][17][18] or chloride precursor phase.…”

“…We have recently demonstrated this phenomenon for Au-catalyzed CO 2 reduction, [10] for which mesostructuring induces transport limitations that suppress the rate of H 2 evolution but leave the rate of CO production largely unchanged. [18] At antalizing alternative possibility,which is entirely unprecedented, is one in which transport limitations serve to promote the desired reaction while simultaneously suppressing the undesired reaction. [18] At antalizing alternative possibility,which is entirely unprecedented, is one in which transport limitations serve to promote the desired reaction while simultaneously suppressing the undesired reaction.…”