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

• Articles • Previous Articles Next Articles

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: Minhua Shao, Changpeng Liu, Meiling Xiao, Wei 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.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

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.

References

[1]	L. Zheng, M. Niu, T. Zeng, X. Ge, Y. Wang, C.-X. Guo, W. Yuan, D. Cao, L.-Y. Zhang, C.-M. Li, eScience, 2024, 4, 100187.
[2]	D. Banham, S. Ye, ACS Energy Lett., 2017, 2, 629-638.
[3]	K. Kodama, T. Nagai, A. Kuwaki, R. Jinnouchi, Y. Morimoto, Nat. Nanotechnol., 2021, 16, 140-147.
[4]	H. Yang, Y. Liu, X. Liu, X. Wang, H. Tian, G. I. N. Waterhouse, P. E. Kruger, S. G. Telfer, S. Ma, eScience, 2022, 2, 227-234.
[5]	Z. Zhao, Z. Liu, A. Zhang, X. Yan, W. Xue, B. Peng, H. L. Xin, X. Pan, X. Duan, Y. Huang, Nat. Nanotechnol., 2022, 17, 968-975.
[6]	P. Rao, D. Wu, T.-J. Wang, J. Li, P. Deng, Q. Chen, Y. Shen, Y. Chen, X. Tian, eScience, 2022, 2, 399-404.
[7]	X. Teng, D. Si, L. Chen, J. Shi, eScience, 2024, 4, 100272.
[8]	Y. Han, Y.-G. Wang, W. Chen, R. Xu, L. Zheng, J. Zhang, J. Luo, R.-A. Shen, Y. Zhu, W.-C. Cheong, C. Chen, Q. Peng, D. Wang, Y. Li, J. Am. Chem. Soc., 2017, 139, 17269-17272.
[9]	Y. Chen, S. Skrabalak, L. Xu, Y. Tang, Abstracts of Papers of the Am. Chem. Soc., 2019, 258, 9.
[10]	Z. Zhang, X. Zhao, S. Xi, L. Zhang, Z. Chen, Z. Zeng, M. Huang, H. Yang, B. Liu, S. J. Pennycook, P. Chen, Adv. Energy Mater., 2020, 10, 2002896.
[11]	L. Kuai, Z. Chen, S. Liu, E. Kan, N. Yu, Y. Ren, C. Fang, X. Li, Y. Li, B. Geng, Nat. Commun., 2020, 11, 48.
[12]	W. Wang, L. Kuai, W. Cao, M. Huttula, S. Ollikkala, T. Ahopelto, A.-P. Honkanen, S. Huotari, M. Yu, B. Geng, Angew. Chem. Int. Ed., 2017, 56, 14977-14981.
[13]	X. Feng, X. Ding, D. Jiang, Chem. Soc. Rev., 2012, 41, 6010.
[14]	N. Huang, P. Wang, D. Jiang, Nat. Rev. Mater., 2016, 1, 16068.
[15]	Q. Xu, Y. Tang, L. Zhai, Q. Chen, D. Jiang, Chem. Commun., 2017, 53, 11690-11693.
[16]	A. P. Côté, A. I. Benin, N. W. Ockwig, M. O’Keeffe, A. J. Matzger, O. M. Yaghi, Science, 2005, 310, 1166-1170.
[17]	C. S. Diercks, O. M. Yaghi, Science, 2017, 355, eaal1585.
[18]	Y. Song, Q. Sun, B. Aguila, S. Ma, Adv. Sci., 2019, 6, 1801410.
[19]	S. Jin, M. Supur, M. Addicoat, K. Furukawa, L. Chen, T. Nakamura, S. Fukuzumi, S. Irle, D. Jiang, J. Am. Chem. Soc., 2015, 137, 7817-7827.
[20]	Y. Yan, T. He, B. Zhao, K. Qi, H. Liu, B.-Y. Xia, J. Mater. Chem. A, 2018, 6, 15905-15926.
[21]	K. Kamiya, R. Kamai, K. Hashimoto, S. Nakanishi, Nat. Commun., 2014, 5, 5040.
[22]	H. B. Aiyappa, J. Thote, D. B. Shinde, R. Banerjee, S. Kurungot, Chem. Mater., 2016, 28, 4375-4379.
