利用介孔碳的限域效应提升氧还原反应中Pt催化剂的耐久性

doi:10.15541/jim20250173

无机材料学报 ›› 2026, Vol. 41 ›› Issue (3): 289-294.DOI: 10.15541/jim20250173 CSTR: 32189.14.jim20250173

利用介孔碳的限域效应提升氧还原反应中Pt催化剂的耐久性

黄应贺¹^,²(), 黄仁兴¹, 石宇星¹, 雷一杰², 于涛¹, 王诚², 顾军¹()

1.南京大学物理学院, 南京 210093
2.清华大学核能与新能源技术研究院, 北京 100084

收稿日期:2025-04-24 修回日期:2025-08-10 出版日期:2025-08-26 网络出版日期:2025-08-26
通讯作者: 顾军, 教授. E-mail: junguca@nju.edu.cn
作者简介:黄应贺(1996-), 男, 博士研究生. E-mail: 602023220030@smail.nju.edu.cn
基金资助:
国家重点研发计划(2022YFE0207600);国家重点研发计划(2021YFB3800401);国家自然科学基金(22372078)

Enhancing Durability of Pt Catalysts in the Oxygen Reduction Reaction by Confinement Effect of Mesoporous Carbon

HUANG Yinghe¹^,²(), HUANG Renxing¹, SHI Yuxing¹, LEI Yijie², YU Tao¹, WANG Cheng², GU Jun¹()

1. School of Physics, Nanjing University, Nanjing 210093, China
2. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China

Received:2025-04-24 Revised:2025-08-10 Published:2025-08-26 Online:2025-08-26
Contact: GU Jun, professor. E-mail: junguca@nju.edu.cn
About author:HUANG Yinghe (1996-), male, PhD candidate. E-mail: 602023220030@smail.nju.edu.cn
Supported by:
National Key R&D Program of China(2022YFE0207600);National Key R&D Program of China(2021YFB3800401);National Natural Science Foundation of China(22372078)

1. 利用介孔碳的限域效应提升氧还原反应中Pt催化剂的耐久性.mp4(2360KB)

摘要/Abstract

摘要：

铂碳(Pt/C)催化剂是质子交换膜燃料电池(PEMFCs)最具前景的阴极催化剂之一, 但其耐久性不佳。这主要是由于铂纳米颗粒(Pt NPs)会发生团聚和迁移, Pt颗粒尺寸变大, 从而使催化活性丧失。本研究通过构建具有串珠状内部孔隙结构的介孔碳载体(IPMC), 研究了Pt NPs在碳载体中的沉积位置, 并将其精准限域在孔道内部, 利用独特的孔隙结构, 实现了Pt NPs的高效限域, 提升了材料稳定性。分析表明, 介孔碳催化剂中的Pt NPs经过30000 圈加速耐久性测试(ADT)循环后平均粒径仅增加了0.46 nm, 而实心碳催化剂中的Pt NPs增加了0.79 nm。介孔碳催化剂的电化学性能损失较小, 电化学活性面积(ECSA)损失率为24.18%, 显著低于实心碳催化剂(32.33%)。介孔碳催化剂耐久性优异主要归因于IPMC独特的孔隙结构所产生的限域效应, 进而抑制内部Pt NPs的奥斯特瓦尔德(Ostwald)熟化和迁移行为, 显著延缓了氧还原反应(ORR)催化活性衰减。本工作揭示了串珠状介孔对Pt NPs的物理限域机制, 即相互连通且具有局部收缩的孔道结构形成空间屏障, 有效阻碍溶解Pt物种的扩散迁移并锚定颗粒位置, 为设计PEMFCs的最佳碳载体提供了更精确的结构蓝图。

关键词: 铂碳催化剂, 介孔碳, 耐久性, Ostwald熟化, ORR催化活性

Abstract:

Platinum-carbon (Pt/C) catalyst is one of the most promising cathode materials for proton exchange membrane fuel cells (PEMFCs). However, it faces significant durability challenges, primarily due to growth and agglomeration of platinum nanoparticles (Pt NPs), which results in increased Pt particle size and consequent loss of catalytic activity. In this study, an internally pearl-like mesoporous carbon (IPMC) support with beaded pore channels was constructed to investigate the deposition sites of Pt NPs within carbon supports. Through precisely confining Pt NPs within the pore channels by leveraging the unique pore architecture, efficient confinement and stabilization of Pt NPs were achieved. Average size of Pt NPs in IPMC increased by only 0.46 nm after 30000 cycles of accelerated durability test (ADT), significantly less than the growth (0.79 nm) observed in conventional solid carbon-supported catalysts. The IPMC-based catalyst also exhibited slower electrochemical performance decay. The electrochemical active area (ECSA) loss rate of the mesoporous carbon catalyst was 24.18%, significantly lower than 32.33% observed for solid carbon catalyst in comparative testing. This superior durability originates from unique pore structure of IPMC, which imposes spatial confinement effects that effectively suppress Ostwald ripening and migration of Pt NPs, thereby mitigating the degradation of oxygen reduction reaction (ORR) activity. This work delivers a precise structural blueprint for optimal carbon carriers of high-stability PEMFCs catalysts by revealing how beaded mesopores confine Pt NPs: interconnected pore channels with local constrictions form spatial barriers which hinder dissolved platinum species diffusion while anchoring particles.

Key words: platinum-carbon catalyst, mesoporous carbon, durability, Ostwald ripening, ORR catalytic activity

中图分类号:

TQ15

黄应贺, 黄仁兴, 石宇星, 雷一杰, 于涛, 王诚, 顾军. 利用介孔碳的限域效应提升氧还原反应中Pt催化剂的耐久性[J]. 无机材料学报, 2026, 41(3): 289-294.

HUANG Yinghe, HUANG Renxing, SHI Yuxing, LEI Yijie, YU Tao, WANG Cheng, GU Jun. Enhancing Durability of Pt Catalysts in the Oxygen Reduction Reaction by Confinement Effect of Mesoporous Carbon[J]. Journal of Inorganic Materials, 2026, 41(3): 289-294.

图/表 15

图1 Pt/IPMC的制备过程示意图

Fig. 1 Schematic diagram of the preparation process for Pt/IPMC Colorful figure is available on website

图2 IPMC的SEM照片

Fig. 2 SEM image of IPMC

图3 IPMC和Pt/IPMC (a, b), ECP600和Pt/ECP600 (c, d)的孔径变化(a, c)和N2吸附-解吸等温线变化(b, d)

Fig. 3 Pore size changes (a, c) and N2 adsorption-desorption isotherm changes (b, d) of IPMC and Pt/IPMC (a, b), ECP600 and Pt/ECP600 (c, d)

图4 Pt/IPMC (a, b)和Pt/ECP600 (c, d)的TEM照片(a, c)和Pt粒径分布(b, d)

Fig. 4 TEM images (a, c) and Pt particle size distributions (b, d) of Pt/IPMC (a, b) and Pt/ECP600 (c, d)

图5 (a) ADT前后Pt/IPMC和Pt/ECP600的CV曲线; (b) 10000、20000和30000圈ADT后的ECSA保留率

Fig. 5 (a) CV curves of Pt/IPMC and Pt/ECP600 before and after ADT cycles; (b) ECSA retention rates after 10000, 20000, and 30000 ADT cycles

图6 Pt/IPMC (a, b)和Pt/ECP600 (c, d)经过30000圈ADT后的TEM照片(a, c)和粒径分布图(b, d)

Fig. 6 TEM images (a, c) and particle size distributions (b, d) of Pt/IPMC (a, b) and Pt/ECP600 (c, d) after 30000 ADT cycles

图S1 IPMC的TEM照片

Fig. S1 TEM image of IPMC

图S2 ECP600和IPMC的拉曼光谱图(a)和FT-IR光谱图(b)

Fig. S2 Raman spectra (a) and FT-IR spectra (b) of ECP600 and IPMC

图S3 Pt/ECP600和Pt/IPMC循环测试前(a)后(b)的XRD图谱

Fig. S3 XRD patterns of Pt/ECP600 and Pt/IPMC before (a) and after (b) cycling test

