Light-Reconfigured Adsorption over Zeolite-Confined Amorphous Multicomponent Alloy Nanoparticles Enables Photothermal Dry Reforming of Methane

Abstract

High-temperature dry reforming of methane (DRM) over Ni-based catalysts is limited by sintering and coking, while competitive adsorption can further restrict efficient utilization of CH4 and CO2. Here, we report a one-step hydrothermal strategy to encapsulate amorphous NiCoCuZnMn multicomponent alloy nanoparticles with partially oxidized Zn/Mn-containing surface domains within a TS-1 zeolite matrix, affording a structurally confined photothermal catalyst (denoted MA@TS-1). Under illumination, MA@TS-1 reaches a CO production rate of 21.85 mmol g–1 h–1 at 450 °C and sustains continuous operation for 500 h. Kinetic analysis, pulse-response experiments, in situ DRIFTS, and illumination-dependent XPS collectively show that irradiation changes both the adsorption response and the surface electronic state of the catalyst. CO2 pre-adsorption strongly suppresses subsequent CH4 net retention in the dark, whereas the corresponding CO2-induced pulse-response loss is markedly attenuated under illumination. Concurrently, opposite XPS shifts of Ni and the Zn/Mn-associated species are consistent with illumination-induced interfacial electronic redistribution accompanied by relative electron enrichment of Ni-rich sites. Control catalysts and qualitative DFT calculations further support a model in which CH4 activation preferentially involves Zn/Mn oxide-associated interfacial regions, whereas CO2 activation is favored at Ni-rich sites. These results show that light-responsive electronic and adsorption modulation can accompany photothermal heating and provide a route to regulating competitive adsorption in multicomponent DRM catalysts.