[23]	S. Cai, Z. Meng, H. Tang, Y. Wang, P. Tsiakaras, Appl. Catal. B, 2017, 217, 477-484.
[24]	G. Zhao, X. Zou, H. Ma, L. Wang, H. Guo, J. Energy Chem., 2025, 108, 83-91.
[25]	G. Zhao, H. Ma, C. Zhang, Y. Yang, S. Yu, H. Zhu, Y. Sun, H. Guo, Nano-Micro Lett., 2025, 17, 21.
[26]	K. Cui, W. Zhong, L. Li, Z. Zhuang, L. Li, J. Bi, Y. Yu, Small, 2019, 15, 1804419.
[27]	F.-D. Chen, Z.-Y. Xie, M.-T. Li, S.-G. Chen, W. Ding, L. Li, J. Li, Z.-D. Wei, J. Electrochem., 2024, 30, 2314007.
[28]	Q. Wang, S. Chen, F. Shi, K. Chen, Y. Nie, Y. Wang, R. Wu, J. Li, Y. Zhang, W. Ding, Y. Li, L. Li, Z. Wei, Adv. Mater., 2016, 28, 10673-10678.
[29]	Z. Liu, Y. Huang, Y. Huang, Q. Yang, X. Li, Z. Huang, C. Zhi, Chem. Soc. Rev., 2020, 49, 180-232.
[30]	S. Pang, M. Más-Montoya, M. Xiao, C. Duan, Z. Wang, X. Liu, R. A. J. Janssen, G. Yu, F. Huang, Y. Cao, Chem. Eur. J., 2019, 25, 564-572.
[31]	A. De la Peña Ruigómez, D. Rodríguez-San-Miguel, K. C. Stylianou, M. Cavallini, D. Gentili, F. Liscio, S. Milita, O. M. Roscioni, M. L. Ruiz-González, C. Carbonell, D. Maspoch, R. Mas-Ballesté, J. L. Segura, F. Zamora, Chem. Eur. J., 2015, 21, 10666-10670.
[32]	T. Shirokura, T. Hirohata, K. Sato, E. Villani, K. Sekiya, C. Yu-An, T. Kurioka, R. Hifumi, Y. Hattori, M. Sone, I. Tomita, S. Inagi, Angew. Chem. Int. Ed., 2023, 62, e202307343.
[33]	D. Zhu, J.-J. Zhang, X. Wu, Q. Yan, F. Liu, Y. Zhu, X. Gao, M. M. Rahman, B. I. Yakobson, P. M. Ajayan, R. Verduzco, Chem. Sci., 2022, 13, 9655-9667.
[34]	G. Li, J. Bai, C. Liu, Z. Jin, M. Xiao, W. Xing, Small, 2025, 21, 2407163.
[35]	P. Weber, D. J. Weber, C. Dosche, M. Oezaslan, ACS Catal., 2022, 12, 6394-6408.
[36]	B.-Y. Xia, H.-B. Wu, N. Li, Y. Yan, X. W. D. Lou, X. Wang, Angew. Chem. Int. Ed., 2015, 54, 3797-3801.
[37]	X. Li, Y. He, S. Cheng, B. Li, Y. Zeng, Z. Xie, Q. Meng, L. Ma, K. Kisslinger, X. Tong, S. Hwang, S. Yao, C. Li, Z. Qiao, C. Shan, Y. Zhu, J. Xie, G. Wang, G. Wu, D. Su, Adv. Mater., 2021, 33, 2106371.
[38]	T. Fuchs, J. Drnec, F. Calle-Vallejo, N. Stubb, D. J. S. Sandbeck, M. Ruge, S. Cherevko, D. A. Harrington, O. M. Magnussen, Nat. Catal., 2020, 3, 754-761.
[39]	L. Yang, D. Cheng, H. Xu, X. Zeng, X. Wan, J. Shui, Z. Xiang, D. Cao, Proc. Natl. Acad. Sci. U. S. A., 2018, 115, 6626-6631.
[40]	L. Du, V. Prabhakaran, X. Xie, S. Park, Y. Wang, Y. Shao, Adv. Mater., 2021, 33, 2008412.
[41]	C. Li, K. Yu, A. Bird, F. Guo, J. Ilavsky, Y. Liu, D. A. Cullen, A. Kusoglu, A. Z. Weber, P. J. Ferreira, J. Xie, Energy Environ. Sci., 2023, 16, 2977-2990.
[42]	G. Zhao, Y. Zhang, Z. Gao, H. Li, S. Liu, S. Cai, X. Yang, H. Guo, X. Sun, ACS Energy Lett., 2020, 5, 1022-1031.
[43]	G. Zhao, H. Li, Z. Gao, L. Xu, Z. Mei, S. Cai, T. Liu, X. Yang, H. Guo, X. Sun, Adv. Funct. Mater., 2021, 31, 2101019.

