物理化学学报 >> 2024, Vol. 40 >> Issue (7): 2306029.doi: 10.3866/PKU.WHXB202306029

所属专题: 电化学前沿

综述 上一篇    下一篇

金属纳米晶体电催化剂的电化学合成:原理、应用与挑战

赵路甜1, 郭杨格1, 罗柳轩1, 闫晓晖1, 沈水云1,2,*(), 章俊良1,2   

  1. 1 上海交通大学机械与动力工程学院, 燃料电池研究所, 上海 200240
    2 上海交通大学, 能源与机械工程教育部重点实验室, 上海 200240
  • 收稿日期:2023-06-14 修回日期:2023-07-30 录用日期:2023-08-23 发布日期:2023-12-01
  • 通讯作者: Email: shuiyun_shen@sjtu.edu.cn (沈水云)
  • 基金资助:
    国家重点研发计划(2021YFB4001301); 上海交通大学“深蓝计划”基金(SL2021ZD105)

Electrochemical Synthesis for Metallic Nanocrystal Electrocatalysts: Principle, Application and Challenge

Lutian Zhao1, Yangge Guo1, Liuxuan Luo1, Xiaohui Yan1, Shuiyun Shen1,2,*(), Junliang Zhang1,2   

  1. 1 Institute of Fuel Cells, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
    2 MOE Key Laboratory of Power & Machinery Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
  • Received:2023-06-14 Revised:2023-07-30 Accepted:2023-08-23 Published:2023-12-01
  • Contact: Email: shuiyun_shen@sjtu.edu.cn (Shuiyun Shen)
  • Supported by:
    the National Key Research and Development Program of China(2021YFB4001301); the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2021ZD105)

摘要:

金属纳米晶体催化剂由于其独特的电子性质,在电化学能源转化反应中表现出优异的催化性能。为了提升催化剂的活性和耐久性,需要精确调控其晶体结构和形貌。然而,传统的制备方法往往需要严苛的条件,如高温、高压和特定的有机物,以控制晶体的生成和生长过程。这限制了能够合成的金属基催化剂的种类,并导致清洗复杂和有机物残留的问题。电化学方法通过电化学响应获取体系过程信息,并可以通过调控参数来调节晶体的生长,特别是非水体系的电化学方法为活泼过渡金属催化剂的合成提供了可行的途径。然而,电化学方法对所处体系的变化十分敏感,这使得从小面积电极制备催化剂扩展到电极级别的催化层制备面临严峻挑战,因为这一转变会导致电化学机理和由此带来的合成方法条件的变化。本文基于晶体生长机理,探讨了电化学制备金属晶体的可行性,并综述了电化学沉积方法制备纳米级金属电催化剂的研究。最后,对电化学制备纳米级金属晶体催化剂面临的挑战进行了分析,并提出了实现更广泛应用的建议。通过电化学方法制备金属纳米晶体催化剂在提高制备的可控性、减少有机物残留等方面具有潜在的优势,但也需要克服相关技术和方法上的难题,以实现其在能源转化等领域的应用。

关键词: 电化学能量转化反应, 纳米金属电催化剂, 高催化性能, 电化学合成, 晶体生长机理

Abstract:

Nanoscale metallic catalysts are garnering increased attention in the advancement of electrochemical energy conversion technologies. The precise control of nanocrystal morphology, size, and crystalline structures offers the ability to manipulate electronic properties and enhance intrinsic catalytic performance. Consequently, a profound understanding of the nanocrystal growth mechanism becomes imperative for the design and production of highly active catalysts. However, mechanism studies in colloidal methods generally depend on operando technics and the development is hindered by expensive cost and limited resources. And high-temperature or high-pressure reaction conditions always bring trouble for the application of the equipment, so the in situ methods have been widely used. While ex situ methods need to detach the samples from the reaction environment, which might lose information about the process and thus fail to reflect the real situation. Furthermore, in conventional methods, the use of macromolecular organics to regulate crystal morphology results in intricate post-treatment processes, and any residual substances can adversely affect catalyst performance. Electrochemical synthesis offers a clean and controllable protocol for producing metallic nanocrystals and supported heterogeneous nanoparticle catalysts. In this review, building upon the classic principles of crystal growth in chemical colloidal methods and electrodeposition, it is proposed that the processes occurring during crystal formation could be visualized or monitored through electrochemical tests. By fine-tuning electrochemical parameters and refining deposition procedures, nucleation density and growth rates along specific facet orientations of nanocrystals can be precisely managed. Electrochemical signals provide insights into in situ reduction and deposition behaviors at the electrode-electrolyte interfaces through professional analysis. The direct loading of nanocrystals onto substrates amplifies their synergistic effects, mitigates exfoliation issues, and consequently enhances catalytic activity and stability. Additionally, due to its broader potential window compared to H2O, non-aqueous liquids hold promise as a solution for preparing active metals and alloys that exhibit distinctive catalytic performance. Furthermore, electrochemical methods facilitate the synthesis of compounds composed of metallic and nonmetal elements, including metal oxides and phosphides. Thus, electrochemical techniques are poised to offer potential high-performance nanoscale metallic catalysts along with profound insights into the crystal growth mechanism. Nevertheless, a critical challenge hindering the application of electrochemical methods lies in bridging the considerable gap between catalysts and the preparation of electrode-level catalyst layers. The electrochemical signal proves highly sensitive to variations in the reaction environment, and discrepancies in electrode and system properties can lead to distinct electrochemical responses. Consequently, thorough investigations are imperative to address these issues.

Key words: Electrochemical energy conversion reaction, Nanoscale metallic electrocatalyst, High catalytic performance, Electrochemical synthesis, Crystal growth mechanism