In this
work, a succession of Keggin-type polyoxometalate (POM)-based metal–bis(pyridyl-tetrazole)
complexes, {Cu2(3-bptzp)3(H2O)4[SiW12O40]}·H2O (1), {Cu2(3-bptzpe)2(H2O)8[SiW12O40]}·4H2O (2), and {Cu2(3-bptzh)3(H2O)6[SiW12O40]} (3)
(3-bptzp = 1,4-bis(5-(3-pyridyl)tetrazolyl)-butane; 3-bptzpe = 1,4-bis(5-(3-pyridyl)tetrazolyl)-pentane;
3-bptzh = 1,4-bis(5-(3-pyridyl)tetrazolyl)-hexane), were prepared
and structurally characterized, which exhibited different architectures.
The title complexes were used directly as electrocatalysts for hydrogen
evolution reaction in alkaline and acidic media. The electrocatalytic
activity for generating hydrogen was reinforced by the introduction
of POMs. Complex 1 possesses the highest electrocatalytic
activity for hydrogen evolution reaction with a low overpotential
of 59.4 mV, achieving the current density of 10 mA·cm–2 in 0.1 M KOH. The different structures of the title complexes showed
effects on the hydrogen evolution performance. For 1,
the insertion of POMs between the ordered 2D metal–organic
layers induced the enhancement of electrocatalytic activity.