Biodeposited Nano-CdS Drives the In Situ Growth of Highly Dispersed Sulfide Nanoparticles during Pyrolysis for Enhanced Oxygen Evolution Reaction.

Abstract

A novel, efficient, and stable graphene-based composite oxygen evolution reaction (OER) catalyst, BG@Ni/Ni3S2, was designed via high-specificity, low-cost biosynthesis and efficient electrostatic self-assembly. In the synthetic process, bacterial cells containing biodeposited CdS nanocrystals, graphene oxide (GO), and Ni2+ ions are assembled into a sandwich-type hybrid precursor. The nanosized sulfur source drives in situ sulfidation during pyrolysis, which induces the uniform formation and growth of Ni/Ni3S2 composite nanoparticles (NPs) on the graphene substrate. Benefiting from the high specific surface area and uniform distribution of NPs, the catalyst has a large number of exposed active sites and exhibits rapid mass transfer. In addition, the skeleton composed of a conductive carbon matrix and metallic Ni-Ni network ensures the excellent electron transfer during the OER, and the synergistic effect of Ni0 and Ni3S2 further optimizes the electronic structure and accelerates the OER kinetics. The dominant catalytic sites at the nanointerface between Ni0 and Ni3S2 provide favorable thermodynamic conditions for the adsorption of OER intermediates. As a result, BG@Ni/Ni3S2 exhibits efficient catalytic performance for the OER: the overpotential and Tafel slope are only 320 mV at 100 mA cm-2 and 41 mV dec-1, respectively. This work provides a novel understanding of the intrinsic activity of transition metal sulfide composites and a biological-based design for OER catalysts.