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

doi:10.15541/jim20250173

Abstract

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

CLC Number:

TQ15

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.

Figures/Tables 15

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

Fig. 2 SEM image of IPMC

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)

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

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

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

Fig. S1 TEM image of IPMC

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

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

Fig. S4 SEM image of ECP600

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

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

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

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

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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