Seeking high-performing non-noble transition metal catalysts for hydrogen evolution from chemical hydrogen storage media is significant. Herein we demonstrate for the first time that anomalous crystal phase engineering coupled with heteroatom doping can remarkably activate transition metal (Ni as a proof-of-concept study) for boosting ammonia borane (AB) dehydrogenation. Ni nanoparticles with designated phase (fcc or hcp phase) encapsulated in carbon (fcc-Ni/C and hcp-Ni/C) can be readily derived from Ni-based MOF. Intriguingly, hcp-Ni/C featuring unconventional hcp phase can remarkably outperform fcc-Ni/C with common fcc phase in AB dehydrogenation. Moreover, by doping Cu, dramatically promoted catalysis can be further achieved for hcp-CuNi/C. From experimental and theoretical results, delicate crystal phase together with heteroatom doping engineering can optimize electronic structure of hcp-CuNi/C, facilitating rate-determining step (H₂O dissociation), thereby boosting AB hydrolysis. This study details the first insight into the phase and doping engineering over non-noble transition metals for promoting AB dehydrogenation.

寻找用于从化学储氢介质中析氢的高性能非贵金属过渡金属催化剂具有重要意义。在此，我们首次证明异常晶相工程与杂原子掺杂相结合可以显着激活过渡金属（Ni 作为概念验证研究）以促进氨硼烷 (AB) 脱氢。具有封装在碳（fcc-Ni/C 和 hcp-Ni/C）中的指定相（fcc 或 hcp 相）的 Ni 纳米粒子可以很容易地从 Ni 基 MOF 中衍生出来。有趣的是，在 AB 脱氢中，具有非常规 hcp 相的 hcp-Ni/C 可以显着优于具有普通 fcc 相的 fcc-Ni/C。此外，通过掺杂 Cu，可以进一步显着促进 hcp-CuNi/C 的催化作用。从实验和理论结果来看，₂ O 解离），从而促进 AB 水解。这项研究详细介绍了对促进 AB 脱氢的非贵过渡金属的相和掺杂工程的首次见解。