Linker engineering in metal–organic frameworks for dark photocatalysis |
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| Authors: | Yating Pan Jingxue Wang Shengyi Chen Weijie Yang Chunmei Ding Amir Waseem Hai-Long Jiang |
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| Affiliation: | Department of Chemistry, University of Science and Technology of China Hefei, Anhui 230026 P. R. China.; School of Energy and Power Engineering, North China Electric Power University, Baoding 071003 P. R. China ; Dalian National Laboratory for Clean Energy, State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 P. R. China ; Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 I. R. Pakistan |
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| Abstract: | Dark reactions featuring continuous activity under light off conditions play a critical role in natural photosynthesis. However, most artificial photocatalysts are inactive upon the removal of the light source, and the artificial photocatalysts with dark photocatalysis abilities have been rarely explored. Herein, we report a Ti-based metal–organic framework (MOF), MIL-125, exhibiting the capability of dark photocatalytic hydrogen production. Remarkably, the introduction of different functional groups onto the linkers enables distinctly different activities of the resulting MOFs (MIL-125-X, X = NH2, NO2, Br). Dynamic and thermodynamic investigations indicate that the production and lifetime of the Ti3+ intermediate are the key factors, due to the electron-donating/-withdrawing effect of the functional groups. As far as we know, this is the first report on dark photocatalysis over MOFs, providing new insights into the storage of irradiation energy and demonstrating their great potential in dark photocatalysis due to the great MOF diversity.A Ti-based MOF with long-lived Ti3+ can achieve dark photocatalysis. The different groups on the organic linker modulate electron storage ability and the lifetime of Ti3+, significantly regulating dark photocatalytic activity in H2 production. |
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