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Substituent group-tunable hydrogen evolution activity observed in isostructural Cu(ii)-based coordination polymer photocatalysts

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Abstract

Elucidations on the structure–activity correlations of non-Pt coordination polymer (CP)-based photocatalysts are highly significant for both the enhancement in catalytic activity and large-scale industrial applications of sustainable hydrogen from water splitting. Herein, three isostructural [Cu(HL)2(R-BDC)]n (denoted as Cu-CP-R, HL = 4′-(4-hydroxyphenyl)-4,2′:6′,4′′-terpyridine, R-BDC = 2-R-1,4-benzenedicarboxylate, R = NO2, OH and Br) CPs were solvothermally synthesized by varying the substituents attached to benzenedicarboxylate, which together with two previously reported analogues (R = NH2 and H) were used as photocatalysts to systematically explore the substitution effect on the hydrogen evolution activity. These five CPs feature isomorphic layered motifs with axially elongated CuII octahedra extended alternately by ditopic HL and R-BDC2− connectors, in which R behaves structurally as a non-coordinate group. The hydrogen production rate over the Cu-CP-R photocatalysts increased from 0.21 to 2.34 mmol g−1 h−1, which followed the order of –NH2 > –NO2 > –H > –OH > –Br. Furthermore, the combined experimental and theoretical investigations reveal that the free R moiety significantly dominates the photocatalytic activity by shifting the d states of the CuII ion towards the Fermi level, controlling the potential of the conduction band and quickening the charge transfer ability. These important findings can provide informative hints for the design of high-performance, earth-abundant non-noble metal CP-based semi-conductive photocatalysts.

Graphical abstract: Substituent group-tunable hydrogen evolution activity observed in isostructural Cu(ii)-based coordination polymer photocatalysts

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Supplementary files

Article information


Submitted
28 Nov 2019
Accepted
23 Dec 2019
First published
26 Dec 2019

Dalton Trans., 2020, Advance Article
Article type
Paper

Substituent group-tunable hydrogen evolution activity observed in isostructural Cu(II)-based coordination polymer photocatalysts

X. Dai, J. Wang, L. Li, B. Ding, Z. Liu, X. Zhao and E. Yang, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT04567H

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