载体特性对Pt/C催化剂上离聚物覆盖度及氧还原性能的影响

doi:10.15541/jim20250004

无机材料学报 ›› 2025, Vol. 40 ›› Issue (12): 1395-1404.DOI: 10.15541/jim20250004

载体特性对Pt/C催化剂上离聚物覆盖度及氧还原性能的影响

李薛茹(), 马哲杰, 郭宇杰, 李平()

华东理工大学化工学院, 绿色化工与工业催化全国重点实验室, 上海 200237

收稿日期:2025-01-03 修回日期:2025-03-20 出版日期:2025-12-20 网络出版日期:2025-04-15
通讯作者: 李平, 教授. E-mail: lipingunilab@ecust.edu.cn
作者简介:李薛茹(2000‒), 女, 硕士研究生. E-mail: y82220019@mail.ecust.edu.cn
基金资助:
国家重点研发计划(2023YFB4006101)

Influence of Support Characteristics on Coverage of Ionomer and Oxygen Reduction Performance for Pt/C Catalysts

LI Xueru(), MA Zhejie, GUO Yujie, LI Ping()

State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2025-01-03 Revised:2025-03-20 Published:2025-12-20 Online:2025-04-15
Contact: LI Ping, professor. E-mail: lipingunilab@ecust.edu.cn
About author:LI Xueru (2000‒), female, Master candidate. E-mail: y82220019@mail.ecust.edu.cn
Supported by:
National Key R&D Program Project of China(2023YFB4006101)

摘要/Abstract

摘要：

碳载体是质子交换膜燃料电池膜电极常用Pt/C催化剂的重要组成部分, 离聚物是构成膜电极催化层的关键成分之一。本研究针对六种不同类型的商业化碳载体(VC、KB1、KB2、BP、SJR、AB), 采用多种表征手段系统分析了碳载体、添加离聚物前后Pt/C催化剂的微观结构与表面化学性质, 并且测试了各类Pt/C催化剂的氧还原反应(ORR)性能, 以探究代表性碳载体负载Pt催化剂的电催化构效关系。研究发现, 具有大比表面积和丰富孔结构的碳载体, 如KB1、KB2、BP, 可减小沉积的Pt粒径。强亲水性的实心碳载体(VC、SJR)上的含氧官能团也有助于分散Pt粒子。同时, 含有大量2~8 nm介孔的碳载体(KB1、KB2)有利于Pt分布在碳颗粒内孔中, 而在微孔(<2 nm)居多的大比表面积碳载体(BP)以及中等与小比表面积碳载体(VC、SJR、AB)上, 绝大部分Pt粒子分布在碳颗粒外表面。进一步结合离聚物加入前后Pt/C样品比表面积与孔结构的变化, 测算离聚物的覆盖度, 并提出了离聚物在催化剂颗粒上的分布模型。在实心碳负载催化剂上, 一定量的离聚物基本覆盖了碳颗粒外表面; 在微孔主导的BP负载催化剂上, 离聚物堵塞微孔, 造成比表面积与孔容大幅下降; 而在介孔碳负载的催化剂上, 相同量的离聚物不足以堵塞全部微孔(<2 nm)与介孔(2~8 nm), 使得覆盖度较低。Pt/C催化剂的ORR活性主要由Pt粒径大小决定, 并且, 分布在碳颗粒内孔的Pt粒子可免受离聚物的毒化作用, 因此, KB系列碳载体负载的Pt催化剂在液相ORR动力学过程中表现优异。

关键词: 载体特性, Pt/C催化剂, 离聚物覆盖度, 氧还原反应, 质子交换膜燃料电池

Abstract:

Carbon support is an important component of Pt/C catalyst commonly used in the membrane electrodes of proton exchange membrane fuel cells, and ionomer is one of the key components that make up the catalytic layer. However, the influence of support characteristics on coverage of ionomer and oxygen reduction performance for Pt/C catalysts is still unknown. Here, six different types of representative commercial carbon supports (VC, KB1, KB2, BP, SJR, and AB) were focused. The microstructure and surface chemical properties of the carbon supports and the Pt/C catalysts prepared with and without addition of ionomer were investigated using various characterization methods. The oxygen reduction reaction (ORR) performance of various Pt/C catalysts was tested to explore the electrocatalytic structure-activity relationship of representative carbon supports for Pt catalysts. As revealed, carbon supports with large specific surface areas and rich pore structures, such as KB1, KB2 and BP, contribute to more uniform distribution of Pt particles. Presence of oxygen-containing functional groups on solid carbon supports with strong hydrophilicity, such as VC and SJR, contributes to dispersion of Pt particles. Meanwhile, carbon supports with abundant mesopores in the range of 2-8 nm (KB1 and KB2) are beneficial for improving location of Pt within pores of carbon particles, while those with high specific surface area and full of micropores (BP) and those with medium or low specific surface area (VC, SJR, and AB) have the most Pt nano-particles distributed on the outer surface of the carbon particles. By combining changes in specific surface area and pore structure of various Pt/C samples before and after addition of ionomer, the coverage of ionomer was calculated, and a distribution model of ionomer on different catalyst particles was proposed. On the solid carbon supported catalysts, a certain amount of ionomer basically covers entire outer surface of carbon particles. For the BP supported catalyst which is dominated by micropores, ionomer can block the micropores, resulting in a significant decrease in specific surface area and pore volume. For the mesoporous carbon supported catalysts, the same amount of ionomer is hard to block all micropores and mesopores, leading to lower coverage. Furthermore, ORR activity of Pt/C catalyst mainly depends on the Pt nano-particle size, and the Pt nano-particles located in the pores inside of the carbon particles can be protected from the poisoning of ionomer. Therefore, Pt catalysts supported on the carbon supports of KB series exhibit excellent performance for the ORR kinetics occurring in liquid-phase.

Key words: support characteristic, Pt/C catalyst, coverage of ionomer, oxygen reduction reaction, proton exchange membrane fuel cell

中图分类号:

TQ426

李薛茹, 马哲杰, 郭宇杰, 李平. 载体特性对Pt/C催化剂上离聚物覆盖度及氧还原性能的影响[J]. 无机材料学报, 2025, 40(12): 1395-1404.

LI Xueru, MA Zhejie, GUO Yujie, LI Ping. Influence of Support Characteristics on Coverage of Ionomer and Oxygen Reduction Performance for Pt/C Catalysts[J]. Journal of Inorganic Materials, 2025, 40(12): 1395-1404.

图/表 15

图1 不同碳载体的(a)氮气吸/脱附等温曲线和(b)孔径分布图

Fig. 1 (a) N2 adsorption-desorption isotherms and (b) pore-size distributions of different carbon supports

图2 不同碳载体的FT-IR谱图

Fig. 2 FT-IR spectra of different carbon supports Colorful figure is available on website

表1 不同碳载体的接触角和Zeta电位

Table 1 Contact angles and Zeta potentials of different carbon supports

Sample	VC	KB1	KB2	BP	SJR	AB
Contact angle/(°)	40	47	125	94	34	137
Zeta potential/mV	9.8	21.0	24.7	15.3	-1.1	-

图3 不同碳载体负载Pt催化剂的STEM照片(二次电子模式)

Fig. 3 STEM images with secondary electron (SE) mode for Pt catalysts loaded on different carbon supports (a) 0° and (b) 180° of PK-Pt/VC; (c) 0° and (d) 180° of Pt/VC; (e) 0° and (f) 180° of PK-Pt/KB1; (g) 0° and (h) 180° of Pt/KB2; (i) 0° and (j) 180° of Pt/BP; (k) 0° and (l) 180° of Pt/SJR; (m) 0° and (n) 180° of Pt/AB

图4 碳载体及Pt/C催化剂的(a)总比表面积和(b)总孔容

Fig. 4 (a) Total specific surface area and (b) total pore volume of different carbon supports and Pt/C catalysts

图5 离聚物加入(a)前(b)后不同Pt/C催化剂的孔径分布曲线

Fig. 5 Pore size distribution curves of different Pt/C catalysts (a) before and (b) after addition of ionomer Colorful figures are available on website

图6 加入离聚物后不同Pt/C催化剂比表面积和孔容的下降率

Fig. 6 Reduction rates of specific surface areas and pore volumes of different Pt/C catalysts after addition of ionomer Numbers in the figure represent coverages of ionomer

