Highly Active and Carbon-Resistant Nickel Single-Atom Catalysts for Methane Dry Reforming

Abstract

The conversion of CH4 and CO2 to syngas using low-cost nickel catalysts has attracted considerable interest in the clean energy and environment field. Nickel nanoparticles catalysts suffer from serious deactivation due mainly to carbon deposition. Here, we report a facile synthesis of Ni single-atom and nanoparticle catalysts dispersed on hydroxyapatite (HAP) support using the strong electrostatic adsorption (SEA) method. Ni single-atom catalysts exhibit excellent resistance to carbon deposition and high atom efficiency with the highest reaction rate of 1186.2 and 816.5 mol.gNi−1.h−1 for CO2 and CH4, respectively. Although Ni single-atom catalysts aggregate quickly to large particles, the polyvinylpyrrolidone (PVP)-assisted synthesis exhibited a significant improvement of Ni single-atom stability. Characterizations of spent catalysts revealed that carbon deposition is more favorable over nickel nanoparticles. Interestingly, it was found that, separately, CH4 decomposition on nickel nanoparticle catalysts and subsequent gasification of deposit carbon with CO2 resulted in CO generation, which indicates that carbon is reacting as an intermediate species during reaction. Accordingly, the approach used in this work for the design and control of Ni single-atom and nanoparticles-based catalysts, for dry reforming of methane (DRM), paves the way towards the development of stable noble metals-free catalysts.