Sequential catalysis controls selectivity in electrochemical CO₂ reduction on Cu

Abstract

A sequential pathway with CO as an intermediate species allows for control of oxygenate selectivity in electrochemical reduction of CO2.

Rational Design of Ag‐Based Catalysts for the Electrochemical CO2 Reduction to CO: A Review

“…It was also reported that structure, morphology, size, and composition of the catalyst can lead to adsorption and decoupling site preferences of different adsorbates of C bound on the surface and further result in the breaking of the linear scaling relationships and tuning of the adsorption strength, eventually exerting a dramatic influence on the ECR performance . Indeed, in addition to polycrystalline and single‐crystalline Ag, some new A types have been developed and characterized recently, such as nanostructured Ag with different sizes, supported Ag catalysts with different substrates including C, TiO 2 , Al 2 O 3 , dopant‐aided Ag, oxide‐derived Ag, and surface‐modified Ag …”

“…Interestingly, although CO is the predominant reaction product for Ag–Cu in the selective ECR, which is derived mainly from synergistic reactions rather than pure dilution effects between Ag and Cu, it should be noted that Cu and Cu‐based catalysts including Ag–Cu also have the potential to convert CO 2 to various hydrocarbons such as C 2 H 6 , CH 4 , or/and oxygenates such as C 2 H 5 OH, CH 3 OH, HCHO . Further studies demonstrated that the selectivity and activity of these bimetallic Ag–Cu electrocatalysts for the ECR to CO were closely related to the atomic distributions and ratios of Ag and Cu …”

Unveiling Electrochemical Reaction Pathways of CO2 Reduction to CN Species at S‐Vacancies of MoS2

“…This can be qualitatively understood by the difference in reaction free energies of competing reactions between HER and CO 2 R. For comparison with the CO 2 R pathway, we present the HER pathway in Figure . It is clear that the HER pathway is expected to be favored over that for the CO 2 R because Δ G (*H)−Δ G (*OCHO) is −0.66 eV at −0.4 V. However, the pathway to 1‐propanol can compete with HER if the reaction starts with formaldehyde rather than CO 2 , resulting in Δ G (*H)−Δ G (*OCH 2 CH 2 OH)=−0.01 eV at −0.4 V. Therefore, cascade catalysts combining V S ‐MoS 2 and other catalysts, which can produce formaldehyde efficiently as a CO 2 R product, such as polyhydride ruthenium complexes, boron‐doped diamond, and Cu, may offer improved selectivity for 1‐propanol production.…”

Electrochemistry at Deep‐Sea Hydrothermal Vents: Utilization of the Thermodynamic Driving Force towards the Autotrophic Origin of Life

“…[106] Therefore, as long as this ratio is different between two competing pathways, the pH will serve to regulate the reaction selectivity. Going further, this may possibly even lead to a multi-step chemical conversion system, either as cascade catalysis, [107][108][109] or as several chemical reactors connected in series. This variability could allow specific reactions to proceed and concentrate in a certain niche environment.…”

“…This variability could allow specific reactions to proceed and concentrate in a certain niche environment. Going further, this may possibly even lead to a multi-step chemical conversion system, either as cascade catalysis, [107][108][109] or as several chemical reactors connected in series. This is a critical difference from previous origin of life theories such as the soup model and pond model, where no pH or potential gradients were available to guide the selectivity of prebiotic reactions.…”