Surface promotion of copper nanoparticles with alumina clusters derived from layered double hydroxide accelerates CO_(2)reduction to ethylene in membrane electrode assemblies

Electrochemical CO_(2)reduction has the vast potential to neutralize CO_(2)emission and valorizes this greenhouse gas into chemicals and fuels under mild conditions.Its commercial realization hinges on catalyst innovation as well as device engineering for enabling reactions at industrially relevant conditions.Copper has been widely examined for the selective production of multicarbon chemicals particularly ethylene,while there is still a substantial gap between the expected and the attainable.In this work,we report that the surface promotion of copper with alumina clusters is a viable strategy to enhance its electrocatalytic performance.AlOx-promoted Cu catalyst is derived from Cu-Al layered double hydroxide nanosheets after alkali etching and cathodic conversion.It can catalyze CO_(2)to ethylene and multicarbon products with great selectivity and stability far superior to pristine copper in both an H-cell and a zero-gap membrane electrode assembly(MEA)electrolyzer.The surface promotion effect is understood via computational simulations showing that alumina clusters can stabilize key reaction intermediates(*COOH and*OCCOH)along the reaction pathway.

Computational high-throughput screening of alloy nanoclusters for electrocatalytic hydrogen evolution

Here,we report a density functional theory(DFT)-based high-throughput screening method to successfully identify a type of alloy nanoclusters as the electrocatalyst for hydrogen evolution reaction(HER).Totally 7924 candidates of Cu-based alloy clusters of Cu55-nMn(M=Co,Ni,Ru,and Rh)are optimized and evaluated to screening for the promising catalysts.By comparing different structural patterns,Cu-based alloy clusters prefer the core–shell structures with the dopant metal in the core and Cu as the shell atoms.Generally speaking,the HER performance of the Cu-based nanoclusters can be significantly improved by doping transition metals,and the active sites are the bridge sites and three-fold sites on the outer-shell Cu atoms.Considering the structural stability and the electrochemical activity,core–shell CuNi alloy clusters are suggested to be the superior electrocatalyst for hydrogen evolution.A descriptor composing of surface charge is proposed to efficiently evaluate the HER activity of the alloy clusters supported by the DFT calculations and machine-learning techniques.Our screening strategy could accelerate the pace of discovery for promising HER electrocatalysts using metal alloy nanoclusters.