Polymetallic Coordination Polymers for Photocatalytic Hydrogen Production

Two different metal–organic frameworks (MOFs) are prepared by the hydrothermal method, and on this basis, by introducing PVP extension, metallic coordination polymers (MCPs) with better activity are obtained. The promotion effect of PVP as a surfactant and morphology regulator is proved. Then, a binary assembled polymetallic coordination polymer (PMCP) with a stepped flower group structure is constructed by a one-pot method without the preparation of template MCPs, and the ion-coordinated self-assembling process of binary polymetallic coordination polymers (Cu-MCPs and Co-MCPs) is successfully realized. A variety of experimental characterization techniques, including XRD, FTIR, XPS, SEM, and TEM, demonstrated the successful realization of the CoCuZn-PMCPs-x (1–7) ion-coordinated self-assembling process and morphology modulation. The application prospects of the CoCuZn-PMCPs-2 system in the field of photocatalysis are proven by BET, UV–vis, photoelectrochemical, EPR, and DFT calculations. As a demonstration case, the CoCuZn-PMCPs-2 photocatalytic system showed excellent catalytic activity (1038.8 μmol·h–1·g–1) and high stability. After introducing different noble metals, oxides, graphdiyne (CnH2n–2), and metal sulfides into the CoCuZn-PMCPs-2 system, the composite catalysts all exhibited excellent hydrogen evolution activity. The application of CoCuZn-PMCPs-2 materials in the photocatalytic field is expanded. This work provides a new direction for the rational design of binary assembled polymetallic coordination-polymer (PMCPs) materials, showing potential utilization in the field of renewable energy production.