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

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 5

References

Related Articles 15

Recommended Articles

Metrics

[1]	Wenao Xie, Zhifang Jia, Chang Shu, Tingxia Wang, Jianhong Xi, Jiaxuan Cai, Xiangyang Song, Yu Che, Xiaoyan Wang, Kewei Wang, Bien Tan. Cyano-functionalized covalent organic frameworks for enhanced photocatalytic hydrogen peroxide production via microenvironment engineering [J]. Chinese Journal of Catalysis, 2026, 83(4): 282-293.
[2]	Tao Wei, Zhanpeng Liang, Boxin Zhang, Yunhao Xu, Zhaoxue Sun, Minghao Duo, Minghui Chen, Sheng Zhang, Bao Zhang. Efficient electrocatalytic CO₂ reduction by crystalline polymetallophthalocyanine covalent organic frameworks unprecedentedly constructed involving 4-dimethylaminopyridine (DMAP)-type nucleophilic catalyst [J]. Chinese Journal of Catalysis, 2026, 83(4): 319-329.
[3]	Yujuan Zhuang, Qingjun Chen, Xingen Lin, Lingwei Meng, Fuwang Hu, Xintao Yu, Geoffrey I. N. Waterhouse, Lishan Peng. Enhancing the stability of Pt/C catalysts for oxygen reduction reaction in PEMFCs via Fe-N-C-mediated 5d-3d/2p orbital hybridization [J]. Chinese Journal of Catalysis, 2026, 83(4): 308-318.
[4]	Donghua Li, Hongyin Hu, Jinye Zhou, Hanyun Miao, Yu Wu, Jinyan Wang, Baochun Guo, Mingliang Du, Shuanglong Lu. Steering product selectivity via metallic site-dependent pathways in porphyrin-based covalent organic frameworks for electrocatalytic nitrite reduction [J]. Chinese Journal of Catalysis, 2026, 83(4): 258-270.
[5]	Ke-Hui Xie, Cong-Xue Liu, Yan Geng, Jing-Lan Kan, Guang-Bo Wang, Yu-Bin Dong. Efficient H₂O₂ photosynthesis through linker engineering of benzotrithiophene-based covalent organic frameworks [J]. Chinese Journal of Catalysis, 2026, 83(4): 271-281.
[6]	Rumeng Zhang, Muke Lin, Yimu Jiao, Cheng Chen, Mengling Hu, Hao Zhou, Dehua Xia. Fe(III)-mediated self-sustaining photo-Fenton system on metal-free pyridine-COF: Interfacial electron transfer for water purification [J]. Chinese Journal of Catalysis, 2026, 82(3): 225-237.
[7]	Wenjie Gong, Yangsen Xu, Hao Liu, Wanbin Lin, Zhiwei Du, Yixuan Huang, Jiang Liu, Yu Chen. An active and durable anode catalytic layer with in-situ exsolved Pd-Ni nanoparticles for protonic ceramic fuel cells on hydrocarbon fuels [J]. Chinese Journal of Catalysis, 2026, 82(3): 125-134.
[8]	Weiping Xiao, Yue Zhang, Na Wang, Xiaofei Yang. Synergistic electrode-electrolyte coupling enabled highly efficient and durable high entropy intermetallic-based electrocatalyst for oxygen reduction reaction [J]. Chinese Journal of Catalysis, 2026, 82(3): 92-104.
[9]	Hui-Min Xu, Xiao-Qi Gong, Kai-Hang Yue, Chen-Jin Huang, Hong-Rui Zhu, Lian-Jie Song, Gao-Ren Li. Fe and Co bimetallic single-atoms coordinated by N and Te as bifunctional oxygen reduction/evolution catalysts for high-performance zinc-air battery [J]. Chinese Journal of Catalysis, 2026, 81(2): 319-332.
[10]	Haihong Zhong, Qianqian Xu, Weiting Yang, Nicolas Alonso-Vante, Yongjun Feng. Composition regulation of iron-group transition metal chalcogenides for the oxygen electrocatalysis: Electronic structure and surface reconstruction [J]. Chinese Journal of Catalysis, 2026, 81(2): 37-68.
[11]	Jiaping Lu, Chao Lin, Chao Li, Hongjie Shi, Nengyi Liu, Wandong Xing, Sibo Wang, Guigang Zhang, Teng-Teng Chen, Xiong Chen. Bipyridine-integrated bisoxazole-based donor-acceptor covalent organic framework for enhanced photocatalytic H₂O₂ synthesis [J]. Chinese Journal of Catalysis, 2026, 81(2): 185-194.
[12]	Bolin Yang, Fei Jin, Zhiliang Jin. Efficient photocatalytic hydrogen production by a heterojunction strategy with covalent organic frameworks loaded with non-precious-metal semiconductors [J]. Chinese Journal of Catalysis, 2026, 81(2): 172-184.
[13]	Xiaofeng Chen, Yixuan Huang, Wanbin Lin, Jiaojiao Xia, Xirui Zhang, Wenjie Gong, Chuqian Jian, Hao Liu, Jiacheng Zeng, Jiang Liu, Yu Chen. Mn-doping induced phase segregation of air electrodes enables high-performance and durable reversible protonic ceramic cells [J]. Chinese Journal of Catalysis, 2026, 81(2): 333-343.
[14]	Wenbo Shi, Kai Zhu, Xiaogang Fu, Chenhong Liu, Yang Yuan, Jialiang Pan, Qing Zhang, Zhengyu Ba. Dual-site confinement strategy tuning Fe-N-C electronic structure to enhance oxygen reduction performance in PEM fuel cells [J]. Chinese Journal of Catalysis, 2026, 80(1): 293-303.
[15]	Shuqi Liang, Zhen Xiao, Jinni Shen, Wenxin Dai, Zizhong Zhang. Tuning radical generation rate for efficient CH₄ photooxidation to CH₃OH over AgPd alloy and Co₃O₄ cascade active sites [J]. Chinese Journal of Catalysis, 2026, 80(1): 189-199.