Cai Zhongjie, Liu Hongwei, Dai Jiajun, Li Bao, Yang Liming, Wang Jingyu, Zhu Huaiyong
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, Wuhan, 430074, China.
Australian Centre for Microscopy and Microanalysis, University of Sydney, Chippendale, NSW, Australia.
Nat Commun. 2025 Mar 16;16(1):2601. doi: 10.1038/s41467-025-57742-5.
Overall artificial photosynthesis, as a promising approach for sunlight-driven CO recycling, requires photocatalysts with efficient light adsorption and separate active sites for coupling with HO oxidation. Here we show a In-based metal-organic framework (MOF) heterostructure, i.e., In-porphyrin (In-TCPP) nanosheets enveloping an In-NH-MIL-68 (M68N) core, via a facile one-pot synthesis that utilises competitive nucleation and growth of two organic linkers with In nodes. The coherent interfaces of the core@shell MOFs assure the structural stability of heterostructure, which will function as heterojunctions to facilitate the efficient transfer of photogenerated charge for overall photosynthesis. The In-TCPP shell in MOFs heterostructure improves CO adsorption capabilities and visible light absorption to enhance the photocatalytic CO reduction. Simultaneously, In-O sites in M68N core efficiently catalyze HO oxidation, achieving high yields of HCOOH (397.5 μmol g h) and HO (321.2 μmol g h) under focused sunlight irradiation. The superior performance of this heterostructure in overall photosynthesis, coupled with its straightforward synthesis, shows great potential for mitigating carbon emissions and producing valuable chemicals using solar energy.
作为一种有前景的阳光驱动二氧化碳循环利用方法，整体人工光合作用需要具有高效光吸附和用于与水氧化耦合的分离活性位点的光催化剂。在此，我们展示了一种基于铟的金属有机框架（MOF）异质结构，即通过一种简便的一锅法合成，利用两种有机连接体与铟节点的竞争成核和生长，使铟卟啉（In-TCPP）纳米片包裹In-NH-MIL-68（M68N）核。核壳MOF的相干界面确保了异质结构的结构稳定性，其将作为异质结促进光生电荷的有效转移以实现整体光合作用。MOF异质结构中的In-TCPP壳层提高了二氧化碳吸附能力和可见光吸收，以增强光催化二氧化碳还原。同时，M68N核中的In-O位点有效地催化水氧化，在聚焦太阳光照射下实现了高产量的甲酸（397.5 μmol g-1 h-1）和氧气（321.2 μmol g-1 h-1）。这种异质结构在整体光合作用中的优异性能，加上其简单的合成方法，显示出在减少碳排放和利用太阳能生产有价值化学品方面的巨大潜力。
