Hou Yuxia, Ma Haizeng, Li Jinyu, Li Suhong, Wang Ji-Chao, Qu Ling-Bo, Lou Tianjun, Cui Cheng-Xing
Department of Chemistry and Chemical Engineering, Institute of Computational Chemistry, Henan Institute of Science and Technology, Xinxiang 453003, PR China.
College of Environmental Science and Engineering, Fujian Key Laboratory of Pollution Control & Resource Reuse, Fujian Normal University, Fuzhou 350117, PR China.
Langmuir. 2024 Aug 6;40(31):16113-16120. doi: 10.1021/acs.langmuir.4c00998. Epub 2024 Jul 25.
The field of artificial photosynthesis, which focuses on harnessing solar light for the conversion of CO to economically valuable chemical products, remains a captivating area of research. In this study, we developed a series of photocatalysts based on Earth abundant elements (Fe, Co, Ni, Cu, and Zn) incorporated into 2D metalloporphyrin-conjugated organic polymers known as MTBPP-BEPA-COPs. These photocatalysts were utilized for the photoreduction of CO employing only HO as the electron donor, without the need for any sacrificial agents or precious-metal cocatalysts. Remarkably, all of the synthesized MTBPP-BEPA-COPs exhibited an exceptional CO photoreduction performance only irradiated by visible light. Particularly, upon optimizing the metal ion coordinated with porphyrin units, ZnTBPP-BEPA-COP outperformed the other MTBPP-BEPA-COPs in terms of photocatalytic activity, achieving an impressive CO reduction yield of 152.18 μmol g after just 4 h of irradiation. The electrostatic potential surfaces calculated by density functional theory suggest the potential involvement of metal centers as binding and catalytic sites for the binding of CO. The calculated adsorption energy of CO with ZnTBPP-BEPA-COP exhibited one of the two smallest values. This may be the reason for the excellent catalytic effect of ZnTBPP-BEPA-COP. Thus, the present study not only demonstrates the potential of porphyrin-based conjugated polymers as highly efficient photocatalysts for CO reduction but also offers valuable insights into the rational design of such materials in the future.
人工光合作用领域专注于利用太阳光将二氧化碳转化为具有经济价值的化学产品，仍然是一个引人入胜的研究领域。在本研究中，我们基于地球上储量丰富的元素（铁、钴、镍、铜和锌）开发了一系列光催化剂，这些元素被掺入二维金属卟啉共轭有机聚合物（称为MTBPP - BEPA - COP）中。这些光催化剂仅以水作为电子供体用于二氧化碳的光还原反应，无需任何牺牲剂或贵金属助催化剂。值得注意的是，所有合成的MTBPP - BEPA - COP在仅可见光照射下均表现出卓越的二氧化碳光还原性能。特别是，通过优化与卟啉单元配位的金属离子，ZnTBPP - BEPA - COP在光催化活性方面优于其他MTBPP - BEPA - COP，在仅4小时的照射后就实现了令人印象深刻的152.18 μmol g的二氧化碳还原产率。通过密度泛函理论计算的静电势表面表明金属中心可能作为二氧化碳结合和催化的位点。计算得出的二氧化碳与ZnTBPP - BEPA - COP的吸附能呈现出两个最小值之一。这可能是ZnTBPP - BEPA - COP具有优异催化效果的原因。因此，本研究不仅证明了卟啉基共轭聚合物作为用于二氧化碳还原的高效光催化剂的潜力，而且为未来此类材料的合理设计提供了有价值的见解。
