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Enhancing the Hydrogen Activation Reactivity of Nonprecious Metal Substrates via Confined Catalysis Underneath Graphene

机译:通过石墨烯下的受限催化提高非贵金属底物的氢活化反应性

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In the hydrogen evolution reaction (HER), the reactivity as a function of the hydrogen adsorption energy on different metal substrates follows a well-known;volcano curve, peaked a the precious inetal Pt. The goal. of turning nonprecious metals into efficient catalysts for HER and other important chemical reactions is a :fundamental challenge; it is-also of technological significance. Here, we present results toward, achieving Ihis goal by exploiting the synergistic power of marginal catalysis and confined catalysis. Using density functional theory calculations, we first show that the volcano curve stays qualitatively intact when van der Waals attractions between a hydrogen adatom and different metal (111) surfaces are included. We further show that the hydrogen adsorption:energy on the metal: surfaces is weakened by 0.11-0.23 eV when hydrogen is confinedbetween graphene and the metal surfaces, with Ni exhibiting the largest change. Inparticular, we find that the graphene-modified volcano curve peaks around Ni, whose bare surface already possesses moderate (or :marginal) reactivity,i and the corresponding HER rate of grapllene-covered comparable to that of bare Pt. A hydrogen adatom has high mobility within the confined geometry. These findings demonstrate that graphene-coyeted Ni is an appealing effective stable, and economical catalytic platform for HER.
机译:在氢气逸出反应(HER)中,反应性随氢气在不同金属基材上的吸附能而变化,遵循众所周知的火山曲线,使珍贵的Int Pt达到峰值。目标。将非贵金属转化为HER和其他重要化学反应的有效催化剂是一项根本性的挑战;它也具有技术意义。在这里,我们介绍了通过利用边际催化和局限催化的协同作用来实现其目标的结果。使用密度泛函理论计算,我们首先表明,当包括氢原子和不同金属(111)表面之间的范德华力吸引力时,火山曲线定性保持完整。我们进一步表明,当氢限制在石墨烯和金属表面之间时,金属表面上的氢吸附能减弱0.11-0.23 eV,其中Ni表现出最大的变化。特别是,我们发现石墨烯修饰的火山曲线在Ni附近出现峰,Ni的裸露表面已经具有中等(或边际)反应性,并且相应的HER gra覆盖率与Pt裸露相当。氢原子在受限的几何形状内具有高迁移率。这些发现表明,石墨烯着色的镍是用于HER的吸引人的有效的稳定且经济的催化平台。

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