Transition Metal-doped Ru Nanoparticles Loaded on Metal Hydrides for Efficient Ammonia Synthesis from First Principles
Transition Metal-doped Ru Nanoparticles Loaded on Metal Hydrides for Efficient Ammonia Synthesis from First Principles
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负载金属氢化物的过渡金属掺杂钌纳米粒子用于从第一原理高效合成氨
DOI：
10.1021/acs.jpcc.9b10544
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发表时间：
2019
期刊：
影响因子：
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通讯作者：
Hosono Hideo
中科院分区：
文献类型：
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作者：
Nakao Takuya;Tada Tomofumi;Hosono Hideo
负载钌的催化剂是低温合成氨的高效催化剂。当使用Ru负载的氢化物催化剂时，高活性的优点如下：（i）电子从Ru注入到Ru，由Ru上的表面氢空位（VH）介导，和（ii）吸附在Ru上的氢可逆迁移反应到表面VHas H-（H + e-参与H-）中。因此，Ru/H_2O催化剂表面VH_2的形成是影响Ru/H_2O催化剂合成氨性能的关键因素。为了促进Ru/氢化物界面的VH形成，我们采用Ru 5 TM/Ca 2NH模型，通过密度泛函理论计算，研究了Ru-过渡金属（TM）簇在典型氢化物Ca 2NH上的电子结构以及Ru-TM/Ca 2NH界面的VH形成和H迁移反应.五个晚期TM（Fe，Co，Rh，Os和Ir）和八个早期TM（Sc，Ti，Y，Zr，Nb，La，Hf和Ta）被确定为促进VH形成。Nb、Hf、Ta、Os和Ir在Ru 5 TM/Ca 2 NH界面处的氢迁移能也比在Ru 6/Ca 2 NH界面处的氢迁移能低。
Ru-loaded hydrides work as efficient catalysts for ammonia synthesis at low temperatures. The advantages of high activity when using Ru-loaded hydride catalysts are as follows: (i) electron injection from the hydrides to Ru, mediated by surface hydrogen vacancies (VH) on the hydrides and (ii) reversible migration reaction of hydrogen adsorbed on Ru into the surface VHas H–(H + e–↔ H–). Therefore, surface VHformation at the Ru/hydride interface is a key factor for ammonia synthesis with Ru/hydride catalysts. To promote VHformation at the Ru/hydride interface, we investigated the electronic structures of Ru–transition metal (TM) clusters loaded on a typical hydride, Ca2NH, and VHformation and H-migration reaction at the Ru–TM/Ca2NH interface using the Ru5TM/Ca2NH model with density functional theory calculations. Five late TMs (Fe, Co, Rh, Os, and Ir) and eight early TMs (Sc, Ti, Y, Zr, Nb, La, Hf, and Ta) were determined to promote VHformation. Nb, Hf, Ta, Os, and Ir can also decrease the H-migration energy at the Ru5TM/Ca2NH interface when compared with that at the Ru6/Ca2NH interface.
影响因子：
21.8
作者：
Arashiba, Kazuya;Miyake, Yoshihiro;Nishibayashi, Yoshiaki
通讯作者：
Nishibayashi, Yoshiaki
CaH2表面的结构和稳定性：金属氢化物中富电子表面用于催化的可能性
影响因子：
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作者：
P. Ong;L. Johnson;H. Hosono;P. Sushko
通讯作者：
P. Sushko