Galvanic‐Cell Deposition Enables the Exposure of Bismuth Grain Boundary for Efficient Electroreduction of Carbon Dioxide

Abstract

Metallic bismuth (Bi) holds great promise in efficient conversion of carbon dioxide (CO2) into formate, yet the complicated synthetic routes and unobtrusive performance hinder the practical application. Herein, a facile galvanic‐cell deposition method is proposed for the rapid and one‐step synthesis of Bi nanodendrites. Compared to the traditional deposition method, it is found that the special galvanic‐cell configuration can promote the exposure of low‐angle grain boundaries. X‐ray absorption spectroscopy, in situ characterizations and theoretical calculations indicate the electronical structures can be greatly tailored by the grain boundaries, which can facilitate the CO2 adsorption and intermediate formation. Consequently, the grain boundary‐enriched Bi nanodendrites exhibit a high selectivity toward formate with an impressively high production rate of 557.2 µmol h‐1 cm‐2 at −0.94 V versus reversible hydrogen electrode, which outperforms most of the state‐of‐the‐art Bi‐based electrocatalysts with longer synthesis time. This work provides a straightforward method for rapidly fabricating active Bi electrocatalysts, and explicitly reveals the critical effect of grain boundary in Bi nanostructures on CO2 reduction.

Clean Synthesis of Bismuth Porous Nanosheets for Efficient CO2 Electroreduction

“…(b) FEs in the potential range from −0.8 to −1.8 V vs RHE. (c) Potential windows with FE HCOO– over 80% of the Bi NPSs and other Bi based catalysts reported in literature. ,,− (d) Long-term stability test of Bi PNSs at −1.0 V vs RHE for 10 h.…”

Photoelectrochemical and electrochemical CO2reduction to formate on post-transition metal block-based catalysts

“…11, the current density is concentrated in the range from −400 mA cm −2 to −50 mA cm −2 with a faradaic efficiency of formate of above 90%. 87–108 Five catalysts exhibited above FE formate of 90% at more negative current density than −400 mA cm −2 . Among them, the current density of Bi NBs and Bi 2 S 3 -derived catalysts can reach ampere class.…”

Breaking K+ Concentration Limit on Cu Nanoneedles for Acidic Electrocatalytic CO2 Reduction to Multi‐Carbon Products

“…Electrocatalytic CO 2 reduction to valuable fuels and chemicals enables CO 2 resource utilization through renewable clean electricity [1–6] . Among the CO 2 reduction products, multi‐carbon products have drawn worldwide attentions due to their high energy density and market value [7–12] . Currently, most of the reported examples for the CO 2 reduction reaction (CO 2 RR) to multi‐carbon products (C 2+ ) are performed in alkaline or neutral electrolyte systems, [13–19] expecting to improve the selectivity of C 2+ products by inhibition of the HER [20–25] .…”