Enhanced oxygen evolution and reduction by phosphorus-doped Co9S8 derived from MOFs: Toward high-performance zinc-air batteries

doi:10.1016/S1872-2067(26)65028-0

Abstract

Abstract:

Developing high-performance electrocatalysts for the oxygen evolution (OER) and reduction reactions (ORR) is key to further developing rechargeable zinc-air batteries (ZABs). In this work, we demonstrate phosphorus-doped hollow cobalt pentlandite (P-Co₉S₈) nanocubes, derived from ZIF-67, which combine MOF-inherited porosity with phosphorus-induced electronic modulation, as a bifunctional oxygen electrocatalyst. As a cathode catalyst, P-Co₉S₈ achieves a high power density of 177 mW cm^-1, a specific capacity of 775 mAh g_Zn^-1, and remarkable cycling stability over 900 h. Comprehensive experiments and density functional theory show that P doping tunes the local coordination environment, optimizes the d-band center, and lowers reaction energy barriers, enabling fast, durable, and selective oxygen electrocatalysis. This study establishes a generalizable strategy for designing advanced chalcogenide-based electrocatalysts for next-generation energy storage devices.

Key words: Metal-organic framework, Phosphorus doping, Cobalt sulfide, Bifunctional electrocatalyst, Oxygen evolution reaction, Oxygen reduction reaction, Zinc-air battery

Xiang Wang, Min Zhou, Xiaobin Liao, Xu Han, Congcong Xing, René Bes, Simo Huotari, Jordi Arbiol, Andreu Cabot. Enhanced oxygen evolution and reduction by phosphorus-doped Co₉S₈ derived from MOFs: Toward high-performance zinc-air batteries[J]. Chinese Journal of Catalysis, 2026, 85: 204-215.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65028-0

https://www.cjcatal.com/EN/Y2026/V85/I6/204

Figures/Tables 6

Fig. 1. (a) Schematic illustration of the synthesis process for P-Co9S8. SEM images of ZIF-67 (b), Co9S8 (c), and P-Co9S8 (d). (e,f) TEM images of P-Co9S8. (g) HRTEM image and corresponding FFT spectrum (insert). The P-Co9S8 lattice fringe distances were measured to be 0.235, 0.288, and 0.296 nm, at 52.92° and 130.11°, which could be interpreted as the cubic Co9S8 phase, visualized along its [011] zone axis. (h,i) HAADF-STEM images and EELS chemical composition maps obtained from the red squared area of the STEM micrograph. Individual Co L2,3-edges at 779 eV (red), P L2,3-edges at 132 eV (green), S L2,3-edges at 165 eV (blue), and composites of Co-P, Co-S, Co-P-S.

Fig. 2. XRD patterns (a) and P 2p (b), S 2p (c), and Co 2p (d) high-resolution XPS spectra of Co9S8 and P-Co9S8. (e) Normalized XANES at the Co K-edge. (f) Calculated Co valence state from the XANES. Corresponding FT-EXAFS spectra (h) and Wavelet transform for the k2-weighted EXAFS signals (i) of Co for Co9S8 and P-Co9S8.

Fig. 3. (a) LSV polarization curves. (b) Corresponding Tafel plots. (c) Overpotential at 10 mA cm-2 and extracted Tafel slopes for the as-prepared catalysts. (d) Capacitive current density. (e) EIS Nyquist responses. (f) LSV curves of P-Co9S8 recorded before and after 5000 cycles. (g) Chronoamperometric stability of P-Co9S8 compared with IrO2. (h) Benchmarking of overpotential at 10 mA cm-2 and Tafel slopes against reported sulfide-based OER catalysts (Table S2).

Fig. 4. LSV polarization curves (a), Tafel plots (b), and Ehalf together with jk (0.85 V vs. RHE) (c) for Co9S8, P-Co9S8, P-Co3S4, and Pt/C measured in O2-saturated 0.1 mol L-1 KOH at 1600 rpm. RDE polarization curves of P-Co9S8 acquired at different rotation rates (d), with the corresponding K-L plots (e). (f) Electron-transfer number and H2O2 yield of P-Co9S8 (inset: RRDE LSV curves at 1600 rpm). (g) Chronoamperometric stability tests. (h) LSV curves of P-Co9S8 before and after 2000 CV cycles. (i) Methanol crossover tolerance at 0.7 V for P-Co9S8 and commercial Pt/C.

Fig. 5. (a) Atomic structure models of P-Co9S8 (b,c) PDOS and d band center of Co9S8 and P-Co9S8. Gibbs free energy evolution for OER of the different P-Co9S8 models at 1.23 V (d), and of Co9S8 and P-Co9S8 at different potentials (e).

Fig. 6. (a) Schematic diagram of an aqueous ZAB. Open circuit potentials (b), discharge polarization curves and corresponding peak powder density (c), specific capacities (d), and long-term charge-discharge cycling stabilities (e) of Pt/C +RuO2, Co9S8 and P-Co9S8 cells.

