Zhang Yaqin, Li Ping, Cui Peng, Hu Xunliang, Shu Chang, Sun Ruixue, Peng Mengjie, Tan Bien, Wang Xiaoyan
Key Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education, Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Luoyu Road No. 1037, 430074, Wuhan, China.
State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing, 210023, China.
Angew Chem Int Ed Engl. 2024 Nov 11;63(46):e202413131. doi: 10.1002/anie.202413131. Epub 2024 Sep 17.
The development of artificial photocatalysts to convert CO into renewable fuels and HO into O is a complex and crucial task in the field of photosynthesis research. The current challenge is to enhance photogenerated charge separation, as well as to increase the oxidation capability of materials. Herein, a molecular junction-type porphyrin-based crystalline photocatalyst (Ni-TCPP-TPyP) was successfully self-assembled by incorporating a nickel porphyrin complex as a reduction site and pyridyl porphyrin as an oxidation site via hydrogen bonding and π-π stacking interactions. The resulting material has a highly crystalline structure, and the formation of inherent molecular junctions can accelerate photogenerated charge separation and transport. Thus, Ni-TCPP-TPyP achieved an excellent CO production rate of 309.3 μmol g h (selectivity, ~100 %) without the use of any sacrificial agents, which is more than ten times greater than that of single-component photocatalyst (Ni-TCPP) and greater than that of the most organic photocatalysts. The structure-function relationship was investigated by femtosecond transient absorption spectroscopy and density functional theory calculations. Our work provides new insight for designing efficient artificial photocatalysts, paving the way for the development of clean and renewable fuels through the conversion of CO using solar energy.
开发将CO转化为可再生燃料以及将H₂O转化为O₂的人工光催化剂是光合作用研究领域一项复杂而关键的任务。当前的挑战是提高光生电荷的分离效率，以及增强材料的氧化能力。在此，通过氢键和π-π堆积相互作用，成功自组装了一种分子结型卟啉基晶体光催化剂（Ni-TCPP-TPyP），其中镍卟啉配合物作为还原位点，吡啶基卟啉作为氧化位点。所得材料具有高度结晶的结构，固有分子结的形成可加速光生电荷的分离和传输。因此，Ni-TCPP-TPyP在不使用任何牺牲剂的情况下，实现了309.3 μmol g⁻¹ h⁻¹的优异CO生成速率（选择性约为100%），这比单组分光催化剂（Ni-TCPP）高出十多倍，且高于大多数有机光催化剂。通过飞秒瞬态吸收光谱和密度泛函理论计算研究了结构-功能关系。我们的工作为设计高效人工光催化剂提供了新的见解，为利用太阳能将CO转化为清洁可再生燃料的发展铺平了道路。
