快速微波合成铂铜合金作为高效氧还原电催化剂

doi:10.19799/j.cnki.2095-4239.2024.1135

摘要/Abstract

摘要：

氧还原反应(ORR)动力学迟缓，质子交换膜燃料电池(PEMFC)阴极需要消耗大量的贵金属铂(Pt)。然而，Pt的稀缺性以及商业Pt/C催化剂的高成本、低ORR活性、差稳定性等问题，严重制约了PEMFC的大规模应用。因此，亟需寻找合适策略以开发具有优异活性、高稳定性、低Pt用量的高效实用催化剂。本工作发展了一种快速微波还原的方法，合成了碳负载的铂铜合金纳米颗粒(PtCu/C)催化剂。透射电镜结果显示，PtCu纳米颗粒均匀分布在碳载体表面，其平均粒径约为2.7 nm，纳米颗粒中Pt、Cu均匀分布，形成了两个原子层厚度的富Pt表面结构；X射线衍射证实了PtCu合金的形成；X射线光电子能谱表明Cu向Pt进行了电子转移，产生了电子相互作用。进一步，系统考察了前体混合物中Pt∶Cu摩尔比以及微波反应的温度、时间、功率等对制备催化剂催化活性的影响。电化学测试结果表明，优化的PtCu/C催化剂在0.9 V (vs. RHE)处的质量活性和面积活性分别为0.280 A/mg和0.346 mA/cm²，均优于商业Pt/C催化剂的0.150 A/mg和0.213 mA/cm²，且稳定性进一步提升，PtCu/C催化剂提高的活性和稳定性主要归因于小粒径的PtCu纳米颗粒、合金化以及富Pt表面结构等。

关键词: 快速微波还原, 铂铜合金, 电催化剂, 氧还原反应

Abstract:

The oxygen reduction reaction (ORR) exhibits sluggish kinetics, leading to substantial platinum (Pt) consumption at the cathodes of proton exchange membrane fuel cells (PEMFCs). However, the scarcity of Pt, along with the high cost, low ORR activity, and poor stability of commercial Pt/C catalysts, severely restricts the large-scale application of PEMFCs. Therefore, the development of efficient and practical catalysts with excellent activity, high stability, and reduced Pt usage is critical. Herein, a rapid microwave reduction method was developed to synthesize carbon-supported platinum-copper alloy nanoparticle (PtCu/C) catalysts. Transmission electron microscopy reveals that PtCu nanoparticles are uniformly distributed on the surface of the carbon support with an average particle size of 2.7 nm. Pt and Cu are evenly distributed within the nanoparticles, forming a Pt-rich surface structure with a thickness of two atomic layers. X-ray diffraction confirms the formation of PtCu alloy. X-ray photoelectron spectroscopy indicates electron transfer from Cu to Pt, facilitating electronic interactions. Furthermore, the effects of the Pt∶Cu molar ratio in the precursor mixture, along with the temperature, time, and power of the microwave reaction, on the catalytic activity are systematically investigated. Electrochemical test results suggest that the optimal PtCu/C catalyst exhibits mass and area activities of 0.280 A/mg and 0.346 mA/cm² at 0.9 V (vs. RHE), respectively, outperforming commercial Pt/C catalyst (0.15 A/mg and 0.213 mA/cm²). Additionally, the PtCu/C catalyst shows enhanced electrochemical stability. The improved activity and stability of the PtCu/C catalyst are mainly attributed to the small PtCu nanoparticle size, alloying effects, and Pt-rich surface structure.

Key words: rapid microwave reduction, platinum-copper alloy, electrocatalyst, oxygen reduction reaction

中图分类号:

O 646

袁程, 沈迁, 张瑞文, 张世明. 快速微波合成铂铜合金作为高效氧还原电催化剂[J]. 储能科学与技术, 2025, 14(3): 1133-1140.

Cheng YUAN, Qian SHEN, Ruiwen ZHANG, Shiming ZHANG. Rapid microwave synthesis of platinum-copper alloy as efficient oxygen reduction electrocatalyst[J]. Energy Storage Science and Technology, 2025, 14(3): 1133-1140.

