Zn单原子微环境结构的调控: 促进氧还原反应的ZnN4P/C活性位点

doi:10.1016/S1872-2067(22)64089-0

催化学报 ›› 2022, Vol. 43 ›› Issue (8): 2193-2201.DOI: 10.1016/S1872-2067(22)64089-0

Zn单原子微环境结构的调控: 促进氧还原反应的ZnN₄P/C活性位点

Syed Shoaib Ahmad Shah^a^,^b, Tayyaba Najam^a^,^c^,^*(), 杨姣^a, Muhammad Sufyan Javed^d, 彭立山^a^,^e^,^f^,^#(), 魏子栋^a^,^$()

^a重庆大学化学与化工学院, 重庆400044, 中国
^b西南大学材料与能源学院, 发光分析与分子传感教育部重点实验室, 重庆400715, 中国
^c深圳大学化学与环境工程学院, 广东深圳518060, 中国
^d兰州大学物理科学与技术学院, 甘肃兰州730000, 中国
^e奥克兰大学化学科学学院, 奥克兰, 新西兰
^f中国科学院赣江创新研究院, 江西赣州341100, 中国

收稿日期:2022-02-23 接受日期:2022-03-24 出版日期:2022-08-18 发布日期:2022-06-20
通讯作者: Tayyaba Najam,彭立山,魏子栋
基金资助:
国家自然科学基金(22075033);国家自然科学基金(21761162015);国家自然科学基金(91834301)

Modulating the microenvironment structure of single Zn atom: ZnN₄P/C active site for boosted oxygen reduction reaction

Syed Shoaib Ahmad Shah^a^,^b, Tayyaba Najam^a^,^c^,^*(), Jiao Yang^a, Muhammad Sufyan Javed^d, Lishan Peng^a^,^e^,^f^,^#(), Zidong Wei^a^,^$()

^aSchool of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China
^bKey Laboratory of Luminescence Analysis and Molecular Sensing, Ministry of Education, School of Materials and Energy, Southwest University, Chongqing 400715, China
^cCollege of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, China
^dSchool of Physical Science and Technology, Lanzhou University, Lanzhou 730000, Gansu, China
^eSchool of Chemical Sciences, The University of Auckland, Auckland 1142, New Zealand
^fGanjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341100, Jiangxi, China

Received:2022-02-23 Accepted:2022-03-24 Online:2022-08-18 Published:2022-06-20
Contact: Tayyaba Najam, Lishan Peng, Zidong Wei
Supported by:
National Natural Science Foundation of China(22075033);National Natural Science Foundation of China(21761162015);National Natural Science Foundation of China(91834301)

摘要/Abstract

摘要：

日益严峻的能源危机及环境污染问题促使人们研发清洁能源转换和存储技术. 燃料电池和金属-空气电池因功率密度高、操作方便而成为备受关注的能量转换器件. 氧还原反应(ORR)是燃料电池和金属-空气电池中必不可少的关键反应. 然而, 由于氧还原反应的动力学缓慢, 极大地限制了反应的快速进行. Pt基电催化剂虽然表现出良好的ORR活性, 但稀缺性和稳定性差的缺点制约了其在燃料电池和金属空气电池领域的大规模商业化应用. 单原子催化剂(SACs)由于具有丰富的活性位点和几乎100%的金属利用率而成为电催化研究的热点. SACs的几何构型和电子构型很大程度取决于其独特的原子微环境调制(MEM), 包括催化中心的局部配位环境和电子状态. 因此, SACs的活性、选择性和稳定性与它们的MEM直接相关. 由于传统催化剂缺乏结构的精确解析和可定制性, 理解和调控催化位点的MEM对多相催化反应性能的影响仍然具有挑战性和局限性.

本文通过两步热解法可控制备N, P双掺杂碳基底负载Zn单原子催化剂(Zn-N₄P/C), 实现对Zn单原子微环境的原子级调控. 实验和理论计算研究表明, N/P配位对Zn单原子催化剂电子结构具有协同调控的作用, 从而改变Zn周围的局部电荷分布, 降低ORR基元反应的势垒. XPS结果显示, Zn-N₄P/C中N和P同时存在, 且其Zn的结合能相对ZnN₄/C向高结合能方向偏移, 表明引入的P与相邻的ZnN₄间发生电荷转移, 影响了Zn单原子的电子结构. XAS结果表明, ZnN₄P/C的结构是由位于第二壳层的P与Zn-N₄相连构成, 且由于P的电负性更强, 导致相邻Zn-N的电子转移到N‒P键, Zn‒N键的键长变长, Zn的价态显著升高. Zn的K边小波转换结果表明, ZnN₄P/C催化剂中Zn原子的最大等高强度中心相对于ZnPc发生了偏移, 进一步表明P的引入对Zn的电子结构产生了影响. 优化后的ZnN₄P/C催化剂在0.1 mol·L^‒1 KOH电解质中的ORR半波电位为0.861 V, 比单金属ZnN₄/C和Pt/C(20%)更高. 此外, 将该催化剂用于锌空电池的阴极ORR催化剂, 所得电池的最大峰值功率密度(249.6 mW cm^‒2)、比电容(779 mAh g^‒1)均优于贵金属Pt/C催化剂, 且该电池能够在10 mA cm^‒2条件下可稳定充放电循环150 h. DFT计算结果表明, ORR活性大幅提高可归因于P的掺杂使电荷在N和Zn周围富集, 从而优化了活性中心与O₂结合能, 并加快了ORR反应的电子转移速度.

