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Weakening CO poisoning over size- and support-dependent Ptn/X-graphene catalyst (X = C, B, N, n = 1–6, 13)

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CO poisoning is one of the obstacles for platinum catalysts toward the electro-catalysis process for proton exchange membrane fuel cell (PEMFC) or direct methanol fuel cell (DMFC). Herein, we aim to weaken the CO poisoning on Pt by varying the cluster sizes and supports via doping graphene with B and N based on DFT + D3 calculations. Energetically, the most favorable Ptn/X-graphene (X = C, B, N; n = 1–6, 13) structures are obtained, and the calculated binding energies between Ptn and X-graphene are size- and support-dependent on a sequence: Ptn/B-g > Ptn/N-g > Ptn/C-g. The low-coordinated and protruded Pt atoms are identified as the active sites. The medium-sized clusters (n = 4–6) display CO poisoning-free properties with an excellent CO oxidation performance, resulting from the moderate locations of d-band center and electronic transfer via the interface. Furthermore, E-R mechanism is revealed to dominate the reaction route with a rate-limiting step of the second CO2 desorption. The corresponding activation energy barriers are 0.53, 0.61 and 0.56 eV for Ptn/B-g (n = 4, 5, 6), respectively. This work provides insights into the theoretical design of CO poisoning-free catalyst Ptn/X-g in the applications of DMFC/PEMFC.

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摘要

一氧化碳中毒是铂基催化剂应用于电催化过程的主要障碍之一。本文基于DFT+D3 计算，通过B 和N 掺杂石墨 烯并改变团簇尺寸以减弱Pt 催化剂的CO 中毒现象。计算得到了能量上最有利的Ptn/X-石墨烯(X = C, B, N; n = 1‒6, 13)结构，且Ptn 和X-石墨烯之间的结合能依赖于团簇尺寸与载体，顺序为：Ptn/B-g > Ptn/N-g > Ptn/C-g。低 配位及突出的原子作为主要活性位点参与反应。由于d 带中心的位置和界面引起的电子转移，中等大小团簇(n = 4‒6)能有效抑制CO 中毒，具有优异的CO 氧化性能。此外揭示了以第二次CO2 解吸为速控步的E-R 机制主导 的反应路线。Ptn/B-g (n = 4,5,6)对应的活化能垒分别为0.53、0.61 和0.56 eV。这项工作为抗CO 中毒的Ptn/Xg 催化剂在燃料电池中的应用与设计提供了理论指导。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (No. 21975136) and the Open Funds from National Engineering Lab for Mobile Source Emission Control Technology (No. NELMS2020A12).

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    Authors and Affiliations

    1. Department of Electronics and Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, Nankai University, Tianjin, 300071, China

      An-Qi Dong, Hui Li & Wei-Chao Wang

    2. College of Information Science and Engineering, Jiaxing University, Jiaxing, 314001, China

      Hui Li

    3. Zhejiang Engineering Research Center of Intelligent Human Health Situation Awareness, Jiaxing University, Jiaxing, 314001, China

      Hui Li

    4. National Engineering Laboratory for Mobile Source Emission Control Technology, China Automotive Technology & Research Center Co., Ltd, Tianjin, 300300, China

      Han-Ming Wu, Kai-Xiang Li, Yuan-Kai Shao & Zhen-Guo Li

    5. Institute National de la Recherche Scientifique (INRS), Centre Énergie Matériaux et Télécommunications, Varennes, Québec, J3X 1P7, Canada

      Shu-Hui Sun

    6. College of Electronic Information and Optical Engineering, Nankai University, Tianjin, 300071, China

      Wei-Bo Hu

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    Dong, AQ., Li, H., Wu, HM. et al. Weakening CO poisoning over size- and support-dependent Ptn/X-graphene catalyst (X = C, B, N, n = 1–6, 13). Rare Met. 42, 1138–1145 (2023). https://doi.org/10.1007/s12598-022-02210-y

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