A Tunable Multivariate Metal-Organic Framework as a Platform for Designing Photocatalysts.

Yang Wang,Aditya Dharanipragada,A Ken Inge,Akhil Tayal,Tom Willhammar,Carlo Alberto Gaggioli,Ben Liu,Xiaodong Zou,Erik Svensson Grape,Hao Lv,Zhehao Huang

doi:10.1021/jacs.1c01764

Abstract

Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO2. Recently, metal–organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal–organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB2OX3 bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 molH2 gcat.–1 min–1, a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10–5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.

Highlights

Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO2
Since the discovery of water photolysis by TiO2,1 it has become the predominant material for photocatalysis due to its high efficiency, high stability, and abundance
Among the various materials developed as photocatalysts,2−6 metal−organic frameworks (MOFs) are a family of inorganic−

Summary

Accession Codes

Authors Yang Wang − College of Chemistry, Sichuan University, Chengdu 610064, China; Key Laboratory for Soft Chemistry and Functional Materials, Nanjing University of Science and Technology, Ministry of Education, Nanjing 210094, China Hao Lv − College of Chemistry, Sichuan University, Chengdu 610064, China Erik Svensson Grape − Department of Materials and Environmental Chemistry, Stockholm University, Stockholm SE-106 91, Sweden; orcid.org/0000-0002-8956-5897 Carlo Alberto Gaggioli − Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States Akhil Tayal − Photon Science, Deutsches ElektronenSynchrotron, Hamburg 22607, Germany; orcid.org/ 0000-0001-8152-4209. Aditya Dharanipragada − Department of Materials and Environmental Chemistry, Stockholm University, Stockholm SE-106 91, Sweden. Tom Willhammar − Department of Materials and Environmental Chemistry, Stockholm University, Stockholm SE-106 91, Sweden; orcid.org/0000-0001-6120-1218. A. Ken Inge − Department of Materials and Environmental Chemistry, Stockholm University, Stockholm SE-106 91, Sweden; orcid.org/0000-0001-9118-1342. Xiaodong Zou − Department of Materials and Environmental Chemistry, Stockholm University, Stockholm SE-106 91, Sweden; orcid.org/0000-0001-6748-6656.

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