关键词: N, P掺杂, 氧还原, 锌-空电池, 单原子催化剂, 微环境调控

Abstract:

The electronic structure of catalytic active sites can be influenced by modulating the coordination bonding of the central single metal atom, but it is difficult to achieve. Herein, we reported the single Zn-atom incorporated dual doped P, N carbon framework (Zn-N₄P/C) for ORR via engineering the surrounding coordination environment of active centers. The Zn-N₄P/C catalyst exhibited comparable ORR activity (E_1/2 = 0.86 V) and significantly better ORR stability than that of Pt/C catalyst. It also shows respectable performance in terms of maximum peak power density (249.6 mW cm^-2), specific capacitance (779 mAh g^-1), and charge-discharge cycling stability for 150 hours in Zn-air battery. The high catalytic activity is attributed to the uniform active sites, tunable electronic/geometric configuration, optimized intrinsic activity, and faster mass transfer during ORR-pathway. Further, theoretical results exposed that the Zn-N₄P configuration is more electrochemically active as compared to Zn-N₄ structure for the oxygen reduction reaction.

Key words: N-, P-doping, Oxygen reduction reaction, Zn-air battery, Single-atom catalyst, Microenvironment modulation

Syed Shoaib Ahmad Shah, Tayyaba Najam, 杨姣, Muhammad Sufyan Javed, 彭立山, 魏子栋. Zn单原子微环境结构的调控: 促进氧还原反应的ZnN₄P/C活性位点[J]. 催化学报, 2022, 43(8): 2193-2201.

Syed Shoaib Ahmad Shah, Tayyaba Najam, Jiao Yang, Muhammad Sufyan Javed, Lishan Peng, Zidong Wei. Modulating the microenvironment structure of single Zn atom: ZnN₄P/C active site for boosted oxygen reduction reaction[J]. Chinese Journal of Catalysis, 2022, 43(8): 2193-2201.

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图/表 6

Scheme 1. Schematic illustration for the fabrication of ZnN4P/C catalyst.

Fig. 1. (a,b) TEM and HR-TEM images of ZnN4P/C. (c) Aberration corrected HAADF-STEM image of ZnN4P/C. (d) HAADF-TEM image and (e) Corresponding element mapping images for ZnN4P/C.

Fig. 2. (a) N2 adsorption-desorption isotherms of ZnN4P/C and ZnN4/C (insert: pore-size distribution). (b) High-resolution XPS spectra of Zn 2p for ZnN4P/C and ZnN4/C. (c) Zn K-edge XANES spectra of ZnN4P/C, ZnO, ZnPc and Zn-foil. (d) Fourier transforms of k3-weighted Zn K-edge EXAFS of ZnN4P/C, ZnO, ZnPc and Zn-foil. (e) Corresponding EXAFS fitting in k and R space foil (inset: suggested structural model of ZnN4P/C). (f) Wavelet transforms for the k3-weighted Zn K-edge EXAFS signals of Zn-foil, ZnO, ZnPc, and ZnN4P/C.

Fig. 3. (a) RRDE curves and corresponding peroxide (%). (b) Tafel plots. (c) Comparative study of half-wave potential calculated from ORR-LSV curves and kinetic current density (Jk). (d) The electron transferred number calculated from RRDE test and corresponding peroxide yield. (e) Comparative study of long-term stability test carried out for 8000 CV-cycles.

Fig. 4. Comparative study of Zn-air battery performance. (a) The peak power density and corresponding discharge voltage curves. (b) Galvanostatic discharge voltage curves at various current densities. (c) Charge-discharge cycling performance at 10 mA cm-2 of current density. (d) Specific capacitance curves calculated at a current density of 20 mA/cm2.

Fig. 5. (a,b) Calculated charge density difference of ZnN4/C and ZnN4P/C (blue and yellow regions represent electron depletion and electron accumulation, respectively). (c) Partial density of states (PDOS) for Zn atoms of ZnN4/C, and ZnN4P/C (inset: structural models of ZnN4/C and ZnN4P/C). (d) Gibbs-free energy diagram of ZnN4/C, and ZnN4P/C calculated at U = 0 V. (e) Gibbs-free energy for the elementary reaction of ORR on ZnN4/C and ZnN4P/C models.

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Zn单原子微环境结构的调控: 促进氧还原反应的ZnN₄P/C活性位点

Modulating the microenvironment structure of single Zn atom: ZnN₄P/C active site for boosted oxygen reduction reaction

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