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参考文献 31

1	RAHMAN A, FARROK O, HAQUE M M. Environmental impact of renewable energy source based electrical power plants: Solar, wind, hydroelectric, biomass, geothermal, tidal, ocean, and osmotic[J]. Renewable and Sustainable Energy Reviews, 2022, 161: 112279. DOI: 10.1016/j.rser.2022.112279.
2	李淼, 盖克荣, 周凤颖, 等. 低温燃料电池在汽车工程中的供储能特性分析[J]. 储能科学与技术, 2024, 13(7): 2483-2485. DOI: 10.19799/j.cnki.2095-4239.2024.0556.
	LI M, GAI K R, ZHOU F Y, et al. Analysis of energy supply and storage characteristics of fuel cells in automotive engineering[J]. Energy Storage Science and Technology, 2024, 13(7): 2483-2485. DOI: 10.19799/j.cnki.2095-4239.2024.0556.
3	TELLEZ-CRUZ M M, ESCORIHUELA J, SOLORZA-FERIA O, et al. Proton exchange membrane fuel cells (PEMFCs): Advances and challenges[J]. Polymers, 2021, 13(18): 3064. DOI: 10.3390/polym13183064.
4	OlABI A G, WILBERFORCE T, AlANAZI A, et al. Novel trends in proton exchange membrane fuel cells[J]. Energies, 2022, 15(14): 4949. DOI: 10.3390/en15144949.
5	CHEN Y Z, ZHANG S M, CHUNG-YEN JUNG J, et al. Carbons as low-platinum catalyst supports and non-noble catalysts for polymer electrolyte fuel cells[J]. Progress in Energy and Combustion Science, 2023, 98: 101101. DOI: 10.1016/j.pecs. 2023.101101.
6	孔晨华, 张建军, 李旺, 等. 燃料电池在无人机高压输电线路验电系统中的应用展望[J]. 储能科学与技术, 2024, 13(2): 492-494. DOI: 10.19799/j.cnki.2095-4239.2024.0012.
	KONG C H, ZHANG J J, LI W, et al. Application prospect of fuel cell in UAVS high voltage transmission line checking system[J]. Energy Storage Science and Technology, 2024, 13(2): 492-494. DOI: 10.19799/j.cnki.2095-4239.2024.0012.
7	胡冶州, 王双, 申涛, 等. 限域型贵金属氧还原反应电催化剂研究进展[J]. 储能科学与技术, 2022, 11(4): 1264-1277. DOI: 10.19799/j.cnki.2095-4239.2022.0108.
	HU Y Z, WANG S, SHEN T, et al. Recent progress in confined noble-metal electrocatalysts for oxygen reduction reaction[J]. Energy Storage Science and Technology, 2022, 11(4): 1264-1277. DOI: 10.19799/j.cnki.2095-4239.2022.0108.
8	CAI J L, CHEN J X, CHEN Y Z, et al. Engineering carbon semi-tubes supported platinum catalyst for efficient oxygen reduction electrocatalysis[J]. iScience, 2023, 26(5): 106730. DOI: 10.1016/j.isci.2023.106730.
9	ZAMAN S, HUANG L, DOUKA A I, et al. Oxygen reduction electrocatalysts toward practical fuel cells: Progress and perspectives[J]. Angewandte Chemie International Edition, 2021, 60(33): 17832-17852. DOI: 10.1002/anie.202016977.
10	AHN C Y, PARK J E, KIM S J, et al. Differences in the electrochemical performance of Pt-based catalysts used for polymer electrolyte membrane fuel cells in liquid half- and full-cells[J]. Chemical Reviews, 2021, 121(24): 15075-15140. DOI: 10.1021/acs.chemrev.0c01337.
11	CAO S, SUN T, LI J R, et al. The cathode catalysts of hydrogen fuel cell: From laboratory toward practical application[J]. Nano Research, 2022, 16(4): 4365-4380. DOI: 10.1007/s12274-022-5082-z.
12	RAO X B, ZHANG S M, ZHANG J J. Effectively controlling the nanostructures and active sites of non-noble carbon catalysts for improving oxygen reduction reaction[J]. Current Opinion in Electrochemistry, 2023, 42: 101416. DOI: 10.1016/j.coelec. 2023.101416.
13	YANG Z L, CHEN Y Z, ZHANG S M, et al. Identification and understanding of active sites of non-noble iron-nitrogen-carbon catalysts for oxygen reduction electrocatalysis[J]. Advanced Functional Materials, 2023, 33(26): 2215185. DOI: 10.1002/adfm. 202215185.
14	LIU L Q, RAO X B, ZHANG S M, et al. Insight into synergy for oxygen reduction electrocatalysis of iron-nitrogen-carbon[J]. Chem, 2024, 10(7): 1994-2030. DOI: 10.1016/j.chempr.2024.06.006.
15	CHEN M H, CHEN Y T, YANG Z L, et al. Synergy of staggered stacking confinement and microporous defect fixation for high-density atomic Fe^Ⅱ-N₄ oxygen reduction active sites[J]. Chinese Journal of Catalysis, 2022, 43(7): 1870-1878. DOI: 10.1016/s1872-2067(21)63992-x.
