Hollow COF-derived carbon supports enable PtCo alloy catalysts with exceptional activity and durability for oxygen reduction reaction in fuel cells

doi:10.1016/S1872-2067(26)64973-X

Chinese Journal of Catalysis ›› 2026, Vol. 83: 294-307.DOI: 10.1016/S1872-2067(26)64973-X

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Hollow COF-derived carbon supports enable PtCo alloy catalysts with exceptional activity and durability for oxygen reduction reaction in fuel cells

Gong Li^a^,^b, Jingsen Bai^a^,^b, Dan Wang^d, Liang Liang^b^,^c, Chunyu Ru^d, Xue Gong^d, Minhua Shao^e^,^f^,^g^,^*(), Changpeng Liu^a^,^b^,^c^,^*(), Meiling Xiao^a^,^b^,^c^,^*(), Wei Xing^a^,^b^,^c^,^*()

^aSchool of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, Anhui, China
^bState Key Laboratory of Electroanalytic Chemistry, Jilin Province Key Laboratory of Low Carbon Chemistry Power, Jilin Provincial Science and Technology Innovation Center of Hydrogen Energy, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, Jilin, China
^cCIAC-HKUST Joint Laboratory for Hydrogen Energy, Changchun 130022, Jilin, China
^dEngine Development Department, General Institute of FAW, Changchun 130013, Jilin, China
^eDepartment of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Hong Kong 999077, China
^fCIAC-HKUST Joint Laboratory for Hydrogen Energy, Energy Institute, The Hong Kong University of Science and Technology, Hong Kong 999077, China
^gGuangzhou Key Laboratory of Electrochemical Energy Storage Technologies, Fok Ying Tung Research Institute, The Hong Kong University of Science and Technology, Guangzhou 511458, Guangdong, China

Received:2025-08-19 Accepted:2025-10-18 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: kemshao@ust.hk (Minhua Shao), liuchp@ciac.ac.cn (C. Liu), mlxiao@ciac.ac.cn (M. Xiao), xingwei@ciac.ac.cn (W. Xing).
Supported by:
National Natural Science Foundation of China(22272160);National Natural Science Foundation of China(U23A20137);Changchun Science and Technology Development Program(23GZZ02);Jilin Province Science and Technology Development Program(20220301011GX);Jilin Province Science and Technology Major Project(222648GX0105103875);Hong Kong Research Grant Council(C6011-20GF);Hong Kong Research Grant Council(JLFS/P-602/24)

Abstract

Abstract:

The development of high-performance and durable oxygen reduction reaction catalysts under harsh working environments remains a key challenge in advancing proton exchange membrane fuel cells. Here, we report a series of hollow-structured covalent organic framework-derived carbon as support materials for PtCo alloy nanocatalysts. These hollow architectures provide unique spatial confinement and encapsulation effects, which not only facilitate efficient mass transport but also protect active sites from degradation in acidic media, thereby ensuring simultaneous enhancement in activity and stability. The optimized PtCo@NC_TAPBT catalyst delivers a peak power density of 1.23 W cm^-2 under H₂-Air conditions and a mass activity of 1.06 A mg_Pt^-1 at 0.9 V, representing 2.41 times higher than that of commercial Pt/C (0.40 A mg_Pt^-1). Moreover, the fuel cell assembled with this catalyst exhibits outstanding durability, showing a voltage degradation of only 8 mV after 30000 cycles at 0.8 A cm^-2 and a mass activity retention of 87.7% (0.93 A mg_Pt^-1). Notably, this performance exceeds the U.S. Department of Energy’s 2025 initial mass activity target (0.44 A mg_Pt^-1) by a factor of 2.1, highlighting the potential of HCOF-derived carbon materials for next-generation fuel cell applications.

Key words: Covalent organic framework, Alloy, Encapsulation structure, Oxygen reduction reaction, Fuel cell

Gong Li, Jingsen Bai, Dan Wang, Liang Liang, Chunyu Ru, Xue Gong, Minhua Shao, Changpeng Liu, Meiling Xiao, Wei Xing. Hollow COF-derived carbon supports enable PtCo alloy catalysts with exceptional activity and durability for oxygen reduction reaction in fuel cells[J]. Chinese Journal of Catalysis, 2026, 83: 294-307.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64973-X

https://www.cjcatal.com/EN/Y2026/V83/I4/294

Figures/Tables 5

Fig. 1. (a) Schematic illustration of the synthesis procedure of TAPB-BTCA-HCOF. (b) TEM images of TAPTA-BTCA-COF. (c) TEM images of TAPB-BTCA-HCOF. (d) XRD patterns of TAPTA-BTCA-COF and TAPTA-BTCA-HCOF. (e) FT-IR spectra of TAPTA-BTCA-COF and TAPTA-BTCA-HCOF.

