Ultradispersed Nickel Phosphide on Phosphorus-Doped Carbon with Tailored d-Band Center for Efficient and Chemoselective Hydrogenation of Nitroarenes,ACS Catalysis

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Ultradispersed Nickel Phosphide on Phosphorus-Doped Carbon with Tailored d-Band Center for Efficient and Chemoselective Hydrogenation of Nitroarenes
ACS Catalysis ( IF 11.3 ) Pub Date : 2018-08-01 00:00:00 , DOI: 10.1021/acscatal.8b02091
Ruijie Gao _{1,

2} , Lun Pan _{1,

2} , Huiwen Wang ₁ , Xiangwen Zhang _{1,

2} , Li Wang _{1,

2} , Ji-Jun Zou _{1,

2}

Affiliation

Nickel phosphide is a promising catalyst for hydrogenation of nitroarenes but suffers from sluggish H desorption and low chemoselectivity. Herein, we overcome these problems through reducing the Ni₂P into subnanosized clusters, tailoring the d-band center of Ni, and coupling them with P-doped carbon. Using density functional theory (DFT) calculations, we predicted that electron transfer from P-doped carbon to Ni₂P cluster results in downshift of d-band center of Ni that promotes H desorption on highly charged antibonding orbital of Ni–H, and reactant is preferentially adsorbed on P-doped carbon surface through nitro group due to the geometrical hindrance on Ni₂P clusters that leads to good selectivity. Then we developed a chemical anchoring method to fabricate Ni₂P supported on P-doped carbon with high dispersion of 81.3%. The synthesized catalyst delivers high activity and selectivity chemoselective hydrogenation of nitroarenes, and outperforms various noble- and transition-metal catalysts. Moreover, we revealed the origins of the superior performance of catalyst by characterizations, and confirmed the conclusion of DFT calculation. Such concept of tailoring d-band center and improving dispersion of active phase can provide insight for design of catalysts for hydrogenation and beyond.

中文翻译：

量身定制的d波段中心，磷掺杂碳上的超分散磷化镍，用于硝基芳烃的高效和化学选择性加氢

磷化镍是用于硝基芳烃加氢的有前途的催化剂，但氢脱附缓慢且化学选择性低。在本文中，我们通过将Ni ₂ P还原为亚纳米尺寸的团簇，定制Ni的d带中心并将它们与P掺杂的碳偶联来克服这些问题。使用密度泛函理论（DFT）计算，我们预测电子从P掺杂碳转移到Ni ₂ P团簇会导致Ni d谱带中心的下移，从而促进Ni-H的高电荷反键轨道上H的解吸以及反应物由于Ni ₂的几何位阻，其优先通过硝基吸附在P掺杂的碳表面上P团簇导致良好的选择性。然后，我们开发了一种化学锚固方法来制备负载在P掺杂碳上的Ni ₂ P，其高分散度为81.3％。合成的催化剂可实现硝基芳烃的高活性和选择性化学选择性加氢，其性能优于各种贵金属和过渡金属催化剂。此外，我们通过表征揭示了催化剂优异性能的起源，并证实了DFT计算的结论。修整d波段中心并改善活性相分散性的这种概念可以为加氢及以上催化剂的设计提供见识。

更新日期：2018-08-01

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