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化学进展 2021, Vol. 33 Issue (7): 1238-1248 DOI: 10.7536/PC210218 前一篇   

• 综述 •

具有三维特殊形貌/纳米结构的Pt基电催化剂

唐向春, 陈家祥, 刘利娜, 廖世军*()   

  1. 华南理工大学化学与化工学院 广州 510641
  • 收稿日期:2021-02-20 修回日期:2021-04-05 出版日期:2021-07-20 发布日期:2021-06-12
  • 通讯作者: 廖世军
  • 基金资助:
    国家重点研发计划项目(2017YFB0102900); 国家重点研发计划项目(2016YFB0101201); 国家自然科学基金项目(51971094); 国家自然科学基金项目(21476088); 国家自然科学基金项目(21776104); 广东省自然科学基金项目(2015A030312007)
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Pt-Based Electrocatalysts with Special Three-Dimensional Morphology or Nanostructure

Xiangchun Tang, Jiaxiang Chen, Lina Liu, Shijun Liao*()   

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, China
  • Received:2021-02-20 Revised:2021-04-05 Online:2021-07-20 Published:2021-06-12
  • Contact: Shijun Liao
  • About author:
    * Corresponding author e-mail:
  • Supported by:
    National Key Research and Development Program of China(2017YFB0102900); National Key Research and Development Program of China(2016YFB0101201); National Natural Science Foundation of China(51971094); National Natural Science Foundation of China(21476088); National Natural Science Foundation of China(21776104); Guangdong Provincial Department of Science and Technology(2015A030312007)

近年来我国的燃料电池技术及产业发展迅猛,然而大量使用Pt基贵金属催化剂所带来的高成本问题仍然是制约其发展最为重要的因素之一。开发和研究具有更高催化效率的Pt基贵金属催化剂对于促进燃料电池技术和产业的发展具有十分重要的意义。具有三维特殊形貌/纳米结构的Pt基催化剂是近年来出现的一类极其重要的低Pt催化剂,这类催化剂由于具有特殊的形貌和结构,其Pt质量比活性可以数倍数十倍地高于目前广泛使用的Pt碳类催化剂。本文着重介绍了近年来具有三维特殊形貌的Pt基催化剂(如纳米框架结构、花状结构、纳米笼结构、海胆结构等)的研究进展以及这类催化剂在燃料电池中的应用的研究进展。同时,指出了这类催化剂尚存在的不足和面临的挑战,并对这类催化剂的未来的研究和应用作了展望。

关键词： 燃料电池, Pt基催化剂, 三维形貌, 催化活性, 稳定性

Fuel cell technology and its industrialization have been developed rapidly in China in recent years. However, the high cost of the fuel cell caused mainly by the using of precious Pt catalysts is still one of the most important factors restricting the development of fuel cell commercialization. It is of great significance to develop low Pt catalysts with much higher catalytic efficiency and lower Pt loadings. In recent years, Pt-based catalysts with three-dimensional morphology or/nanostructures have been emerged as a type of ultra-important low Pt catalysts, due to their special morphology/structures, their catalytic activity are usually much higher than that of the widely used Pt/C catalysts. In this paper, the research progress of Pt-based catalysts with special three-dimensional morphology(such as nanoframe structure, flower-like structure, nanocage structure, sea urchin structure, etc.) and their applications in fuel cells are reviewed. Meanwhile, some weaknesses and challenges of these catalysts are concluded. Furthermore, the future development and application of these catalysts are prospected.