Fig. 2. TEM images of PtCo@NCTPDV (a), PtCo@NCTPTF (b) and PtCo@NCTAPBT (c). STEM images of PtCo@NCTPDV (d), PtCo@NCTPTF (e) and PtCo@NCTAPBT (f) (the enclosure of ultrafine nanoparticle by HCOF indicated by white arrows). (g) XRD patterns of PtCo@NCTPDV, PtCo@NCTPTF and PtCo@NCTAPBT. (h) XRD patterns of PtCo@NCTAPBT annealing at different temperatures. (i) N2 adsorption-desorption isotherms of PtCo@NCTAPBT.

Fig. 3. (a) High-resolution XPS spectra Pt 4f of PtCo@NCTPDV, PtCo@NCTPTF and PtCo@NCTAPBT. (b) High-resolution XPS spectra N 1s of PtCo@NCTPDV, PtCo@NCTPTF and PtCo@NCTAPBT. Pt L3-edge (c) and Co K-edge (d) XANES spectra of PtCo@NCTPDV, PtCo@NCTPTF and PtCo@NCTAPBT with metal foils as references. Insert: image from the partially enlarged view. Fourier transforms of k3-weight Pt L3-edge (e) and Co K-edge (f) EXAFS spectra for PtCo@NCTPDV, PtCo@NCTPTF and PtCo@NCTAPBT, Pt foil and Co foil. (g) Wavelet transforms for the Pt L3-edge EXAFS data of PtCo@NCTPDV, PtCo@NCTPTF, PtCo@NCTAPBT and Pt foil.

Fig. 4. (a) ORR polarization curves of PtCo@NCTPDV, PtCo@NCTPTF, PtCo@NCTAPBT and Pt/C. (b) The corresponding Tafel plots of PtCo@NCTPDV, PtCo@NCTPTF, PtCo@NCTAPBT and Pt/C. (c) Comparison of MA and SA for PtCo@NCTAPBT and Pt/C at 0.90 V (vs. RHE). (d) ORR polarization curves of PtCo@NCTAPBT and Pt/C before and after 50k. (e) Cyclic voltammetry curve of PtCo@NCTAPBT before and after ADT 50k. (f) The electron transfer number (n) at different potentials (left) and HO2? yield (right) for PtCo@NCTAPBT and Pt/C catalysts.

Fig. 5. Polarization and power density curves of PtCo@NCTPDV, PtCo@NCTPTF, PtCo@NCTAPBT and Pt/C in H2-O2 fuel cells (a) and H2-Air fuel cells (b) at 80 °C with 200 kPa back pressure and 100% Relative Humidity (RH) with the cathode metal loading of 0.1 mgPt cm?2. (c) Rtot of the cathode for PtCo@NCTAPBT PtCo@NCTAPBT-COF and Pt/C in the PEMFC at various total cathode pressures. (d) Polarization and power density curves of PtCo@NCTAPBT in H2-O2 fuel cells at 80 °C with the back pressure of 200 kPa and 100% RH with the cathode metal loading of 0.1 mgPt cm?2 after 30k potential cycles. (e) MA at 0.9 V and voltage loss at 0.8 A cm?2 at the begin of life (BOL), 10k and 30k. Note: the purple and yellow dashed lines indicate DOE targets for MA at BOL and end of life (EOL) after 30k potential cycles, respectively. The blue dashed line indicates the DOE target for voltage drop at 0.8 A cm?2 after 30k potential cycles. (f) Comparison of stability retain and MA after load cycles between PtCo@NCTAPBT with the state-of-art in the literature. (f) Current density as a function of time for PtCo@NCTAPBT with a 0.1 mgPt?cm?2 loading at 0.6 V in H2-Air conditions.

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Hollow COF-derived carbon supports enable PtCo alloy catalysts with exceptional activity and durability for oxygen reduction reaction in fuel cells

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