Stable operations for catalytic dry reforming of methane (DRM) are essential for industrial applications. High stability for syngas production can be achieved via a kinetic balance between formation of carbon species and their removal by oxygen species on the metal surface, which clears the surface for further reaction steps. This study reports highly stable performance by a boron-doped cobalt catalyst as a non-noble-metal coking-free catalyst. Although the precise location of doped boron could not be identified experimentally because of its low concentration, density functional theory calculations suggested that interstitial boron (B) is most likely present in the subsurface region of cobalt (Co) surfaces. B-doping was shown both experimentally and computationally to increase the reactivity of Co catalysts toward both methane (CH₄) and carbon dioxide (CO₂). Moreover, B-doping was found to balance the amounts of surface C and O and maintain the reduced state of Co surfaces while in a steady-state. Nevertheless, a negative kinetic order with respect to CO₂ partial pressure indicates that steady-state surface coverage of oxygen species originating from CO₂ dissociation was prevalent on B-doped Co, consistent with the coking-free nature of the catalyst. This study introduces a promising Co–B catalyst design for controlling metal surface reactivity toward DRM and relevant catalytic reactions.

甲烷催化干重整（DRM）的稳定操作对于工业应用至关重要。合成气生产的高稳定性可以通过碳物质的形成与金属表面上的氧物质的去除之间的动力学平衡来实现，这可以清除表面以用于进一步的反应步骤。这项研究报告称，掺硼钴催化剂作为一种非贵金属无焦化催化剂具有非常稳定的性能。尽管由于浓度低而无法通过实验确定掺杂硼的精确位置，但密度泛函理论计算表明，间隙钴（B）最有可能存在于钴（Co）表面的地下区域。实验和计算表明B掺杂可提高Co催化剂对甲烷（CH）的反应性₄）和二氧化碳（CO ₂）。而且，发现B掺杂使表面C和O的量平衡，并且在稳态时保持Co表面的还原态。然而，相对于CO ₂分压的负动力学次序表明，源自CO ₂离解的氧物种的稳态表面覆盖在B掺杂的Co上普遍存在，这与催化剂的无焦化性质一致。这项研究介绍了一种有前景的Co-B催化剂设计，用于控制金属对DRM和相关催化反应的反应性。