Asymmetric Dual-Atom Ru Anchored in Boron Nitride Nanolayer Triggers Mechanism Transition for Stable Dry Reforming

Methane dry reforming represents a promising approach to reduce greenhouse gas emissions and to utilize natural gas for value-added products. However, this process is challenged by limited reactivity and severe coking at low temperatures. Here, we report a dual-atom ruthenium catalyst anchored in a boron nitride nanolayer. The spatially distinct coordination of the Ru atomic pair gives rise to the asymmetric charge distribution of the active center. The synergy effect of Ru dimer achieves the CH₄ and CO₂ conversions of 69% and 76% at 650 °C, respectively, which are near thermodynamic equilibrium, while maintaining an exceptional stability of 1000 h at 600 °C with negligible coking. Mechanism studies reveal that an electron-deficient Ru site facilitates the C-H cleavage in CH₄ via an enhanced polarization effect, while another electron-rich Ru site promotes CO₂ activation with a bidentate adsorption configuration. Furthermore, this unique dual-atom Ru structure enables a Langmuir-Hinshelwood pathway with a reduced barrier of the coupling reaction between CH₄ and CO₂ to form *CH₂O intermediate and produce syngas rather than excessive C-C binding and coke deposition. This work provides a strategy for designing multifunctional catalysts to solve the seesaw issue of reactivity and stability for methane dry reforming.