Graphene-oxide-supported covalent organic polymers based on zinc phthalocyanine for efficient optical limiting and hydrogen evolution

In this contribution, two constituent-tunable metallophthalocyanine covalent organic polymers (MPc-COPs) covalently attached to graphene oxide (GO-PcP 1 and GO-PcP 2) were rationally designed and fabricated for optoelectronics and electrocatalysis. The resultant GO-PcP nanohybrids exhibit markedly enhanced nonlinear optical and optical limiting performances over those of their components and physical mixtures at 532 nm in the nanosecond pulse range. The optical nonlinearity can be further optimized by tuning the linkage type between the four-branched tetraamine metallophthalocyanine units. The hydrogen evolution reaction (HER) is investigated by linear sweep voltammetry in a 0.5-M H2SO4 aqueous solution. Under optimal conditions, the overpotentials needed to reach 1 mA cm(-2) are measured as 237 and 210 mV for GO-PcP 1 and GO-PcP 2, respectively, which places GO-PcP 2 as the best metallophthalocyanine polymer-based HER catalyst to be reported in the literature. The improved performances were ascribed to the positive synergistic effects between MPc-COPS and GO. Notably, the present study introduces a new strategy for the precise preparation of MPc-COP-based nanomaterials while exploring their applications to develop highly efficient optical limiters and electrocatalysts. (C) 2019 Elsevier Inc. All rights reserved.