图7 含离聚物催化剂样品(a)Pt/VC和(b)Pt/KB2的TEM照片

Fig. 7 TEM images of catalysts containing ionomer for (a) Pt/VC and (b) Pt/KB2 Yellow arrows: ionomer film covering the outer surface of the catalyst particles

图8 离聚物在不同特征Pt/C颗粒上的分布示意图

Fig. 8 Schematic diagrams of the coverage states of ionomer on catalysts with different characteristics (a) PK-Pt/KB1, Pt/KB2; (b) Pt/BP; (c) Pt/VC, Pt/SJR and Pt/AB Black dot: Pt particle; Blue area: ionomer; Gray area: C

图9 不同Pt/C催化剂的(a) CV曲线、(b) LSV曲线以及(c) ECSA和MA比较

Fig. 9 (a) CV curves, (b) LSV curves, (c) calculated ECSA and MA of different Pt/C catalysts Colorful figures are available on website

表S1 不同碳载体的总比表面积、孔容及其分布

Table S1 Specific surface areas, pore volumes and distributions of different carbon supports

Sample	Specific surface area/(m²·g^-1)	Pore area/(m²·g^-1)			Pore volume/(cm³·g^-1)
Sample	Specific surface area/(m²·g^-1)	<2 nm	2-8 nm	>8 nm	<2 nm	2-8 nm	>8 nm	Total
VC	206.9	125.1	43.5	38.3	0.035	0.039	0.478	0.582
KB1	811.1	372.8	353.1	85.2	0.194	0.308	0.730	1.232
KB2	1361.0	291.3	834.3	235.4	0.167	0.807	1.613	2.587
BP	1313.1	903.6	249.0	160.5	0.444	0.204	1.909	2.577
SJR	121.2	15.1	33.4	72.7	0.009	0.032	0.757	0.798
AB	65.6	5.5	42.1	18.0	0.004	0.039	0.135	0.178

表S2 不同碳载体上负载Pt粒子的平均粒径及负载量

Table S2 Average particle sizes and loading amounts of Pt particles on different carbon supports

Catalyst	PK-Pt/VC	Pt/VC	PK-Pt/KB1	Pt/KB2	Pt/BP	Pt/SJR	Pt/AB
Pt loading/% (in mass)	38.6	32.0	38.3	35.8	35.8	37.0	31.9
Average Pt particle size/nm	3.9	3.0	2.5	2.4	2.5	2.6	2.8

表S3 Pt颗粒在不同碳载体的碳颗粒内外表面分布的百分比

Table S3 Percentages of Pt particles distributed inside and outside of the carbon particles for different carbon supports

Catalyst	PK-Pt/VC	Pt/VC	PK-Pt/KB1	Pt/KB2	Pt/BP	Pt/SJR	Pt/AB
Exterior frequency/%	92	90	34	28	85	100	100
Interior frequency/%	8	10	66	72	15	0	0

表S4 不同Pt/C催化电极上ORR反应测试结果

Table S4 Testing results of ORR on various Pt/C catalytic electrodes

Catalyst	j_lim/(mA·cm^-2)	j_k/(mA·cm^-2)	E_onset/V	E_1/2/V
PK-Pt/VC	5.9	4.3	1.037	0.88
Pt/VC	5.9	3.5	1.033	0.88
PK-Pt/KB1	6.0	5.6	1.048	0.90
Pt/KB2	6.1	5.9	1.042	0.90
Pt/BP	6.1	4.5	1.039	0.88
Pt/SJR	6.0	4.0	1.046	0.87
Pt/AB	5.5	2.7	1.014	0.84

图S1 不同碳载体负载Pt催化剂的HRTEM照片以及粒径分布图

Fig. S1 HRTEM images and histograms of particle size distributions of different Pt catalysts (a, a1) PK-Pt/VC; (b, b1) Pt/VC; (c, c1) PK-Pt/KB1; (d, d1) Pt/KB2; (e, e1) Pt/BP; (f, f1) Pt/SJR; (g, g1) Pt/AB

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载体特性对Pt/C催化剂上离聚物覆盖度及氧还原性能的影响

Influence of Support Characteristics on Coverage of Ionomer and Oxygen Reduction Performance for Pt/C Catalysts

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