Zhao Yuanyuan, Gao Kangjie, Li Jiaxin, Liu Huanhuan, Chen Fang, Wang Wentao, Zhong Yijun, Hu Yong
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, Jinhua, 321004, China.
Institute of Nanocatalysis and Energy Conversion, College of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou, 311300, China.
Nanoscale Horiz. 2025 Aug 21;10(9):2045-2054. doi: 10.1039/d5nh00355e.
Selective photocatalytic CO reduction (PCR) to CH remains challenging due to the sluggish charge transfer kinetics and the involved complicated C intermediates. Herein, deliberate engineering of Lewis acid-base interfaces in CuS/ZnInS hollow hetero-nanocages (HHNCs) was carried out, and enhanced PCR activity and selectivity were achieved due to accelerated electron transfer and stabilized intermediates. Both experimental and theoretical results have demonstrated the construction of a Lewis base interface with CuS and a Lewis acid interface with ZnInS, which exhibited strong CO adsorption and reduction of the Gibbs free energy in the hydrogenation step (*CO to *CHO). As a consequence, a CH yield of 23.3 μmol g h under visible light irradiation ( > 400 nm) was obtained with the CuS/ZnInS HHNCs, approximately 13.7, 10.1 and 6.3 times higher than those of bare CuS, ZnInS and a physically mixed sample (CuS/ZnInS-mix), respectively. The product selectivity of CH was as high as 93.2%, in sharp contrast with 59.5% for the CuS/ZnInS-mix, 53.1% for CuS and 35.4% for ZnInS. This work demonstrates a rational strategy to engineer heterogenous Lewis acid-base interfaces for improving PCR activity and selectivity.
由于电荷转移动力学缓慢以及涉及复杂的碳中间体，将选择性光催化CO还原（PCR）为CH仍然具有挑战性。在此，我们对CuS/ZnInS空心异质纳米笼（HHNCs）中的路易斯酸碱界面进行了精心设计，由于加速了电子转移并稳定了中间体，从而实现了增强的PCR活性和选择性。实验和理论结果均表明构建了与CuS的路易斯碱界面和与ZnInS的路易斯酸界面，它们在氢化步骤（CO到CHO）中表现出强烈的CO吸附并降低了吉布斯自由能。结果，在可见光照射（>400 nm）下，CuS/ZnInS HHNCs的CH产率达到23.3 μmol g⁻¹ h⁻¹，分别比裸CuS、ZnInS和物理混合样品（CuS/ZnInS-mix）高约13.7、10.1和6.3倍。CH的产物选择性高达93.2%，与CuS/ZnInS-mix的59.5%、CuS的53.1%和ZnInS的35.4%形成鲜明对比。这项工作展示了一种合理的策略，用于设计异质路易斯酸碱界面以提高PCR活性和选择性。
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