Photothermal Dry Reforming of Methane Over Supported Bimetal Dual-Atom Pairs

Dry reforming of methane (DRM, CH₄ + CO₂ → 2H₂ + 2CO) offers a promising route for converting two greenhouse gases into valuable syngas. However, conventional thermal catalysis requires extreme temperatures (>800 °C) to overcome high energy barrier, leading to significant energy consumption and catalyst deactivation. Herein, we develop a Pt₁-Ni₁/CeO₂ photothermal catalyst with atomically dispersed Pt₁-Ni₁ paired active sites for DRM under mild conditions. At 450 °C under light illumination, the catalyst exhibits high H₂ and CO production rates of 4.62 and 4.65 mmol g_catalyst^-1 min^-1, respectively, with a H₂/CO ratio close to unity (0.99). Mechanistic investigations reveal that light irradiation induces photogeneration of electrons and holes in CeO₂, which directionally transfer to atomic Ni and Pt sites, respectively, inducing asymmetric charge polarization that promotes the activation of reactants. Steady-state isotope transient kinetic analysis combined with diffuse reflectance infrared Fourier transform spectroscopy (SSITKA-DRIFTS) measurement identifies the critical *CH_<i>x</i>O intermediate formed via *CH_<i>x</i> + *O → *CH_<i>x</i>O, a key step that suppresses deep dehydrogenation and carbon deposition. This work elucidates the regulation of parallel reactions over asymmetric dual-atom pairs in the transformation of CH₄ + CO₂ via photothermal synergy, paving the way for the targeted conversion of C1 molecules under mild conditions.