Abstract The hybrid nanostructures of nitrogen doped carbon materials and nonprecious transition metals are among the most promising electrocatalysts to replace noble metal catalysts for renewable energy applications. However, the fundamental principles governing the catalytic activity of such hybrid materials remain elusive. Herein, we systematically explore the electrocatalytic properties of transition metals, transition metal oxides and carbides substrates covered by nitrogen-doped graphitic sheets for hydrogen evolution reaction (HER). Our first-principles calculations show that the graphitic sheet is prominently activated by the nitrogen doping and the coordinate bond with metal (compound) substrate through intralayer and interlayer charge transfer. Such hybrid materials can provide optimal binding capability for HER catalysis with Tafel barrier down to 1.0 eV. The HER activity can be correlated to the C pz band center, which is in turn governed by the electronic coupling strength between the graphitic sheet and metal substrate, thus paving a way to rational design of graphitic carbon/transition metal hybrid electrocatalysts of high performance.

中文翻译：

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N掺杂石墨碳材料与过渡金属（化合物）杂化用于析氢反应：从原子水平理解协同效应

摘要 掺氮碳材料和非贵金属过渡金属的混合纳米结构是最有前途的电催化剂，可替代贵金属催化剂用于可再生能源应用。然而，控制这种混合材料催化活性的基本原理仍然难以捉摸。在此，我们系统地探索了由氮掺杂石墨片覆盖的过渡金属、过渡金属氧化物和碳化物基材的电催化性能，用于析氢反应 (HER)。我们的第一性原理计算表明，通过层内和层间电荷转移，氮掺杂和与金属（化合物）基板的配位键显着激活了石墨片。这种杂化材料可以为 HER 催化提供最佳结合能力，Tafel 势垒低至 1.0 eV。HER活性可以与C pz 带中心相关，而C pz 带中心又受石墨片和金属基材之间的电子耦合强度控制，从而为合理设计高性能石墨碳/过渡金属杂化电催化剂铺平了道路。