Nature of the Active Sites of Copper Zinc Catalysts for Carbon Dioxide Electroreduction

Zhen, Shiyu; Zhang, Gong; Cheng, Dongfang; Gao, Hui; Li, Lulu; Lin, Xiaoyun; Ding, Zhijun; Zhao, Zhi‐Jian; Gong, Jinlong

doi:10.1002/anie.202201913

Cited by 49 publications

(25 citation statements)

References 45 publications

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“…(b) Construction of thermodynamically stable models for CuZn NPs and high-throughput screening of surface C–C coupling active sites. Reproduced with permission from ref . Copyright 2022 John Wiley and Sons.…”

Section: Design and Synthesis Of Copper-based Catalystsmentioning

confidence: 99%

“…Following this research framework, we also identified the active sites for C 2+ products on the surface of CuZn catalysts. Neural network-accelerated global optimization based on an algorithm of stochastic surface walking (NN-SSW) was utilized to search the global minima (GM) of CuZn nanoparticles (NPs, Figure b) . Using a high-throughput calculation method based on the NN potential, more than 2000 surface sites were evaluated, and 2 types of active sites were clarified, namely, the balanced Cu–Zn sites and Zn-heavy Cu–Zn sites.…”

Section: Design and Synthesis Of Copper-based Catalystsmentioning

confidence: 99%

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Electrochemical Approaches to CO₂ Conversion on Copper-Based Catalysts

Zhang

Zhao

et al. 2022

Acc. Mater. Res.

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Conspectus As one of the essential pathways to carbon neutrality or carbon negativity, the electrochemical reduction of CO2 offers tremendous prospects for platform chemicals and fuel production. Copper (Cu) is currently the only metal material that is able to reduce CO2 to multicarbon (C2+) products. Despite the fact that copper-based materials have been investigated for decades, we still confront numerous challenges on the path to the fundamental understanding and large-scale deployment of copper-based electrocatalysts for CO2 reduction. For fundamental investigations, it remains a variety of open questions about the CO2 reduction mechanisms. The convoluted C–C coupling pathways and product bifurcation processes confuse the design of efficient catalysts. The active sites of copper-based catalysts remain ambiguous due to surface reconstruction. As for theoretical calculations, the construction of electrolyte–electrode models and the investigation of solvation effects are premature for obtaining confident conclusions. In addition, simple and easily scalable techniques for catalyst synthesis still need to be continuously developed. For practical applications, the CO2 electrolyzer with copper-based materials must be operated with high current densities, high Faradaic efficiencies, high energetic efficiencies, high single-pass conversion rates (high product concentration), and long stability. Nevertheless, due to the intricate nature of electrochemical systems, a high-performance copper-based electrocatalyst alone is not sufficient to meet all of the above commercialization requirements. Therefore, reactor design involving mass transfer enhancement calls for more research input. Based on the above background and the urgency of the net-zero goal, we initiated our research on CO2 electrolysis using copper-based materials with an emphasis on active site identification and mass transfer enhancement. This Account describes our contribution to the field of C2+ products formation. We first discuss the synthesis of copper-based materials with a controlled atomic arrangement and valence states based on neural network-accelerated computational simulations. Using the synthesized catalyst, the selectivity of the target product is improved and the energy consumption of CO2 electrolysis is reduced. Then, we describe the efforts to investigate the reaction mechanisms, such as using first-principles calculations at the atomic level, in situ surface-enhanced vibrational spectroscopies at the micrometer level, and electrochemical kinetics studies at the apparent performance level. We also overview our efforts in the field of reaction system engineering, consisting of a vapor-fed CO2 three-compartment flow cell and a large-scale CO2 membrane electrode assembly, which can increase the reaction rates and single-pass yield. Furthermore, we put forward the main technical obstacles that currently need to be surmounted and provide insights into the commercial application of CO2 electrolysis technology.

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Section: Design and Synthesis Of Copper-based Catalystsmentioning

confidence: 99%

Section: Design and Synthesis Of Copper-based Catalystsmentioning

confidence: 99%

Electrochemical Approaches to CO₂ Conversion on Copper-Based Catalysts

Zhang

Zhao

et al. 2022

Acc. Mater. Res.

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“…The root-mean-square errors (RMSE) of CuZnCHO.pot and CuAgAu.pot potentials are 2.991 and 3.591 meV/atom, respectively. The comparison between NN potential predicted adsorption energy of *CO and *COOH (Figure S1) on Cu-based NPs and that from density functional theory (DFT) calculation has been reported in our recent publication, and the results indicate that the accuracy of NN potential can reach the level of DFT calculation such that this can be used for high-throughput active sites screening.…”

Section: Models and Methodsmentioning

confidence: 60%

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

et al. 2023

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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.

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“…Sargent et al [101] investigated 244 different intermetallic crystals containing copper from the Materials Project and enumerated 12,229 surfaces and 228,969 adsorption sites based on these crystals to train a machine learning model, and finally proved CuÀ Al as the most promising candidate for CO 2 RR (Figure 7a). In addition, Gong et al [102] obtained realistic active sites on CuZn catalysts at the atom level through a neural network based global optimization combined with density functional theory calculations. There are two kinds of typical active sites, which are balanced CuÀ Zn sites and Zn-heavy CuÀ Zn sites, respectively.…”

Section: Advanced Theoretical Methodsmentioning

confidence: 99%

Positive Valent Metal Sites in Electrochemical CO₂ Reduction Reaction

Lou

Zhao

et al. 2023

ChemPhysChem

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The discovery of high-performance catalysts for the electrochemical CO 2 reduction reaction (CO 2 RR) has faced an enormous challenge for years. The lack of cognition about the surface active structures or centers of catalysts in complex conditions limits the development of advanced catalysts for CO 2 RR. Recently, the positive valent metal sites (PVMS) are demonstrated as a kind of potential active sites, which can facilitate carbon dioxide (CO 2 ) activation and conversation but are always unstable under reduction potentials. Many advanced technologies in theory and experiment have been utilized to understand and develop excellent catalysts with PVMS for CO 2 RR. Here, we present an introduction of some typical catalysts with PVMS in CO 2 RR and give some understanding of the activity and stability for these related catalysts.

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Nature of the Active Sites of Copper Zinc Catalysts for Carbon Dioxide Electroreduction

Cited by 49 publications

References 45 publications

Electrochemical Approaches to CO₂ Conversion on Copper-Based Catalysts

Electrochemical Approaches to CO₂ Conversion on Copper-Based Catalysts

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

Positive Valent Metal Sites in Electrochemical CO₂ Reduction Reaction

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Nature of the Active Sites of Copper Zinc Catalysts for Carbon Dioxide Electroreduction

Cited by 49 publications

References 45 publications

Electrochemical Approaches to CO2 Conversion on Copper-Based Catalysts

Electrochemical Approaches to CO2 Conversion on Copper-Based Catalysts

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

Positive Valent Metal Sites in Electrochemical CO2 Reduction Reaction

Contact Info

Product

Resources

About

Electrochemical Approaches to CO₂ Conversion on Copper-Based Catalysts

Electrochemical Approaches to CO₂ Conversion on Copper-Based Catalysts

Positive Valent Metal Sites in Electrochemical CO₂ Reduction Reaction