金属插层联苯双层中的氧还原反应与氧析出反应研究
Understanding the Oxygen Reduction Reaction and Oxygen Evolution Reaction in Metal Intercalated Biphenylene Bilayers
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中文总结 AI 辅助
本研究通过从头算方法分析金属插层联苯双层的ORR和OER性能，确定Cu、Pt等为高活性ORR催化剂，Fe为最佳OER催化剂，发现电子描述符可预测其催化行为。
中文摘要 AI 辅助
我们对金属封装联苯双层结构B/M/B（其中M为Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Nb、Ru、W、Os和Pt）中的氧还原反应（ORR）和氧析出反应（OER）开展了从头算研究。在大多数体系中，插层金属位于联苯晶格的正方形碳位点（C$^{468}$）。采用计算氢电极方法，我们评估了这些活性位点的反应能学。多个B/M/B体系展现出具有竞争力的ORR和OER性能：在所研究的体系中，Cu、Pt、Ru和Mn的ORR过电位最低，分别为0.42 V、0.44 V、0.50 V和0.56 V；Fe被确定为OER活性最高的催化剂，过电位为0.44 V。为理解催化趋势，我们通过金属d带中心、C$^{468}$的pz带中心及相应轨道电荷布居分析电子结构。带中心与过电位无简单多项式依赖关系，但能为最佳催化剂指明有利的电子范围；而封装金属的d轨道电荷布居与活性（尤其对OER）的相关性最清晰，呈现火山型曲线。据此，B/Fe/B是最佳OER催化剂，B/Mn/B最接近ORR最优值；活性碳位点的p轨道布居也能捕捉主要趋势，但相关性较弱。总体而言，这些结果表明，简单的电子描述符可预测金属封装联苯双层的催化行为，为寻找碳骨架本身驱动反应性的高效催化剂提供指导。
英文摘要
We conducted an {\it ab initio} study of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in metal-encapsulated biphenylene bilayers, B/M/B, with M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Ru, W, Os and Pt. In most systems, the intercalated metal sits at the square carbon sites (C$^{468}$) of the biphenylene lattice. Using a computational hydrogen electrode approach, we evaluated the reaction energetics at these active sites. Several B/M/B systems show competitive ORR and OER performance. Among the investigated systems, Cu, Pt, Ru, and Mn exhibit the lowest ORR overpotentials of 0.42, 0.44, 0.50, and 0.56 V, respectively, while Fe is identified as the most active catalyst for OER with an overpotential of 0.44 V. To understand the catalytic trends, we looked at the electronic structure through the metal $d-$band centers, the C$^{468}$ $p_z-$band centers, and the corresponding orbital charge populations. The band centers did not give a simple polynomial dependence on the overpotentials, though they did point to favorable electronic ranges for the best catalysts. The $d-$orbital charge population of the encapsulated metal, however, correlated most clearly with activity-especially for OER-yielding volcano-type plots. From these, B/Fe/B emerges as the best OER catalyst, while B/Mn/B lies closest to the ORR optimum. The $p-$orbital population at the active carbon site also captures the main trends, albeit less strongly. Overall, these results show that straightforward electronic descriptors can predict catalytic behavior in metal-encapsulated biphenylene bilayers and guide the search for efficient catalysts where the carbon framework itself drives the reactivity.
