Lyu Wenyuan, Liu Yang, Chen Datong, Wang Fengliang, Li Yingwei
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.
Guangdong Provincial Key Laboratory of Petrochemical Pollution Process and Control, School of Environmental Science and Engineering, Guangdong University of Petrochemical Technology, Maoming, Guangdong, 525000, China.
Nat Commun. 2024 Dec 4;15(1):10589. doi: 10.1038/s41467-024-54988-3.
Photocatalytic conversion of CO into syngas is highly appealing, yet still suffers from the undesirable product yield due to the sluggish carrier transfer and the uncontrollable affinity between catalytic sites and intermediates. Here we report the fabrication of Co sites with tunable electron localization capability on two dimensional (2D) nanosheets assembled three dimensional (3D) ordered macroporous framework (3DOM-NS). The as-prepared Co-based 3DOM-NS catalysts exhibit attractive photocatalytic performances toward CO reduction, among which the cobalt sulfide one (3DOM Co-SNS) shows the highest syngas generation rate up to 347.3 μmol h under the irradiation of visible light and delivers a remarkable catalytic activity (1150.7 μmol h) in a flow reaction system under natural sunlight. Mechanism studies reveal that the high electron localization of metal sites in 3DOM Co-SNS strengthens the interaction between Co and HCOO* via the orbital interactions of d/d-p and s-s, thus facilitating the cleaving process of C-O bond. Additionally, the ordered macroporous framework with nanosheet subunits elevates the transfer efficiency of photoexcited electrons, which contributes to its high activity.
将CO光催化转化为合成气极具吸引力，但由于载流子转移缓慢以及催化位点与中间体之间的亲和力难以控制，其产物收率仍不理想。在此，我们报道了在二维（2D）纳米片组装的三维（3D）有序大孔框架（3DOM-NS）上制备具有可调电子定位能力的Co位点。所制备的Co基3DOM-NS催化剂对CO还原表现出有吸引力的光催化性能，其中硫化钴催化剂（3DOM Co-SNS）在可见光照射下显示出高达347.3 μmol h的最高合成气生成速率，并且在自然阳光下的流动反应体系中具有显著的催化活性（1150.7 μmol h）。机理研究表明，3DOM Co-SNS中金属位点的高电子定位通过d/d-p和s-s的轨道相互作用增强了Co与HCOO*之间的相互作用，从而促进了C-O键的裂解过程。此外，具有纳米片亚基的有序大孔框架提高了光激发电子的转移效率，这有助于其高活性。
