铂基空心纳米框架的合成及其在直接醇燃料电池中的应用

doi:10.3866/PKU.WHXB202009035

物理化学学报 >> 2021, Vol. 37 >> Issue (9): 2009035.doi: 10.3866/PKU.WHXB202009035

所属专题：燃料电池

铂基空心纳米框架的合成及其在直接醇燃料电池中的应用

黄磊, Zaman Shahid, 王志同, 牛慧婷, 游波, 夏宝玉()

华中科技大学化学与化工学院，能量转换与存储材料化学教育部重点实验室，材料化学与服役失效湖北省重点实验室，武汉光电国家研究中心，武汉 430074

收稿日期:2020-09-09 录用日期:2020-10-12 发布日期:2020-10-23
通讯作者: 夏宝玉 E-mail:byxia@hust.edu.cn
作者简介:Dr. Bao Yu Xia is currently a full professor in the School of Chemistry and Chemical Engineering at Huazhong University of Science and Technology (HUST), China. He received his Ph.D. degree in materials science at Shanghai Jiao Tong University (SJTU) in 2010. He worked at Nanyang Technological University (NTU) from 2011 to 2016. His research involves functional materials in sustainable energy and clean environment technologies including fuel cells, batteries, and electrocatalysis
基金资助:
国家自然科学基金(22075092);华中科技大学学术前沿青年团队项目(2018QYTD15);国家青年千人计划资助

Synthesis and Application of Platinum-Based Hollow Nanoframes for Direct Alcohol Fuel Cells

Lei Huang, Shahid Zaman, Zhitong Wang, Huiting Niu, Bo You, Bao Yu Xia()

Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Key Laboratory of Material Chemistry and Service Failure, Wuhan National Laboratory for Optoelectronics, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

Received:2020-09-09 Accepted:2020-10-12 Published:2020-10-23
Contact: Bao Yu Xia E-mail:byxia@hust.edu.cn
About author:Bao Yu Xia, Email: byxia@hust.edu.cn
Supported by:
the National Natural Science Foundation of China(22075092);the Program for HUST Academic Frontier Youth Team(2018QYTD15);the National 1000 Young Talents Program of China

摘要/Abstract

摘要：

与其他铂基纳米晶体材料相比，铂基纳米框架催化剂因其独特的结构特征和优异的催化性能引起研究者的广泛关注。开放的空间结构设计和组分可控调制不仅提高了铂的原子利用率，而且能在减少铂消耗的同时改善其电催化活性。本文简要综述了铂基纳米框架电催化剂的最新进展。在介绍不同的铂基纳米框架制备和蚀刻策略之后，也对框架晶体的结构演变及其在醇燃料电池中氧还原反应和醇氧化反应的催化应用进行了总结。此外，基于纳米框架材料的类型、合成方法、结构形态和催化性能，对铂基纳米框架的当前存在的挑战和未来的发展前景进行了总结和展望。基于铂基纳米框架材料的改进机制和规模化制备策略，我们相信纳米框架材料将会在醇燃料电池等技术中发挥更大作用。

关键词: 燃料电池, 电催化剂, 铂合金, 纳米框架, 蚀刻

Abstract:

Although platinum (Pt)-based catalysts are suffering from high costs and limited reserves, they are still irreplaceable in a short period of time in terms of catalytic performance. Structural optimization, composition regulation and carrier modification are the common strategies to improve the activity and stability of Pt-based catalyst. Strikingly, the morphological evolution of Pt-based electrocatalyst into nanoframes (NFs) have attracted wide attention to reduce the Pt consumption and improve the electrocatalytic activity simultaneously. Contrary to Pt-based solid nanocrystalline materials, Pt-based NFs have many advantages in higher atomic utilization, open space structure and larger specific surface area, which facilitate electron transfer, mass transport and weaken surface adsorption by more unsaturated coordination sites. Here we introduce the detailed preparation strategies of Pt-based NFs with different etching methods (oxidative etching, chemical etching, galvanic replacement and carbon monoxide etching), crystal structure evolution and formation mechanism, efficient applications for oxygen reduction reaction (ORR), methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) in direct alcohol fuel cells (DAFCs). Based on the high-efficiency atom utilization, open space structure and diverse alloy composition, Pt-based NFs exhibit superior activity, stability and anti-poisoning than commercial counterparts in the application of DAFCs. The current challenges and future development of Pt-based NFs are prospected on the type of NFs materials, synthesis and etching methods, crystal control and catalytic performance. We propose a series of improvement mechanisms of Pt-based NFs, such as small size effect, high-energy facets, Pt-skin construction and Pt-C integration, thereby weakening the molecule absorption, increasing the Pt utilization, strengthening the intrinsic stability, and alleviating the metal dissolution and support corrosion. Additionally, the scale-up synthesis of catalytic materials, membrane electrodes assembly, and development of the start-stop system and the circulation system design are essential for the commercial application of Pt-based NFs and industrial manufacturing of DAFCs. More importantly, the reaction mechanism, active site distribution and dynamic changes in the catalytic material during the catalytic reaction are crucial to further explain the maintenance and evolution of catalytic performance, which will open a window to elucidate the improvement mechanism of the catalyst in the fuel cell reactions. This review work would promote continuous upgradations and understandings on Pt-based NFs in the future development of DAFCs.

