Promoting Methane Dry Reforming over Ni Catalysts via Modulating Surface Electronic Structures of BN Supports by Doping Carbon

Methane dry reforming (MDR) attracts great attention due to the comprehensive conversion and utilization of CO2 and CH4 into an equimolar ratio of H2/CO. Boron nitride-supported Ni-based catalysts show great promise for the efficient coking resistance but exhibit weak interactions with active sites and poor gas adsorption capacity. Herein, carbon-doped boron nitride (BCN) was originally developed to anchor Ni nanoparticles on the boundary or near the boundary between layers with strong interactions, which exhibited excellent MDR activity and high coking resistance. It has been demonstrated that the modification of the electronic structure of BN surfaces by doping carbon strengthens the interactions between Ni and BCN as well as the CO2 activation capacity. The stable ID/IG ratio observed during the MDR process implies that carbon doping effectively inhibits the formation of graphitic carbon by weakening the occurrence of side reaction and makes the catalysts possess excellent coking resistance. Abundant active intermediates, such as −OH groups and formate species as well as CO, were observed over Ni/BCN catalysts signifying the strong activation of CO2 and CH4 cleavage capacity, which can facilitate the MDR process. This discovery presents in-depth insights into the relationship of surface electronic structure and gas activation over Ni/BCN catalysts and also paves the way for the development of highly efficient coking- and sintering-resistant Ni-based catalysts.