Liu Yongqin, Huang Liang, Fang Youxing, Zhu Xinyang, Nan Jianli, Dong Shaojun
College of Chemistry, Jilin University, Changchun, Jilin 130012, P. R. China.
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun, Jilin 130022, P. R. China.
ACS Appl Mater Interfaces. 2022 Mar 16;14(10):12304-12313. doi: 10.1021/acsami.1c25240. Epub 2022 Mar 3.
Ammonia (NH), which serves as a fertilizer supply, is struggling to satisfy the ever-growing population requirements over the world. The electrocatalytic nitrogen reduction to NH production is highly desired but shows the extremely poor activity and selectivity of reported electrocatalysts. In this work, we rationally design a novel Rh atomic layer-decorated SnO heterostructure catalyst through the interfacial engineering strategy, simultaneously achieving the highest NH yield rate (149 μg h mg) and Faradaic efficiency (11.69%) at -0.35 V vs the reversible hydrogen electrode. This result is superior to the optimum response of previously reported SnO- or Rh-based catalysts for electrochemical nitrogen reduction. Both X-ray absorption spectra characterization and density functional theory calculations reveal the strong electron interaction between the Rh atomic layer and the SnO heterostructure, which effectively regulated the interfacial electron transfer and d-band center. The downshift of the d-band center results in the greatly reduced H adsorption energy and the highly accelerated reaction kinetics for nitrogen reduction. This work endows a new insight into the interfacial electron regulation for weakening H adsorption and further enhancing the electrocatalytic N reduction.
作为肥料供应的氨（NH₃）正难以满足全球不断增长的人口需求。电催化氮还原制氨备受期待，但已报道的电催化剂活性和选择性极低。在这项工作中，我们通过界面工程策略合理设计了一种新型的铑原子层修饰的二氧化锡（SnO₂）异质结构催化剂，在相对于可逆氢电极 -0.35 V 的电位下，同时实现了最高的氨产率（149 μg h⁻¹ mg⁻¹）和法拉第效率（11.69%）。这一结果优于先前报道的基于二氧化锡或铑的电化学氮还原催化剂的最佳响应。X射线吸收光谱表征和密度泛函理论计算均表明，铑原子层与二氧化锡异质结构之间存在强烈的电子相互作用，有效调控了界面电子转移和d带中心。d带中心的下移导致氢吸附能大幅降低，氮还原反应动力学显著加快。这项工作为通过界面电子调控削弱氢吸附并进一步增强电催化氮还原提供了新的见解。
