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

Abstract

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

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.

Figures/Tables 14

References 106

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

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