图S4 ECP600的SEM照片

Fig. S4 SEM image of ECP600

图S5 (a) ADT循环前后Pt/IPMC和Pt/ECP600的LSV曲线; (b) 10000、20000和30000圈ADT循环后的MA保留率

Fig. S5 (a) LSV curves of Pt/IPMC and Pt/ECP600 before and after ADT cycles; (b) MA retention rate after 10000, 20000 and 30000 ADT cycles

表S1 Pt/IPMC和市售Pt/ECP600在耐久性能测试中MA的变化

Table S1 Changes in MA during durability test of Pt/IPMC and commercial Pt/ECP600

Sample	MA after 3 cycles/(mA∙mg^-1)	MA after 10000 cycles/(mA∙mg^-1)	MA after 20000 cycles/(mA∙mg^-1)	MA after 30000 cycles/(mA∙mg^-1)	MA retention rate/%
Pt/ECP600	144	113	93.6	86.0	60.0
Pt/IPMC	269	233	213	189	70.2

表S2 Pt/IPMC和市售Pt/ECP600在耐久性能测试中SA的变化

Table S2 Changes in SA during durability test of Pt/IPMC and commercial Pt/ECP600

Sample	SA after 3 cycles/(µA∙cm^-2)	SA after 10000 cycles/(µA∙cm^-2)	SA after 20000 cycles/(µA∙cm^-2)	SA after 30000 cycles/(µA∙cm^-2)	SA retention rate/%
Pt/ECP600	145	134	125	128	88.3
Pt/IPMC	296	271	295	273	92.2

表S3 Pt/IPMC和市售Pt/ECP600在耐久性能测试中ECSA的变化

Table S3 Changes in ECSA during durability test of Pt/IPMC and commercial Pt/ECP600

Sample	ECSA after 3 cycles/(m²∙g^-1)	ECSA after 10000 cycles/(m²∙g^-1)	ECSA after 20000 cycles/(m²∙g^-1)	ECSA after 30000 cycles/(m²∙g^-1)	ECSA retention rate/%
Pt/ECP600	99	84	75	67	67.67
Pt/IPMC	91	86	72	69	75.82

表S4 本研究与文献中介孔碳催化剂的耐久性对比

Table S4 Comparison of durability of mesoporous carbon catalysts in this study and literatures

Sample	ECSA/(m²∙g^-1, initial)	ECSA retention rate	Pt particle size change/nm	Testing environment
Pt/ECP600	99	67.67% (after 30000 cycles)	2.62→3.41	0.1 mol·L^-1 HClO₄, 0.6-0.1 V, 100 mV·s^-1
Pt/IPMC	91	75.82% (after 30000 cycles)	2.60→3.06	0.1 mol·L^-1 HClO₄, 0.6-0.1 V, 100 mV·s^-1
Pt/C^[S2]	58	~47.5% (after 6000 cycles)	-	0.1 mol·L^-1 HClO₄, 0.6-1.0 V, 50 mV·s^-1
Pt/HCSs^[S2]	63	~58.6% (after 6000 cycles)	-	0.1 mol·L^-1 HClO₄, 0.6-1.0 V, 50 mV·s^-1
Pt/Vulcan^[S3]	-	(after 3600 cycles)	~3.48→~4.00	0.1 mol·L^-1 HClO₄, 0.4-1.4 V, 1 V·s^-1
Pt@HGS^[S3]	-	(after 3600 cycles)	~3.80→~3.75	0.1 mol·L^-1 HClO₄, 0.4-1.4 V, 1 V·s^-1
Pt/VC^[S4]	69	54% (after 2000 cycles)	-	0.5 mol·L^-1 H₂SO₄, 0-1.1 V, 20 mV·s^-1
Pt@CS^[S4]	81	21% (after 2000 cycles)	-	0.5 mol·L^-1 H₂SO₄, 0-1.1 V, 20 mV·s^-1

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利用介孔碳的限域效应提升氧还原反应中Pt催化剂的耐久性

Enhancing Durability of Pt Catalysts in the Oxygen Reduction Reaction by Confinement Effect of Mesoporous Carbon

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