Zhang Xiao-Yu, Wang Peng, Zhang Ya, Cheng Xiao-Mei, Sun Wei-Yin
Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, China.
ACS Appl Mater Interfaces. 2023 Jan 18;15(2):3348-3356. doi: 10.1021/acsami.2c19236. Epub 2023 Jan 4.
Exposing different facets on metal-organic frameworks (MOFs) is an efficient approach to regulate their photocatalytic performance for CO reduction. Herein, Fe-soc-MOFs exposed with different facets were successfully synthesized, and the morphologies of Fe-soc-MOF exposed with eight {111} facets (Fe-soc-O) and that exposed with eight {111} and six {100} crystal facets (Fe-soc-M) are first reported. Fe-soc-MOFs have facet-dependent active sites on their surface and correspondingly different catalytic performance for photocatalytic CO reduction. Fe-soc-O has the highest CO production of 1804 μmol g h, while the Fe-soc-MOF exposed with six {100} facets (Fe-soc-C) has the best CO selectivity of 94.7%. Density functional theory (DFT) calculations demonstrate that the (111) facet has more favorable thermodynamic potential for CO reduction and H evolution compared with the (100) one, deriving from its facet-dependent active sites. This work shows that utilizing the facet-engineering strategy to regulate the active sites exposed on the surface of MOFs is feasible. The results display the relation between the facet of MOFs and the photocatalytic behavior for CO reduction.
暴露金属有机框架（MOFs）的不同晶面是调节其光催化还原CO性能的有效方法。在此，成功合成了暴露不同晶面的Fe-soc-MOFs，并首次报道了暴露八个{111}晶面的Fe-soc-MOF（Fe-soc-O）和暴露八个{111}晶面及六个{100}晶面的Fe-soc-MOF（Fe-soc-M）的形貌。Fe-soc-MOFs表面具有依赖于晶面的活性位点，相应地对光催化还原CO具有不同的催化性能。Fe-soc-O的CO产量最高，为1804 μmol g h，而暴露六个{100}晶面的Fe-soc-MOF（Fe-soc-C）具有94.7%的最佳CO选择性。密度泛函理论（DFT）计算表明，与（100）晶面相比，（111）晶面在CO还原和析氢方面具有更有利的热力学势，这源于其依赖于晶面的活性位点。这项工作表明利用晶面工程策略调节MOFs表面暴露的活性位点是可行的。结果展示了MOFs晶面与光催化还原CO行为之间的关系。
