News Source: School of Materials Science

and Engineering, Chen Wenxing

Editor: Mou Xuejiao Translation:Long Xiaofei

On March 11, Nature communications published a research article online entitled "Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu₂-CuN₃clusters for CO₂reduction to ethanol". Electrochemical conversion of carbon dioxide into value-added products using sustainable energies is environmentally friendly and economical approach. However, complex product selectivity limits the development and application of CO₂reduction. Copper-based materials are effective catalysts for the reduction of CO₂to multi-carbon products. Revealing the local structure and the electronic state of active sites is of great significance for studying the reaction pathway and catalytic mechanism of CO₂to C₂₊products. With few studies on in-situ monitoring of reaction systems in multiple dimensions, the influence mechanism of the atomic structure-activity relationship of electrocatalysts on activity and selectivity is still unclear. In this paper, a high-performance CO₂RR catalyst composed of CuO clusters supported on N-doped carbon nanosheets was synthesized, which exhibited Faradaic efficiency of 51% for ethanol at -1.1V vs. RHE. The authors evidenced catalyst restructuring and tracked the variation of the active states under reaction condition, which experimentally and theoretically explained the atomic structure-activity relationship at the catalytic interface. Operando XAS, XANES simulations, and Quasi-in-situ XPS analysis identified a reversible potential-dependent transition from dispersed CuO clusters to metastable charge-asymmetric Cu₂-CuN₃clusters which are the optimal sites. By adjusting the charge distribution between the Cu atoms and N-doped carbon interface, the excellent stability and high activity of Cun clusters can be maintained. By combining Operando FTIR and DFT calculations, it was recognized that the Cu₂-CuN₃clusters displayed charge-asymmetric sites, which were intensified by CH₃* adsorbing, beneficial to the formation of the high-efficiency asymmetric ethanol.

The corresponding authors of this article are Assistant Professor Chen Wenxing from Beijing Institute of Technology and Researcher Wang Yu from Shanghai Advanced Research Institutes, Chinese Academy of Sciences. This research has been supported by Youth Project of National Natural Science Foundation of China, Beijing Institute of Technology Talent Introduction Project, Youth Innovation Promotion Association of Chinese Academy of Sciences, Shanghai Synchrotron Radiation Facility Operation Research Project, Large-scale Scientific Equipment Maintenance and Reconstruction Project of Chinese Academy of Sciences , National Major Scientific Research Instrument Development Project, Excellent User Program of Hefei Science Center of Chinese Academy of Sciences etc.

Figure 1 The Operando XAFS characterization of the catalyst and the reversible formation scheme of catalytically active Cu_n-CuN₃cluster based on Operando XAS and Quasi-in situ XPS analysis. (rufous, O; gray, C; purple, N; blue, Cu bond to both N and Cu; green, Cu just bond to Cu)

Paper Information: Su, X., Jiang, Z., Zhou, J. et al. Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol. Nat Commun 13, 1322 (2022).

Paper link:https://www.nature.com/articles/s41467-022-29035-8