Chen Chen, Liu Yi, Yu Xuefang, Li Zhongwei, Li Wenzuo, Li Qingzhong, Zhang Xiaolong, Xiao Bo
Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai, Shandong 264005, People's Republic of China.
Yantai Gogetter Technology Company, Limited, Yantai, Shandong 264005, People's Republic of China.
ACS Appl Mater Interfaces. 2024 Dec 4;16(48):66149-66158. doi: 10.1021/acsami.4c15263. Epub 2024 Nov 20.
Recently, dual-metal catalysts have attracted much attention due to their abundant active sites and tunable chemical properties. On the other hand, metal borides have been widely applied in splitting the inert chemical bonds in small molecules (such as N) because of their excellent catalytic performances. As a combination of the above two systems, in this work, 11 kinds of transition metal atoms (TM = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, and W) were selected to embed in boron-doped graphene (BG) to construct 66 dual-metal-boron systems, and their performances toward the N reduction reaction (NRR) were examined using first-principles simulations. Our results revealed that such a dual-TM@BG system exhibits excellent thermodynamic and electrochemical stabilities, which facilitate the experimental synthesis. In particular, Fe-Fe- and Fe-Co-doped BG exhibit excellent performance for NRR, with the limiting potentials of -0.29 and -0.32 V, respectively, and both of them exhibit inhibitory effects on the H evolution reaction. Remarkably, the microkinetic modeling analysis revealed that the turnover frequency for the NH production on FeFe@BG reaches up to 7.27 × 10 s site at 700 K and 100 bar, which further confirms its ultrafast reaction rate. In addition, the machine learning method was employed to further understand the catalytic mechanism, and it is found that the NRR performances of dual-TM@BG catalysts are closely related to the sum of radii of two TM atoms. Therefore, our work not only proposed two promising electrocatalysts for NRR but also verified the feasibility for the application of a dual-metal-boron system in NRR.
近年来，双金属催化剂因其丰富的活性位点和可调控的化学性质而备受关注。另一方面，金属硼化物因其优异的催化性能，已被广泛应用于小分子（如N）中惰性化学键的断裂。作为上述两种体系的结合，在本工作中，选择了11种过渡金属原子（TM = Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Mo和W）嵌入硼掺杂石墨烯（BG）中，构建了66种双金属硼体系，并使用第一性原理模拟研究了它们对氮还原反应（NRR）的性能。我们的结果表明，这种双TM@BG体系表现出优异的热力学和电化学稳定性，这有利于实验合成。特别是，Fe-Fe和Fe-Co掺杂的BG对NRR表现出优异的性能，其极限电位分别为-0.29和-0.32 V，并且它们对析氢反应均表现出抑制作用。值得注意的是，微观动力学建模分析表明，在700 K和100 bar条件下，FeFe@BG上NH生成的周转频率高达7.27×10 s site，这进一步证实了其超快的反应速率。此外，采用机器学习方法进一步理解催化机理，发现双TM@BG催化剂的NRR性能与两个TM原子半径之和密切相关。因此，我们的工作不仅提出了两种有前景的NRR电催化剂，还验证了双金属硼体系在NRR中应用的可行性。
