过渡金属碳化物负载的金属簇的原子和电子结构：对催化的影响,Journal of Materials Chemistry A

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过渡金属碳化物负载的金属簇的原子和电子结构：对催化的影响
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2021-12-20 , DOI: 10.1039/d1ta08468b
Hector Prats ₁ , Michail Stamatakis ₁

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在过去十年中，人们探索了使用过渡金属碳化物 (TMC) 作为金属纳米团簇的催化活性载体的新研究途径，尽管块状金属的反应性（甚至惰性）较差，但仍显示出高催化活性。据推测，TMCs 极化吸附金属颗粒的电子密度，其催化活性最终优于分散在更传统的金属氧化物载体上的那些。在此，我们研究了以 1:1 化学计量比（TiC、ZrC、HfC、 VC、NbC、TaC、MoC 和 WC）通过周期性密度泛函理论计算。我们的高通量筛选研究表明，不仅可以在 TMC 表面上牢固结合并稳定分散的金属纳米粒子，而且还可以通过为主体 TMC 和金属簇仔细选择具有所需电负性的元素来操纵它们的电荷。通过这样做，可以调整簇空心位置上的电荷密度量，这可以促进某些分子的键合。此外，我们将六边形 TMC (001) 面上支持的 Pt、Pd 和 Rh 簇确定为具有最高潜在催化活性（通过簇电子密度的显着极化估计）和稳定性（由强负值量化）的候选者每个原子的吸附能和形成能。

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Atomistic and electronic structure of metal clusters supported on transition metal carbides: implications for catalysis

Novel research avenues have been explored over the last decade on the use of transition metal carbides (TMCs) as catalytically active supports for metal nanoclusters, which display high catalytic activity despite the poor reactivity (or even inertness) of the bulk metal. It has been postulated that TMCs polarise the electron density of adsorbed metal particles in such a way that their catalytic activity ends up being superior to those dispersed on more traditional metal oxide supports. Herein, we investigate the structural and electronic properties of small clusters of precious metals (Rh, Pd, Pt and Au) and more affordable metals (Co, Ni and Cu) supported on TMCs with 1 : 1 stoichiometry (TiC, ZrC, HfC, VC, NbC, TaC, MoC and WC) by means of periodic density functional theory calculations. Our high-throughput screening studies indicate that it is possible not only to have strongly bonded and stably dispersed metal nanoparticles on TMC surfaces, but also to manipulate their charge by carefully selecting elements with desired electronegativity for the host TMC and the metal cluster. By doing so, it is possible to tune the amount of charge density on the cluster hollow sites, which can facilitate the bonding of certain molecules. Moreover, we identify Pt, Pd and Rh clusters supported on hexagonal TMC (001) facets as the candidates with the highest potential catalytic activity—as estimated by the significant polarisation of the cluster electron density—and stability—as quantified by the strongly negative values of adsorption energy per atom and formation energy.

更新日期：2022-01-04

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