16	CAMPOS-ROLDAN C A, JONES D J, ROZIEREJ, et al. Platinum-rare earth alloy electrocatalysts for the oxygen reduction reaction: A brief overview[J]. ChemCatChem, 2022, 14(19): e202200334. DOI: 10.1002/cctc.202200334.
17	SUN L Y, CHEN Y Z, ZHANG R W, et al. Synergy of porous network nanostructuring and nonmetallic phosphorus alloying for efficient oxygen reduction of platinum[J]. Journal of Alloys and Compounds, 2024, 985: 173988. DOI: 10.1016/j.jallcom. 2024. 173988.
18	PARKASH A, JIA Z, TIAN T, et al. A new generation of platinum-copper electrocatalysts with ultra-low concentrations of platinum for oxygen-reduction reactions in alkaline media[J]. ChemistrySelect, 2020, 5(11): 3391-3397. DOI: 10.1002/slct.202000256.
19	YUAN C, ZHANG S M, ZHANG J J. Oxygen reduction electrocatalysis: From conventional to single-atomic platinum-based catalysts for proton exchange membrane fuel cells[J]. Frontiers in Energy, 2024, 18(2): 206-222. DOI: 10.1007/s11708-023-0907-3.
20	CHEN T, NINGF H, Qi J Z, et al. PtFeCoNiCu high-entropy solid solution alloy as highly efficient electrocatalyst for the oxygen reduction reaction[J]. iScience, 2023, 26(1): 105890. DOI: 10.1016/j.isci.2022.105890.
21	CHEN Y Z, ZHANG R W, SUN L Y, et al. Boron-alloyed porous network platinum nanospheres for efficient oxygen reduction in proton exchange membrane fuel cells[J]. Chemical Engineering Journal, 2024, 485: 149998. DOI: 10.1016/j.cej.2024.149998.
22	YANG C D, GAO Y, MA T, et al. Metal alloys-structured electrocatalysts: Metal-metal interactions, coordination microenvironments, and structural property-reactivity relationships[J]. Advanced Materials, 2023, 35(51): e2301836. DOI: 10.1002/adma.202301836.
23	KIM D G, SOHN Y, JANG I, et al. Formation mechanism of carbon-supported hollow PtNi nanoparticles via one-step preparations for use in the oxygen reduction reaction[J]. Catalysts, 2022. 12(5): 513. DOI: 10.3390/catal12050513.
24	LU B A, TIAN N, SUN S G. Surface structure effects of platinum-based catalysts for oxygen reduction reaction[J]. Current Opinion in Electrochemistry, 2017, 4(1): 76-82. DOI: 10.1016/j.coelec. 2017.09.024.
25	CHEN Y Z, ZHAO X, YAN H L, et al. Manipulating Pt-skin of porous network Pt-Cu alloy nanospheres toward efficient oxygen reduction[J]. Journal of Colloid and Interface Science, 2023, 652: 1006-1015. DOI: 10.1016/j.jcis.2023.08.134.
26	PARKASH A. Metal-organic framework derived ultralow-loading platinum-copper catalyst: A highly active and durable bifunctional electrocatalyst for oxygen-reduction and evolution reactions[J]. Nanotechnology, 2021, 32(32): 325703. DOI: 10.1088/1361-6528/abfb9b.
27	ZHANG H M, GUOX Y, LIU W H, et al. Regulating surface composition of platinum-copper nanotubes for enhanced hydrogen evolution reaction in all pH values[J]. Journal of Colloid and Interface Science, 2023, 629(Part A): 53-62. DOI: 10.1016/j.jcis.2022.08.116.
28	SU L, SHRESTHA S J, ZHANG Z H, et al. Platinum-copper nanotube electrocatalyst with enhanced activity and durability for oxygen reduction reactions[J]. Journal of Materials Chemistry A, 2013, 1(39): 12293-12301. DOI: 10.1039/c3ta13097e.
29	CUI S K, GUO D J. Microwave-assisted preparation of PtCu/C nanoalloys and their catalytic properties for oxygen reduction reaction[J]. Journal of Alloys and Compounds, 2021, 874: 159869. DOI: 10.1016/j.jallcom.2021.159869.
30	CAI J L, CHEN Y Z, ZHANG R W, et al. Interfacial Pt-N coordination for promoting oxygen reduction reaction[J]. Chinese Chemical Letters, 2025, 36(2): 110255. DOI: 10.1016/j.cclet. 2024.110255.
31	蔡佳琳, 陈艺哲, 容忠言, 等. 微波合成碳载铂用于氧还原电催化[J]. 储能科学与技术, 2022, 11(12): 3800-3807. DOI: 10.19799/j.cnki. 2095-4239.2022.0473.
	CAI J L, CHEN Y Z, RONG Z Y, et al. Microwave synthesis of carbon supported platinum for oxygen reduction electrocatalysis[J]. Energy Storage Science and Technology, 2022, 11(12): 3800-3807. DOI: 10.19799/j.cnki.2095-4239.2022.0473.

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