文献类型：期刊文献

英文题名：Atomically Dispersed Praseodymium-Modified Ni Active Sites Boost the Direct Cleavage of Carbonate Intermediates for Photothermal CO2 Conversion

作者：Rao, Zhiqiang[1,2];Huang, Zeai[1,2];Chen, Guoxing[3];Zhang, Liangzhu[4];Wang, Kaiwen[5];Cao, Yuehan[2];Chen, Yaolin[2];Yang, Yuantao[2];Feng, Qianyue[2];Weidenkaff, Anke[3,6];Zhou, Ying[1,2]

机构：[1]Southwest Petr Univ, State Key Lab Oil & Gas Reservoir Geol & Exploitat, Chengdu 610500, Peoples R China;[2]Southwest Petr Univ, Sch New Energy & Mat, Chengdu 610500, Peoples R China;[3]Tech Univ Darmstadt, Dept Mat & Earth Sci, Alarich Weiss Str 2, D-64287 Darmstadt, Germany;[4]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China;[5]Beijing Univ Technol, Beijing Key Lab Microstruct & Properties Adv Mat, Beijing 100124, Peoples R China;[6]Fraunhofer Res Inst Mat Recycling & Resource Strat, Brentanostr 2a, D-63755 Alzenau, Germany

年份：2025

卷号：19

期号：28

起止页码：25904

外文期刊名：ACS NANO

收录：;EI(收录号：20252818773125);WOS:【SCI-EXPANDED(收录号:WOS:001528212500001)】；

基金：This research was financially supported by the National Science Fund for Distinguished Young Scholars (52325401), the National Natural Science Foundation of China (22209136, W2412080), and Sichuan Provincial Key Research (23ZDYF0179). We thank the Vacuum Interconnected Nanotech Workstation of the Suzhou Institute of Nanotech and Nanobionics, Chinese Academy of Sciences. We also thank the staff at the SuperXAS X10DA beamline of the Paul Scherrer Institute for their assistance with the XAFS.

语种：英文

外文关键词：CO2 conversion; photothermal catalysis; Ni/CeO2; single-atom catalysts; operando SSITKA-DRIFTS

摘要：Photothermal catalytic reduction of carbon dioxide (CO2) into valuable chemical feedstocks represents a sustainable approach for storing intermittent renewable energy and reducing CO2 emissions. However, this process is still impeded by the inherent inertness of CO2 and the production of multiple intermediates. Herein, we propose a strategy that facilitates the direct cleavage of carbonate intermediates to boost photothermal catalytic CO2 conversion. A highly efficient catalyst featuring active sites designed to improve the carbonate coverage was successfully constructed, composed of atomically dispersed praseodymium-modified ceria loaded with highly dispersed nickel species (Ni/Pr-CeO2). The fine structure of the prepared catalysts was revealed by high-resolution, high-angle annular dark-field scanning transmission electron microscopy, and X-ray absorption fine structure. Multiple in situ/operando spectroscopy techniques confirmed the active participation of interface oxygen species from Ni/Pr-CeO2 in enhancing carbonate (CO3*) and bicarbonate (HCO3*) intermediates coverage and transformation. In particular, under light irradiation, the C & boxH;O bonds within these intermediates are effectively weakened and cleaved, overcoming the high energy barrier associated with CO2 activation and enabling efficient CO production. As a result, the Ni/Pr-CeO2 catalyst demonstrates a high CO yield of 27.2 mol mol(Ni)(-1) min(-1), which is nearly three times higher than that of the Ni/CeO2 catalyst and maintains exceptional stability over 110 h without deactivation. Our findings contribute to the development of efficient catalytic systems that not only recycle greenhouse gases but also facilitate the integration of intermittent renewable energy sources into the chemical production landscape.