High Selectivity Towards Formate Production by Electrochemical Reduction of Carbon Dioxide at Copper–Bismuth Dendrites

Abstract

The electrochemical reduction of CO2 provides an alternative carbon‐neutral path for renewable synthesis of fuels and value‐added chemicals. This work demonstrates that dendritic, bimetallic Cu–Bi electrocatalysts with nanometer‐sized grains are capable of formate generation with a high selectivity. Optimizing composition of electrocatalyst could achieve a faradic efficiency of 90 % at −0.8 to −0.9 VRHE, and a partial current of more than 2 mA cm−2. The combination of Cu with Bi enables modulation of the adsorption strength of intermediates. This leads to an increased selectivity and suppressed formation of spurious species, especially hydrogen and CO. Comparison of product distribution for Cu–In versus Cu–Bi indicated that Bi is essential to induce a favorable adsorption configuration of the intermediate species and to promote formate production.

Electrochemical recovery of tellurium from metallurgical industrial waste

“…4b), the Te and Bi deposits are porous in nature and tend to form dendritic-type structures, as previously is observed for both elements in electrodeposition studies [70,71]. Moreover, it is known that the application of an overpotential can lead to dendrite growth [72] and in this case, the dendritic growth is most likely due to the overpotential applied during the electrodeposition of the sacrificial elements (mostly Cu) as has been shown previously for copper [72][73][74][75][76]. After the deposition of the sacrificial elements, the redox replacement process is followed and the dendritic structure remains as tellurium replaces the sacrificial elements on the electrode surface wherever they have been deposited, i.e.…”

Recent Advances in the Catalyst Design and Mass Transport Control for the Electrochemical Reduction of Carbon Dioxide to Formate

“…Specifically, consistent with the Sabatier principle, a higher formate partial current density is achieved with a Sn catalyst with a moderate *HCOO binding affinity than with transition metals with much stronger or much weaker *HCOO binding affinities, including Ni, Cu, Pt, Ag, and Au [23]. The nature of the intermediate binding energy can be tailored by synthesizing a bimetallic or doped catalyst to change the electronic structure from that of the pristine catalyst [24][25][26]. Tuning the intermediate binding energy grants control over the selectivity and the overall reaction pathway as a result [27].…”

“…Controlling the composition of bimetallic compounds is an important strategy for tuning the electronic behavior of nanomaterials to enhance their selectivity and catalytic activity [24,62,63]. Bimetallic compounds can change the electronic structure of a catalyst, which affects the intermediate binding energy, which in turn controls the overall reaction pathway [27].…”

“…Bimetallic compounds can change the electronic structure of a catalyst, which affects the intermediate binding energy, which in turn controls the overall reaction pathway [27]. Many previously reported bimetallic compounds have shown enhanced catalytic activity compared to the corresponding pristine-metal-based catalysts, such as Ag-Sn [63], Cu-Bi [24,64], In-Sn [41], Sn-Cu [65,66], Pd-Ni [67], and Bi-Sn [47].…”

Surface Modification of Tin Dioxide via (Bi, S) Co‐Doping for Photoelectrocatalytic Reduction of CO2 to Formate

“…The emission of carbon dioxide (CO 2 ) from the consumption of fossil fuels has resulted in detrimental environmental changes, such as global warming, desertification, so mitigating the effects caused by the excessive emission of CO 2 has become an urgent issue to the current society. currently converting CO 2 into useful fuels or chemicals such as hydrocarbons, methanol and formate via diverse methods including biochemical, electrochemical, photochemical and thermochemical reaction have attracted attention for alleviating the environmental problems but also obtaining value chemical sources. Electrochemical CO 2 reduction (ECR) is a desirable route with unique advantages, which includes operating under ambient temperature and pressure, moderate efficiency and controllable selectivity .…”