Mesostructure‐Specific Configuration of *CO Adsorption for Selective CO₂ Electroreduction to C₂₊ Products

Abstract

Abstract The multi‐carbon (C 2+ ) alcohols produced by electrochemical CO 2 reduction, such as ethanol and n ‐propanol, are considered as indispensable liquid energy carriers. In most C−C coupling cases, however, the concomitant gaseous C 2 H 4 product results in the low selectivity of C 2+ alcohols. Here, we report rational construction of mesostructured CuO electrocatalysts, specifically mesoporous CuO (m‐CuO) and cylindrical CuO (c‐CuO), enables selective distribution of C 2+ products. The m‐CuO and c‐CuO show similar selectivity towards total C 2+ products (≥76 %), but the corresponding predominant products are C 2+ alcohols (55 %) and C 2 H 4 (52 %), respectively. The ordered mesostructure not only induces the surface hydrophobicity, but selectively tailors the adsorption configuration of *CO intermediate: m‐CuO prefers bridged adsorption, whereas c‐CuO favors top adsorption as revealed by in situ spectroscopies. Computational calculations unravel that bridged *CO adsorbate is prone to deep protonation into *OCH 3 intermediate, thus accelerating the coupling of *CO and *OCH 3 intermediates to generate C 2+ alcohols; by contrast, top *CO adsorbate is apt to undergo conventional C−C coupling process to produce C 2 H 4 . This work illustrates selective C 2+ products distribution via mesostructure manipulation, and paves a new path into the design of efficient electrocatalysts with tunable adsorption configuration of key intermediates for targeted products.