Li Yanru, Li Hongwei, Zhao Yan, Ji Dong, Guo Peng, Li Guixian, Zhao Xinhong
School of Petrochemical Technology, Lanzhou University of Technology, Lanzhou, 730050, China.
Key Laboratory of Low Carbon Energy and Chemical Engineering of Gansu Province, Lanzhou, 730050, China.
Small. 2023 Nov;19(46):e2303065. doi: 10.1002/smll.202303065. Epub 2023 Jul 21.
Stabilization of the Pt in N-doped carbon materials is an effective method to improve the performance of electrocatalytic methanol oxidation reaction (MOR). Nevertheless, the roles of different N configurations (pyridinic N, pyrrolic N, and graphitic N) toward the electrochemical performance of Pt-based catalysts remain unclear. Herein, Density Functional Theory calculations are adopted to elucidate the synergistic promotion of MOR by different N-configurations with Pt nanoparticles (NPs). Guided by the theoretical study, a series of MOR electrocatalysts with different ratios of pyridinic N and pyrrolic N (denoted as Pt/N-CNT-X (500, 600, 700, 800, and 900)) are designed and synthesized. Surprisingly, the electrocatalytic activity of Pt/N-CNT-600 with a suitable ratio of pyrrolic-N and pyridinic-N for MOR reaches 2394.7 mA mg and 5515.8 mA mg in acidic and alkaline media, respectively, which are superior to the Pt/CNTs, commercial Pt/C, and the ever-reported Pt-based electrocatalysts. The strong metal-support interaction induced by the N-doping is the crucial reason for the superior electrocatalytic performance. More importantly, the ability of pyrrolic-N and pyridinic-N in promoting the adsorption and oxidation of CH OH and the oxidation of CO is substantiated for the first time in methanol oxidation. This work provides new insights on the design of efficient electrocatalysts for MOR.
将铂稳定在氮掺杂碳材料中是提高电催化甲醇氧化反应（MOR）性能的有效方法。然而，不同氮构型（吡啶氮、吡咯氮和石墨氮）对铂基催化剂电化学性能的作用仍不清楚。在此，采用密度泛函理论计算来阐明不同氮构型与铂纳米颗粒（NPs）对MOR的协同促进作用。在理论研究的指导下，设计并合成了一系列具有不同吡啶氮和吡咯氮比例的MOR电催化剂（表示为Pt/N-CNT-X（500、600、700、800和900））。令人惊讶的是，具有合适吡咯氮和吡啶氮比例的Pt/N-CNT-600对MOR的电催化活性在酸性和碱性介质中分别达到2394.7 mA mg和5515.8 mA mg，优于Pt/CNTs、商业Pt/C以及以往报道的铂基电催化剂。氮掺杂诱导的强金属-载体相互作用是优异电催化性能的关键原因。更重要的是，首次在甲醇氧化中证实了吡咯氮和吡啶氮促进CH₃OH吸附和氧化以及CO氧化的能力。这项工作为设计高效的MOR电催化剂提供了新的见解。
