Accessing the Nature of Active Sites and Particle Size Effect for Reduction of Carbon Dioxide over Copper-Based Catalysts

Abstract

Although electrocatalytic conversion of CO 2 (CO 2 ER) over bimetallic Cu-based catalysts has been regarded as a promising and compelling route for the sustainable synthesis of fuels and feedstock when combined by carbon-free electricity, questions still remain concerning the fundamental understanding of the reaction mechanism and the nature of active sites, hampering the rational design of catalyst with great activity and selectivity a priori. We report a global optimization in large scale to obtain serious realistic nanoparticles (NPs) models of different particle sizes and the identification of atom-level structures of active sites for CO products on CuZn and CuAu NPs catalysts during CO 2 ER, using machine learning and density functional theory calculations. After the analysis of 300 surface sites (600 computational data points) through neural network (NN) potential based high-throughput testing, we demonstrate that the bimetallic Cu-based NPs have superior CO 2 ER because there are many bimetallic synergistic effect sites that significantly stabilize the carboxyl intermediate during CO 2 reduction to CO, breaking the inherent linear relationship. This work shed light on the structure− performance relationship over more realistic large NPs, facilitating the rational design of Cu-based catalysts in CO 2 ER.

Recent Progress on Copper‐Based Bimetallic Heterojunction Catalysts for CO2 Electrocatalysis: Unlocking the Mystery of Product Selectivity

“…Zn element at the Cu/Zn heterojunction also results in uncertain selectivity for such catalysts. [175][176][177] Cu-Zn heterojunctions are known to catalyze the reduction of CO 2 with high selectivity to CO, and dendritic Cu-Zn catalysts have achieved a Faraday efficiency of 83%. [178] In some cases, Cu components with a rich interface structure exhibit higher eCO 2 RR activity, resulting in improved selectivity of the catalysts for CO. Wan et al [179] explored the relationship between the interface structure of the catalyst and the two-phase interaction of the metal.…”

“…In addition, the diffusion of the Zn element at the Cu/Zn heterojunction also results in uncertain selectivity for such catalysts. [ 175 , 176 , 177 ]…”

Early-Career and Emerging Researchers in Physical Chemistry Volume 2

“…Heterogeneous catalysis occurs commonly on nanoparticles, but atomic-level information about the active site is difficult to obtain using traditional techniques. Zhao and co-workers, by using large-scale machine learning global optimization, revealed the likely CO 2 hydrogenation catalytic active site on CuZn and CuZn nanoparticles. They established a quantitive model to correlate the particle size with the concentration of surface step sites, the active sites to produce CO. To understand the role of hydrogen–solid interaction in energy and catalysis, adsorption, and diffusion phenomena, Zhou and co-workers studied the interaction of deuterium atoms with rutile TiO 2 (011) by temperature-programmed desorption (TPD) and ultraviolet photoelectron spectroscopy (UPS).…”

NxC-Induced Switching of Methane and Ethylene Products’ Selectivity from CO2 Electroreduction over Cu Catalyst

“…A lot of effort has been devoted to suppress HER and improve the Faradaic efficiency (FE) of the required products on Cu-based materials. And some strategies were proposed, such as controlling the size and morphology, − regulating oxidation state, − controlling crystal facets, − , and constructing a surface environment. − These strategies are believed to improve the adsorption of the CO intermediate, which is a key intermediate for deeper reduction to enhance the hydrocarbon and oxygenate products generation on the Cu surface. For example, Wang et al introduced Au in Cu to promote CO intermediate protonation by suppressing C–C coupling and weakening the adsorbed H, leading to FE of (56 ± 2)% CH 4 at a production rate of (112 ± 4) mA/cm –2 .…”