Ordered scalable solar-driven dry reforming of methane via synergy of plasmonic catalysts with biomimetic reactors

Solar-driven dry reforming of methane (DRM) presents a sustainable path to close the carbon cycle but suffers from low solar-fuel efficiency and coke-induced instability. Here, we propose the synergy of plasmonic meta-nanoalloy catalysts with butterfly wing-inspired foam reactors to achieve ordered, scalable solar-driven DRM. Developed NiCoZn/MgAlO _x catalysts exhibit a benchmark solar-fuel efficiency of 42.4%, a high H₂/CO ratio of 0.95, and a CO₂ conversion rate that surpasses thermodynamic equilibrium values. The underlying mechanism is attributed to plasmonic activation of the initial C–H bonding of CH₄ and C–O bonding of CO₂ while suppressing complete methane cracking, steering the reaction toward an ordered pathway (^∗CH + ^∗O = ^∗CHO) instead of disordered route (^∗CH = ^∗C + ^∗H). Further depositing plasmonic catalysts on biomimetic dual-gradient foam reactors enables the synergy of plasmonic catalysis with light transport, reactants flow, and fluid-solid energy exchange. A bench-scale solar-driven DRM system demonstrates a remarkable solar-fuel efficiency of 41.11% and durable performance of nearly 10,000 min.