Contents

1 Introduction

2 Pt-based electrocatalysts with three-dimensional nanoframe structures

3 Pt-based electrocatalysts with three-dimensional nanoflower morphologies

4 Pt-based electrocatalysts with other three-dimensional structures

5 Conclusions and outlooks

Key words: fuel cell, Pt-based catalysts, three-dimensional morphology, catalytic activity, stability
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图1 贵金属纳米框架的两种常用合成方法[21]
Fig. 1 Two usually used methods for the synthesis of metal nanoframes[21]. Copyright 2016, Oxford Univ Press
图2 Pt立方体纳米框架合成示意图[26]
Fig.2 Schematic diagram of synthesis of Pt cube nanoframe[26]. Copyright 2016, Wiley
图3 PtNi3纳米多面体演变成Pt3Ni NFs/C-with Pt-skin的结构示意图及对应的TEM图[16]
Fig. 3 Structural schematic diagram of PtNi3nanometer polyhedron evolving into Pt3Ni NFs/C-With Pt-Skin and corresponding TEM images[16]. Copyright 2014, AAAS
图4 (a,b)Pt/C,solid PtNi/C,Pt3Ni/C 纳米框架,Pt3Ni/C 纳米框架/IL在0.95V下的面积比活性与质量比活性比较(c)Pt3Ni NFs/C-with Pt-skin催化剂的电化学稳定性测试及(d,e)Pt3Ni NFs/C-with Pt-skin的HRTEM图[16]
Fig. 4 (a,b) Comparison of specific activity and mass activity of Pt/C, solid PtNi/C, Pt3Ni/C nanoframe, Pt3Ni/C nanoframes /IL at 0.95V (c) Electrochemical stability test of Pt3Ni NFS /C-with Pt-Skin catalyst and (d,e)HRTEM images of Pt3Ni NFS/C- with Pt-Skin catalyst[16]. Copyright 2014, AAAS
图5 PtCu八角纳米框架的(a)TEM图;(b)a的放大图;(c)球差TEM图;(d)HAADF-STEM图EDS mapping图[33]
Fig. 5 (a) TEM image of the PtCu octagonal nanoframe; (b) An enlarged view of image a; (c) Spherical aberration TEM image; (d) Images of the HAADF-STEM and EDS mapping[33]. Copyright 2016, Wiley
图6 PtCu菱形十二面体纳米框架的TEM图[34]
Fig. 6 TEM image of PtCu rhombus dodecahedron nanoframe[34]. Copyright 2015, RSC
图7 PtCu@PtCuNi核壳纳米框架的合成示意图[35]
Fig. 7 Synthesis schematic diagram of PtCu@PtCuNi core-shell nanoframe[35]. Copyright 2017, ACS
图8 PtCu@PtCuNi催化剂的电化学性能图[35]
Fig. 8 Electrochemical performance diagram of PtCu@PtCuNi catalyst[35]. Copyright 2017, ACS
图9 O-PtCu NFs/C的合成示意图(a)及对应不同阶段的TEM图(b~d)[39]
Fig. 9 Synthesis diagram of O-PtCu NFs/C (a) and corresponding TEM images of different stages (b~d)[39]. Copyright 2020, ACS
图10 Pt、D-PtCu NFs/C及O-PtCu NFs/C的(a)CV曲线,(b)ORR极化曲线,(c,d)ADT测试前后的SA和MA比较[39]
Fig. 10 (a)CV curves, (b) ORR polarization curves, (c,d) SA and MA comparison of Pt, D-PtCu NFs/C and O-PtCu NFs/C before and after ADT test[39]. Copyright 2020, ACS
图11 Pt66Ni34 NFs的合成示意图[50]
Fig. 11 Schematic illustration of the formation mechanism of Pt66Ni34 NFs[50]. Copyright 2018, Elsevier
图12 Pt66Ni34 NFs的(a)低倍率TEM图(b)中倍率TEM图(c)高倍率TEM图(d,e)高分辨透射电镜图(f)对应的选区电子衍射(SAED)图[50]
Fig. 12 Low- (a) medium- (b) high- (c) magnification and high-resolution (d,e) TEM images of Pt66Ni34 NFs (f) The corresponding SAED pattern[50]. Copyright 2018, Elsevier
图13 Pd@Pt核壳纳米粒子的(a)HAADF 图,(b)BF图,(c)Pd,和(d)Pd的EDX分布图,以及(e)Pd-Pt界面的原子分辨率的HAADF-STEM 图[68]
Fig. 13 Simultaneously acquired (a) HAADF and (b) BF images of Pd-Pt core-shell nanoparticles. (c) Pd and (d) Pt signal of EDX mapping. (e) Atomically resolved HAADF-STEM image of Pd-Pt interface[68]. Copyright 2016, ACS
图14 G-PtNi NS的形成过程示意图[78]
Fig. 14 Synthesis schematic diagram of G-PtNi NS[78]. Copyright 2018, RSC
表1 不同形貌的Pt基催化剂的ORR活性及ECSA
Table 1 ORR activity and ECSA of Pt-based catalysts with different morphologies
3D morphology Catalyst Electrolyte MAa@0.9V
(A/mgPt)		 SAb@0.9V
(mA/c m Pt 2)		 ECSAc
(m2/gPt)		 ref
nanoframe Pt frame/C 0.1 M HClO4 0.45 0.53 85 26
Pt3Ni NFs/C 0.1 M HClO4 5.70 NAd NAd 16
PtNi mutiframes/C 0.1 M HClO4 5.03 7.06 71 24
PtCu OFAs 0.1 M HClO4 3.26 5.98 55 33
PtCu@PtCuNi
Dentrite@Frame		 0.1 M HClO4 2.45 7.20 34 35
Co-PtCu RNF/C 0.1 M HClO4 1.56 5.03 31 36
PtCu RNF/C 0.1 M HClO4 0.77 2.56 30 36
Pt3Cu/TiN 0.1 M HClO4 2.43 5.32 46 37
O-PtCu NF/C 0.1 M HClO4 2.47 4.69 35 39
PtCo NFs 1.0 M KOH 0.55 1.09 50 40
PtCo ND-NFs 0.1 M HClO4 0.94 2.62 36 41
nanoflower Pt/C nanoflower 0.1 M HClO4 0.23 1.00 23 86
PtNiCo nanoflower 0.1 M HClO4 0.50 2.47 22 87
Au-Pd-Pt NFs/rGO 0.1 M HClO4 0.21 0.48 44 88
Pt-Pd-Ag nanoflowers 0.1 M HClO4 0.21 0.526 39 89
other 3D Pt-Pd-Ni 0.1 M HClO4 1.17 3.80 32 90
Pt nanocage 0.1 M HClO4 1.12 2.48 45 68
SOCT CuPt nanocage 0.1 M HClO4 0.30 0.70 43 91
G-PtNi 0.1 M HClO4 1.15 1.95 77 78
PtNi hollow nanochains 0.1 M HClO4 0.34 0.48 71 71
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