The efficient evolution of hydrogen through electrocatalysis is considered a promising approach to the production of clean hydrogen fuel. Platinum (Pt)‐based materials are regarded as the most active hydrogen evolution reaction (HER) catalysts. However, the low abundance and high cost of Pt hinders the large‐scale application of these catalysts. Active, inexpensive, and earth‐abundant electrocatalysts to replace Pt‐based materials would be highly beneficial to the production of cost‐effective hydrogen energy. Herein, a novel organoimido‐derivatized heteropolyoxometalate, Mo4‐CNP, is designed as a precursor for electrocatalysts of the HER. It is demonstrated that the carbon, nitrogen, and phosphorus sources derived from the Mo4‐CNP molecules lead to in situ confined carburization, phosphorization, and chemical doping on an atomic scale, thus forming nitrogen‐doped porous molybdenum carbide and phosphide hybrids, which exhibit remarkable electrocatalytic activity for the HER. Such an organically functionalized polyoxometalate‐assisted strategy described here provides a new perspective for the development of highly active non‐noble metal electrocatalysts for hydrogen evolution.

中文翻译：

---

碳基质上的氮掺杂多孔碳化钼和磷杂化物作为氢生成反应的高效电催化剂

通过电催化有效地释放氢气被认为是生产清洁氢气燃料的一种有前途的方法。基于铂（Pt）的材料被认为是活性最高的析氢反应（HER）催化剂。但是，Pt含量低，成本高阻碍了这些催化剂的大规模应用。活性，廉价且富含地球的电催化剂替代基于Pt的材料将对生产具有成本效益的氢能非常有利。本文中，一种新型的有机亚氨基衍生化的杂多金属氧酸盐（Mo4-CNP）被设计为HER的电催化剂的前体。事实证明，源自Mo4-CNP分子的碳，氮和磷源导致原子范围内的原位受限渗碳，磷化和化学掺杂，从而形成了氮掺杂的多孔碳化钼和磷化杂化物，对HER表现出显着的电催化活性。本文所述的这种有机功能化的多金属氧酸盐辅助策略为开发用于放氢的高活性非贵金属电催化剂提供了新的视角。