物理化学学报 >> 2026, Vol. 42 >> Issue (7): 100287.doi: 10.1016/j.actphy.2026.100287

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电子结构不对称碳介导的Pd电荷重分布促进乙醇氧化反应

周鑫灿1,2,†, 王雪瑶1,3,†, 陈小康1,4,†, 兰笛2, 高宇庭5, 王晓霞1, 李道浩1, 张树超1,6,*(), 张立杰1,*(), 吴广磊1,*()   

  1. 1 青岛大学材料科学与工程学院, 生物纤维与生态纺织国家重点实验室, 山东 青岛 266071
    2 湖北汽车工业学院汽车材料学院, 湖北 十堰 442002
    3 山东大学环境科学与工程学院, 山东 青岛 266237
    4 山东大学化学与化工学院前沿化学研究院, 山东 青岛 266237
    5 山东省科学技术情报研究院, 山东 济南 250101
    6 青岛大学附属医院输血科, 山东 青岛 266003
  • 收稿日期:2025-12-19 修回日期:2026-03-12 录用日期:2026-03-12 发布日期:2026-05-22
  • 通讯作者: Email: zhangshuchao@qdu.edu.cn (张树超)lijiezh@qdu.edu.cn (张立杰)wuguanglei@qdu.edu.cn/wuguanglei@mail.xjtu.edu.cn (吴广磊)
  • 作者简介:

    †这些作者对这项工作做出了同等贡献

Charge redistribution on Pd mediated by electronically asymmetric carbon for boosting ethanol oxidation

Xincan Zhou1,2, Xueyao Wang1,3, Xiaokang Chen1,4, Di Lan2, Yuting Gao5, Xiaoxia Wang1, Daohao Li1, Shuchao Zhang1,6,*(), Lijie Zhang1,*(), Guanglei Wu1,*()   

  1. 1 State Key Laboratory of Bio-fibers and Eco-textiles, College of Materials Science and Engineering, Qingdao University, Qingdao 266237, Shandong Province, China
    2 School of Automotive Materials, Hubei University of Automotive Technology, Shiyan 442002, Hubei Province, China
    3 School of Environmental Science and Engineering, Shandong University, Qingdao 266237, Shandong Province, China
    4 Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Qingdao 266237, Shandong Province, China
    5 Shandong Institute of Scientific and Technical Information, Jinan 250101, Shandong Province, China
    6 Department of Blood Transfusion, The Affiliated Hospital of Qingdao University, Qingdao University, Qingdao 266003, Shandong Province, China
  • Received:2025-12-19 Revised:2026-03-12 Accepted:2026-03-12 Published:2026-05-22
  • Contact: Email: zhangshuchao@qdu.edu.cn (Shuchao Zhang)lijiezh@qdu.edu.cn (Lijie Zhang)wuguanglei@qdu.edu.cn/wuguanglei@mail.xjtu.edu.cn (Guanglei Wu)

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摘要：

作为一类具有应用前景的乙醇氧化反应(EOR)催化剂，Pd基材料仍然本征受限于表面电子结构在乙醇吸附与CH3CO中间体脱附之间的权衡关系。本文合成了负载于N/S共掺杂碳上的Pd催化剂(Pd@SNC)，其中掺杂的S和N原子能够向Pd转移适量电子，从而赋予Pd更为适宜的电子结构。此外，d带中心的适度负移表明，该适宜的Pd电子结构不仅能够增强对乙醇和OH−的吸附，还能够促进中间体(CH3CO*)的脱附，从而有利于反应动力学。结果表明，Pd@SNC表现出最高的EOR催化活性，其质量活性达到945.49 mA mgPd−1，明显优于Pd@NC和Pd@C。理论计算结果进一步表明，由于共掺杂N和S原子对Pd电子结构进行了有效调控，Pd@SNC在EOR过程中脱氢步骤表现出最低的反应能垒。

关键词: Pd基催化剂, 乙醇氧化, 杂原子掺杂, 金属-载体相互作用, 电子结构

Abstract:

Pd-based materials as the promising catalysts for ethanol oxidation reaction (EOR) are still intrinsically limited by the surface electronic-structure trade-off between ethanol adsorption and CH3CO intermediate desorption. Herein, the Pd supported on N/S co-doped carbon (Pd@SNC) catalyst is synthesized, in which the doped S and N atoms could transfer moderate amounts electron to Pd, leading to opportune electron structure of Pd. Moreover, the moderate negative shift of d-band center demonstrate that the opportune Pd electron structure can strengthen adsorption of ethanol/OH− and promote the desorption of intermediate (CH3CO*), which may facilitate the kinetics. As a result, Pd@SNC exhibiting the highest catalytic activity for EOR (945.49 mA mgPd−1), surpassing to that of Pd@NC and Pd@C. Due to the fact that the electronic structure of Pd is properly regulated by co-doped N and S atoms, as shown by the theoretical calculation results, Pd@SNC exhibits the lowest reaction energy barrier of the dehydrogenation during the process of EOR.

Key words: Pd-based catalyst, Ethanol oxidation, Heteroatoms doping, Metal-support interaction, Electronic structure