Tang Wangzhong, Cao Heng, Ma Peiyu, Ding Tao, Huang SiShi, Wang Jiajun, Li Qunxiang, Xu Xiaoliang, Yang Jinlong
School of Chemistry and Materials Science & Hefei National Research Center for Physical Sciences at the Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, Anhui 230026, China.
Tianjin Key Laboratory of Structure and Performance for Functional Molecules; College of Chemistry, Tianjin Normal University, Tianjin 300387, China.
Nano Lett. 2024 May 1;24(17):5317-5323. doi: 10.1021/acs.nanolett.4c01064. Epub 2024 Apr 18.
Exploring high-efficiency photocatalysts for selective CO reduction is still challenging because of the limited charge separation and surface reactions. In this study, a noble-metal-free metallic VSe nanosheet was incorporated on g-CN to serve as an electron capture and transfer center, activating surface active sites for highly efficient and selective CO photoreduction. X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and femtosecond transient absorption spectroscopy (fs-TAS) unveiled that VSe could capture electrons, which are further transferred to the surface for activating active sites. diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations revealed a kinetically feasible process for the formation of a key intermediate and confirmed the favorable production of CO on the VSe/PCN (protonated CN) photocatalyst. As an outcome, the optimized VSe/PCN composite achieved 97% selectivity for solar-light-driven CO conversion to CO with a high rate of 16.3 μmol·g·h, without any sacrificial reagent or photosensitizer. This work offers new insights into the photocatalyst design toward highly efficient and selective CO conversion.
由于电荷分离和表面反应有限，探索用于选择性CO还原的高效光催化剂仍然具有挑战性。在本研究中，一种无贵金属的金属VSe纳米片被引入到g-CN上，作为电子捕获和转移中心，激活表面活性位点以实现高效和选择性的CO光还原。X射线光电子能谱（XPS）、软X射线吸收光谱（sXAS）和飞秒瞬态吸收光谱（fs-TAS）表明，VSe可以捕获电子，并将其进一步转移到表面以激活活性位点。漫反射红外傅里叶变换光谱（DRIFTS）和密度泛函理论（DFT）计算揭示了形成关键中间体的动力学可行过程，并证实了VSe/PCN（质子化CN）光催化剂上CO的良好生成。结果，优化后的VSe/PCN复合材料在无任何牺牲试剂或光敏剂的情况下，实现了97%的太阳光驱动CO转化为CO的选择性，转化率高达16.3 μmol·g·h。这项工作为高效和选择性CO转化的光催化剂设计提供了新的见解。
