Singh Munendra Pal, Xu Jiebing, Li Peng, Yang Xuan, Xia Zhonghao, Dong Ronghua, He Jiangang, Ju Qiang, Fang Zhenlan
State Key Laboratory of Flexible Electronics (LOFE) & Institute of Advanced Materials (IAM), School of Flexible Electronics (Future Technologies), Nanjing Tech University (Nanjing Tech), Nanjing 211816, China.
School of Mathematics and Physics, University of Science and Technology Beijing, Beijing 100083, China.
Inorg Chem. 2025 Jun 23;64(24):12313-12321. doi: 10.1021/acs.inorgchem.5c01754. Epub 2025 Jun 9.
Photoreduction of CO into high value-added products offers a promising approach to mitigating the global energy crisis. Coordination polymers (CPs) show promising potential in CO photoreduction due to their tunable structures. However, CP-based catalysts for CO photoreduction are limited by their poor recyclability and weak light absorption. Here, we have designed a new Zn-based CP {Zn-CP: [Zn(Bipn)Br]}, via the self-assembly of Zn ions and Bipn [,-bis(3-imidazol-1-ylpropyl)naphthalenediimide]. Zn-CP shows high reactivity toward CO photoreduction with HO, mainly due to the strong wide light absorption and high photoelectric conversion ability of the large conjugated naphthalenediimide rings of Bipn. Most importantly, the evolution rate of CHOH (4.00 μmol g h) is maintained after 10 photocatalytic cycles, while that of CO (45.28 μmol g h) is maintained after 7 photocatalytic cycles and then significantly increased by ∼1.33 times for the next three photocatalytic cycles, demonstrating excellent catalytic stability of Zn-CP. The excellent recyclability of Zn-CP is much better than that of the most reported CP-based photocatalysts. The catalytic mechanism of Zn-CP toward CO photoreduction has been proposed based on experimental data combining with the DFT-calculated results. This work offers a promising strategy for developing efficient and ultrastable CP-based photocatalysts for solar-driven CO reduction.
将CO光还原为高附加值产品为缓解全球能源危机提供了一种很有前景的方法。配位聚合物（CPs）由于其可调节的结构，在CO光还原方面显示出有前景的潜力。然而，用于CO光还原的基于CP的催化剂受到其较差的可回收性和较弱的光吸收的限制。在此，我们通过锌离子和Bipn [,-双（3-咪唑-1-基丙基）萘二酰亚胺]的自组装设计了一种新型的基于锌的CP {Zn-CP: [Zn(Bipn)Br]}。Zn-CP对用HO进行的CO光还原显示出高反应活性，这主要归因于Bipn的大共轭萘二酰亚胺环具有强的宽光吸收和高的光电转换能力。最重要的是，在10次光催化循环后，CHOH的析出速率（4.00 μmol g h）得以保持，而在7次光催化循环后，CO的析出速率（45.28 μmol g h）得以保持，并且在接下来的三次光催化循环中显著增加了约1.33倍，这表明Zn-CP具有优异的催化稳定性。Zn-CP优异的可回收性比大多数已报道的基于CP的光催化剂要好得多。基于实验数据并结合DFT计算结果，提出了Zn-CP对CO光还原的催化机理。这项工作为开发用于太阳能驱动的CO还原的高效且超稳定的基于CP的光催化剂提供了一种有前景的策略。
