Polyoxometalate-Based Metal-Organic Frameworks as Visible-Light-Induced Photocatalysts

Xiuxia Zhao; Shaowei Zhang; Junqing Yan; Landong Li; Guangjun Wu; Wei Shi; Guangming Yang; Naijia Guan; Peng Cheng

doi:10.1021/acs.inorgchem.8b00098

Polyoxometalate-Based Metal-Organic Frameworks as Visible-Light-Induced Photocatalysts

Inorg Chem. 2018 May 7;57(9):5030-5037. doi: 10.1021/acs.inorgchem.8b00098. Epub 2018 Apr 18.

Authors

Xiuxia Zhao¹, Shaowei Zhang^{1

2}, Junqing Yan¹, Landong Li¹, Guangjun Wu¹, Wei Shi¹, Guangming Yang¹, Naijia Guan¹, Peng Cheng^{1

3}

Affiliations

¹ College of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE) , Nankai University , Tianjin , 300071 , China.
² Key Laboratory of Theoretical Organic Chemistry and Functional Molecule of the Ministry of Education, School of Chemistry and Chemical Engineering , Hunan University of Science and Technology , Xiangtan , Hunan 411201 , China.
³ Collaborative Innovation Center of Chemical Science and Engineering , Nankai University , Tianjin 300071 , China.

PMID: 29667839
DOI: 10.1021/acs.inorgchem.8b00098

Abstract

Two stable 3D polyoxometalate-based metal-organic frameworks (PMOFs), [Cu^I₁₂(trz)₈(H₂O)₂][α-SiW₁₂O₄₀]·2H₂O (1) and [Cu^I₁₂(trz)₈Cl][α-PW₁₂O₄₀] (2) (Htrz = 1- H-1,2,4-triazole) based on Keggin-type POMs were successfully obtained and fully characterized. The basic building units of the two PMOFs are [Cu^I₁₂(trz)₈], but polyoxoanion (POA) template effect leads to different structures and properties: 1 represents an interesting example that [α-SiW₁₂O₄₀]^4- locate in the nine-membered Cu-trz rings through Cu···O weak interactions to form a 3D framework, whereas 2 shows a 3D structure constructed from 2D bilayer cationic network [Cu^I₁₂(trz)₈Cl]³⁺ and [α-PW₁₂O₄₀]^3- lying in the adjacent layers via Cu···O weak interactions. PMOF 1 as unusual visible-light photocatalyst exhibit significantly enhanced photocatalytic activity under visible-light and excellent stability during the photocatalysis process for recovering and recycling, as well as photocatalytic hydrogen evolution activity.