2D Metal Oxyhalide‐Derived Catalysts for Efficient CO₂ Electroreduction

Abstract

Electrochemical reduction of CO is a compelling route to store renewable electricity in the form of carbon-based fuels. Efficient electrochemical reduction of CO requires catalysts that combine high activity, high selectivity, and low overpotential. Extensive surface reconstruction of metal catalysts under high productivity operating conditions (high current densities, reducing potentials, and variable pH) renders the realization of tailored catalysts that maximize the exposure of the most favorable facets, the number of active sites, and the oxidation state all the more challenging. Earth-abundant transition metals such as tin, bismuth, and lead have been proven stable and product-specific, but exhibit limited partial current densities. Here, a strategy that employs bismuth oxyhalides as a template from which 2D bismuth-based catalysts are derived is reported. The BiOBr-templated catalyst exhibits a preferential exposure of highly active Bi ( ) facets. Thereby, the CO reduction reaction selectivity is increased to over 90% Faradaic efficiency and simultaneously stable current densities of up to 200 mA cm are achieved-more than a twofold increase in the production of the energy-storage liquid formic acid compared to previous best Bi catalysts.

Promises of Main Group Metal–Based Nanostructured Materials for Electrochemical CO2 Reduction to Formate

“…In a follow‐up study, we observed that if Bi 2 O 2 CO 3 nanosheets were instead used, only mesoporous Bi nanosheets were yielded after the cathodic conversion due to the structural mismatch between Bi 2 O 2 CO 3 and Bi . Sargent and co‐workers started with BiOBr as the precatalyst and template, and obtained metallic Bi with a preferential exposure of highly active (1−10) planes after the electrochemical reduction . When assessed in the flow‐cell configuration, this electrocatalyst sustained large current density up to 200 mA cm −2 and >90% formate selectivity in 1 m KHCO 3 .…”

Bi‐Based Metal‐Organic Framework Derived Leafy Bismuth Nanosheets for Carbon Dioxide Electroreduction

“…However, the activity, stability, and selectivity to formic acid of Bi‐based materials are still unacceptable, especially in high faradaic efficiency (FE) (90%) over large current density (>200 mA cm −2 ). Recently, because of the poor hydrogen chemisorption energy and strong activation for CO 2 •− intermediates, by in situ reduction of Bi‐based materials, such as Bi, [ 9e,18 ] BiOX (Cl, Br, I), [ 19 ] Bi 2 O 2 CO 3 , [ 20 ] Bi 2 O 3 , [ 21 ] have revealed a high catalytic activity for the formic acid production. Further insight can be gained by considering that adopting those nonporous precursors could not only conceal active sites under in situ reduction but also accelerate the agglomeration.…”

Improved Photoelectric Performance of UV Photodetector Based on ZnO Nanoparticle‐Decorated BiOCl Nanosheet Arrays onto PDMS Substrate: The Heterojunction and Ti3C2Tx MXene Conduction Layer

“…Bismuth oxide halides, BiOX (X = Cl, Br, and I), consist of tetragonal [Bi 2 O 2 ] 2+ positive slabs interleaved by double negative slabs of halide atoms along the c axis. [ 1 ] They have been widely applied as photocatalysts, [ 2 ] electrocatalysts, [ 3 ] as well as electrode materials in energy storage [ 4 ] and photoelectrochemical devices, [ 5–7 ] owing to their layered structures and excellent optical, catalytic, and electrical properties. [ 8,9 ] The layered structure and the as‐induced dipole can cause the efficient separation of the electron–hole pair, which can achieve enhanced photocatalytic activity and photoconductivity.…”