Electro‐induced Crystallization Over Amorphous Indium Hydroxide Gels Toward Ampere‐Level Current Density Formate Electrosynthesis

Electrochemical CO2 reduction reaction (CO2RR) provides a promising way for producing value‐added fuels and chemicals via renewable electricity. However, the dynamic reconstruction of electrocatalysts of atomic active sites hinders in‐depth understanding of catalytic mechanism and further industrial application, especially under ampere‐level current density conditions. In this work, electro‐induced crystallization is reported over an amorphous Indium hydroxide gel (In gel) catalyst, which generates active sites for efficient and selective CO2RR. Molecular dynamic calculation reveals the crystallization process can maintain amorphous In‐OH species on the surface while generating crystallized metallic In under electroreduction condition; structural characterizations prove that the derived partially crystallized In gel is stable consisting of amorphous/crystalline interface, even biased at a high polarization potential of −4 V versus reversible hydrogen electrode. The resultant partially crystalized In gel exhibits a highly selective CO2RR performance toward formate under an ampere‐level current density up to 1200 mA cm−2 simultaneously with 91.89% Faradaic efficiency, which can motivate a high formate generation rate of 20.55 mmol h−1 cm−2. The operando Raman spectroscopic and density functional theoretic results demonstrate the optimized adsorption of *HCOO intermediate for the enhanced formate activity and selectivity over the partially crystallized In gel. A stable amorphous/crystalline structure of In(OH)3/In interface is reconstructed from an amorphous In‐based hydroxide gel through an electro‐induced crystallization process, which can deliver a high selectivity toward formate of over 90% under a current density of over 1.0 A cm−2 in a flow cell reactor.