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Transition Metal Ion‐Directed Coordination Polymers with Mixed Ligands: Synthesis, Structure, and Photocatalytic Activity for Hydrogen Production and Rhodamine B Degradation
Author(s) -
Zhao Yan,
Liu ZhongYi,
Wang XiuGuang,
Zhao XiaoJun,
Yang EnCui
Publication year - 2020
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202000299
Subject(s) - rhodamine b , photocatalysis , isostructural , octahedron , coordination polymer , transition metal , chemistry , ligand (biochemistry) , metal ions in aqueous solution , crystallography , catalysis , metal , inorganic chemistry , photochemistry , crystal structure , organic chemistry , biochemistry , receptor
Three mixed‐ligand transition metal coordination polymers with the formula of {[Cu I 2 Cu II (tpt) 2 (L)] · 15H 2 O} n ( 1 ) and {[M 2 (H 2 O) 5 (tpt)(L)] · 6H 2 O} n [M = Ni for 2 and Co for 3 ; tpt = 2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine and L = 3,3'‐disulfonyl‐4,4'‐biphenyldicarboxylate] were hydrothermally synthesized by varying the cheap paramagnetic metal ions and used as photocatalysts for hydrogen evolution from water splitting and rhodamine B (RhB) degradation. Single‐crystal structural determinations reveal that 1 is a robust pillared‐layer framework with unusual 72‐membered {Cu 6 (tpt) 6 } macrocycle‐based layers supported by tetratopic L 4– connectors. Both 2 and 3 are isostructural (4 4) sheets with octahedral Ni II and Co II ions extended by ditopic L 4– and tpt linkages, in which the third pyridyl group of tpt is capped by pentahydrated metal ions. Due to the narrowed bandgap and good charge transport of the mixed‐valence Cu I/II centers, 1 exhibits improved dual‐functional catalytic activities than 2 and 3 with the visible‐light‐driven hydrogen evolution rate and RhB degradation efficiency up to 588 μmol · g –1 · h –1 and 72 % after 180‐minute irradiation. These interesting results indicate the importance of the metal ions and the dimensionality of the coordination polymers on the activity of the non‐Pt coordination polymer photocatalytic systems.