青岛科技大学刘希恩团队报道了部分间隙注入硅的钌作为碱性析氢的高效电催化剂。相关研究成果发表在2024年12月17日出版的《德国应用化学》。

为了增强碱性析氢反应（HER），从根本上理解和合理调节潜在的催化位点是至关重要的，但也是具有挑战性的。

该文中，研究证实，尽管计算了Ru顶部位点的低水离解能垒和适当的H吸附自由能（ΔG*H），但金属Ru对碱性HER的活性相对较差。这主要是因为与具有强ΔG*H的相邻Ru空心位点相比，作为潜在H吸附位点的Ru顶部位点是隐性催化位点。为了促进Ru顶部位点从隐性催化位点向显性催化位点的转变，间隙Si原子被注入空心位点。

然而，完全间隙注入导致RuSi金属间化合物表面的高水离解能势垒。因此，研究人员提出了一种部分间隙掺入策略来形成Ru-RuSi异质结构，该异质结构不仅将Ru顶部位点从隐性催化位点转化为显性催化位点，而且保留了Ru表面的低水离解能势垒。此外，自发形成的内置电场双向优化了Ru位点的吸附能力，从而大大降低了热力学能垒，增强了碱性HER。

附：英文原文

Title: Partially Interstitial Silicon-Implanted Ruthenium as an Efficient Electrocatalyst for Alkaline Hydrogen Evolution

Author: Liqiang Hou, Zijian Li, Haeseong Jang, Min Gyu Kim, Jaephil Cho, Wenwu Zhong, shangguo Liu, Xien Liu

Issue&Volume: 2024-12-17

Abstract: To enhance the alkaline hydrogen evolution reaction (HER), it is crucial, yet challenging, to fundamentally understand and rationally modulate potential catalytic sites. In this study, we confirm that despite calculating a low water dissociation energy barrier and an appropriate H adsorption free energy (ΔG*H) at Ru-top sites, metallic Ru exhibits a relatively inferior activity for the alkaline HER. This is primarily because the Ru-top sites, which are potential H adsorption sites, are recessive catalytic sites, compared with the adjacent Ru-hollow sites that have a strong ΔG*H. To promote the transformation of Ru-top sites from recessive to dominant catalytic sites, interstitial Si atoms are implanted into the hollow sites. However, complete interstitial implantation leads to a high water dissociation energy barrier at the RuSi intermetallic surface. Thus, we present a partial interstitial incorporation strategy to form a Ru–RuSi heterostructure that not only converts the Ru-top sites from recessive to dominant catalytic sites but also preserves the low water dissociation energy barrier at the Ru surface. Moreover, the spontaneously formed built-in electric fields bidirectionally optimize the adsorption ability of the Ru sites, thereby greatly reducing the thermodynamic energy barrier and enhancing the alkaline HER.

DOI: 10.1002/anie.202423756

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202423756