Key words: Fuel cell, Electrocatalyst, Platinum alloy, Nanoframe, Etching

黄磊, Zaman Shahid, 王志同, 牛慧婷, 游波, 夏宝玉. 铂基空心纳米框架的合成及其在直接醇燃料电池中的应用[J]. 物理化学学报, 2021, 37(9), 2009035. doi: 10.3866/PKU.WHXB202009035

Lei Huang, Shahid Zaman, Zhitong Wang, Huiting Niu, Bo You, Bao Yu Xia. Synthesis and Application of Platinum-Based Hollow Nanoframes for Direct Alcohol Fuel Cells[J]. Acta Phys. -Chim. Sin. 2021, 37(9), 2009035. doi: 10.3866/PKU.WHXB202009035

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202009035

https://www.whxb.pku.edu.cn/CN/Y2021/V37/I9/2009035

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Synthesis method	Shape and composition of Pt-based NFs
Oxidative etching	Rhombic dodecahedral PtCu ^32-35	Rhombic dodecahedral PtCuNi ³⁶	Cubic PtPdCu ³⁷
	Octopod cubic PtCu ³⁸	Five-Fold-Twinned PtCu ³⁹	Concave cubic PtCu ⁴⁰
	Rhombic dodecahedral PtCuRh ⁴¹	Octahedral PtCu ^{17, 42}	Five-Fold-Twinned PtCuMn ⁴³
Chemical etching	Rhombic dodecahedral PtNi ^44-47	Vertex-Reinforced PtCuCo ²⁴	Truncated octahedral PtNiAu ⁴⁸
	Spiny rhombic dodecahedral PtCu ⁴⁹	Vertex-Reinforced PtCuRh ⁵⁰	Octahedral PtNi ^{26, 51}
	Rhombic dodecahedral PtRuNi ⁵²	Rhombic dodecahedral PtCuNi ³⁶	Skeletal octahedral PtNi ⁵³
	Rhombic dodecahedral PtRhNi ⁵⁴	Rhombic dodecahedral PtCo ⁵⁵	Polyhedral PtCo ⁵⁶
	Core-Shell AgAuPt ⁵⁷	Truncated octahedral PtAu ⁵⁸	PtAu bipyramid ⁵⁹
	Ultra-Small PtPdRhAg ⁶⁰	Porous Pt-Bi(OH)₃ ⁶¹	Dendrite-Embedded PtNi ⁶²
Galvanic replacement	Cubic PtPdCu ³⁷	Triangular PtAg ⁶³
CO etching	Tetrahexahedral PtNi ⁶⁴

Electrocatalytic reaction	Shape and composition of Pt-based NFs
Oxygen reduction	Rhombic dodecahedral PtCu ^32-34	Rhombic dodecahedral PtCuNi ³⁶	Cubic PtPdCu ³⁷
	Octopod cubic PtCu ³⁸	Rhombic dodecahedral PtNi ^{44-47, 83}	Cubic Pt ^{25, 84}
	Five-Fold-Twinned PtCu ³⁹	Rhombic dodecahedral PtCo ^{55, 85}	Tetrahexahedral PtNi ⁶⁴
	Vertex-Reinforced PtCuCo ²⁴	Spiny rhombic dodecahedral PtCu ⁴⁹	Skeletal octahedral PtNi ⁵³
	Octahedral PtCu ⁴²	Five-Fold-Twinned PtCuMn ⁴³	Dendrite-Embedded PtNi ⁶²
Methanol oxidation	Rhombic dodecahedral PtCuRh ⁴¹	Rhombic dodecahedral PtCu ^{34, 35}	Cubic PtCu ⁸⁶
	Concave cubic PtCu ⁴⁰	Five-Fold-Twinned PtCu ³⁹	Tetrahexahedral PtNi ^{23, 64}
	Vertex-Reinforced PtCuCo ²⁴	Octahedral PtNi ²⁶	Truncated octahedronal PtNiAu ⁴⁸
	Rhombic dodecahedral PtRuNi ⁵²	Rhombic dodecahedral PtCo ⁵⁵	Octahedral PtCu ⁴²
	Core-Shell AgAuPt ⁵⁷	truncated octahedral PtAu ⁵⁸	AuPt bipyramid ⁵⁹
	Ultra-Small PtPdRhAg ⁶⁰
Ethanol oxidation	Rhombic dodecahedral PtCuRh ⁴¹	Vertex-Reinforced PtCuRh ⁵⁰	Porous Pt-Bi(OH)₃ ⁶¹
Ethanol oxidation	Rhombic dodecahedral PtRhNi ⁵⁴

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铂基空心纳米框架的合成及其在直接醇燃料电池中的应用

Synthesis and Application of Platinum-Based Hollow Nanoframes for Direct Alcohol Fuel Cells

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