Atomically-precise Janus polyoxometalate catalyst with tunable water splitting activity

作     者：Zhimin Wang Xing Xin Zheng Li Mo Zhang Jiangwei Zhang Yeqin Feng Junhao Zhang Hongjin Lv Guo-Yu Yang Zhimin Wang;Xing Xin;Zheng Li;Mo Zhang;Jiangwei Zhang;Yeqin Feng;Junhao Zhang;Hongjin Lv;Guo-Yu Yang

作者机构：MOE Key Laboratory of Cluster ScienceBeijing Key Laboratory of Photoelectroic/Electrophotonic Conversion MaterialsSchool of Chemistry and Chemical EngineeringBeijing Institute of TechnologyBeijing 102488China College of Chemistry and Chemical EngineeringInner Mongolia UniversityHohhot 010021China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2023年第66卷第6期

页      面：1771-1780页

核心收录：

学科分类：081702[工学-化学工艺] 081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 080502[工学-材料学] 0805[工学-材料科学与工程（可授工学、理学学位）] 

基　　金：supported by the National Natural Science Foundation of China(21871025,21831001,21701168) the Recruitment Program of Global Experts(Young Talents) BIT Excellent Young Scholars Research Fund the National Key R&D Program of China(2020YFA0406101) 

主　　题：Janus polyoxometalate catalyst mixed-transition-metal substitution X-ray absorption fine structure(XAFS) H evolution O evolution 

摘      要：The development of bifunctional catalysts for solar-driven hydrogen and oxygen evolution has been regarded as a challenging but interesting research *** promising multi-electron-transfer catalysts,previously reported polyoxometalate(POM)-based catalysts often contain only a single type of transition metal substitution for driving either hydrogen production or oxygen ***,a viable two-step parental substitution approach has been developed to synthesize two structurally-new mixed-transition-metal-substituted polyoxometalates(mixed TMSPs),K_(6)Na_(4)[Mn_(2)Ni_(2)(H_(2)O)2(PW_(9)O_(34))2]·21H_(2)O({Mn_(2)Ni_(2)})and K10[Mn_(2)Co_(2)(H_(2)O)2(PW_(9)O_(34))2]·35H_(2)O({Mn_(2)Co_(2)}),using Na_(12)[Mn_(2)Na_(2)(PW_(9)O_(34))2]·36H_(2)O({Mn_(2)Na_(2)})as the *** results confirmed the nearly quantitative substitution of Na+with Ni_(2)+and Co_(2+)ions.X-ray absorption fine structure(XAFS)spectroscopy revealed that the Mn atoms are preferentially located in the internal positions of the central belt while Ni and Co atoms preferentially reside in the external,solvent-accessible *** from the second substitution of catalytically active transition metals,the resulting{Mn_(2)Ni_(2)}and{Mn_(2)Co_(2)}can be utilized as Janus catalysts towards H_(2) evolution and O_(2) evolution under visible light irradiation with greatly-enhanced activity compared to that of parental{Mn_(2)Na_(2)}.The introduction of mixed transition metals into POM structures not only enriches the POMs family,but also provides an effective strategy to control electronic structures and catalytic properties of POM-based catalysts at the atomic level.