References

[1]	Q. Wang, S. Kaushik, X. Xiao, Q. Xu, Chem. Soc. Rev., 2023, 52, 6139-6190.
[2]	L. Li X,. Tang B,. Wu B,. Huang K,. Yuan Y. Chen, Adv. Mater., 2024, 36, 2308326.
[3]	J. Zhang, Z. Zhao, Z. Xia, L. Dai, Nat. Nanotechnol., 2015, 10, 444-452.
[4]	L. Yang, R. He, M. Botifoll, Y. Zhang, Y. Ding, C. Di, C. He, Y. Xu, L. Balcells, J. Arbiol, Y. Zhou, A. Cabot, Adv. Mater., 2024, 36, 2400572.
[5]	R. He L,. Yang Y,. Zhang D,. Jiang S,. Lee S,. Horta Z,. Liang X,. Lu A,. Ostovari Moghaddam J,. Li M,. Ibáñez Y,. Xu Y,. Zhou A. Cabot, Adv. Mater., 2023, 35, 2303719.
[6]	R. He S,. Wang L,. Yang S,. Horta Y,. Ding C,. Di X,. Zhang Y,. Xu M,. Ibáñez Y,. Zhou S,. Mebs H,. Dau J. N., Hausmann W,. Huo P. W., Menezes A. Cabot, Energy Environ. Sci., 2024, 17, 7193-7208.
[7]	C. He L,. Yang C,. Dong X,. Peng Y,. Ibraheem O,. Usoltsev L,. Simonelli R,. He A,. Cabot Y. Lu, Angew. Chem. Int. Ed., 2025, 64, e202419083.
[8]	N. Liu Z,. Peng J,. Sun Y,. Tian L,. Mei G,. Lv R,. He A,. Cabot J. Zhang, Adv. Funct. Mater., 2025, 35, 2419515.
[9]	X. Chen, Q. Liu, T. Bai, W. Wang, F. He, M. Ye, Chem. Eng. J., 2021, 409, 127237.
[10]	S. Chandrasekaran, L. Yao, L. Deng, C. Bowen, Y. Zhang, S. Chen, Z. Lin, F. Peng, P. Zhang, Chem. Soc. Rev., 2019, 48, 4178-4280.
[11]	D. Lyu S,. Yao A,. Ali Z.-Q., Tian P,. Tsiakaras P.-K. Shen, Adv. Energy Mater., 2021, 11, 2101249.
[12]	N. Wang, D. Chen, S. Ning, J. Lao, J. Xu, M. Luo, W. Zhang, J. Chen, M. Yang, F. Xie, Y. Jin, S. Sun, H. Meng, Adv. Mater., 2024, 36, 2306138.
[13]	C. Yang, J. Chen, L. Yan, Y. Gao, J. Ning, Y. Hu, Appl. Catal. B, 2024, 352, 124060.
[14]	L. Wu S,. Li L,. Li H,. Zhang L,. Tao X,. Geng H,. Yang W,. Zhou C,. Sun D,. Ju B. An, Appl. Catal. B, 2023, 324, 122250.
[15]	Z. Wang, Z. Lin, J. Deng, S. Shen, F. Meng, J. Zhang, Q. Zhang, W. Zhong, L. Gu, Adv. Energy Mater., 2021, 11, 2170020.
[16]	P. Bai P,. Wang J,. Mu Y,. Zhao C,. Du Y. Su, Appl. Catal. B, 2024, 349, 123882.
[17]	B. Tian, L. Sun, D. Ho, Adv. Funct. Mater., 2023, 33, 2210298.
[18]	Y. Park, H. K. Kim, T. Kwon, M. Jun, D. Kim, T. Kim, B. Kim, H. Baik, K.-J. Kim, J. Y. Lee, J. Y. Kim, M.-H. Baik, K. Lee, Adv. Energy Mater., 2025, 15, 2405035.
[19]	S. Zhang, F. Ling, L. Wang, R. Xu, M. Ma, X. Cheng, R. Bai, Y. Shao, H. Huang, D. Li, Y. Jiang, X. Rui, J. Bai, Y. Yao, Y. Yu, Adv. Mater., 2022, 34, 2201420.
[20]	F. Zhang, Y. Song, Z. Fei, Y. Ding, Y. Xie, Y. Wu, R. Chen, Y. Qian, D. J. Kang, H. Pang, Chem. Eng. J., 2025, 515, 163531.
[21]	H. Wang, J. Xu, Q. Zhang, S. Hu, W. Zhou, H. Liu, X. Wang, Adv. Funct. Mater., 2022, 32, 2112362.
[22]	L. Wu F,. Su T,. Liu G.-Q., Liu Y,. Li T,. Ma Y,. Wang C,. Zhang Y,. Yang S.-H. Yu, J. Am. Chem. Soc., 2022, 144, 20620-20629.
[23]	J. Sheng, S. Sun, G. Jia, S. Zhu, Y. Li, ACS Nano, 2022, 16, 15994-16002.
[24]	D. Wang, Y.-P. Deng, Y. Zhang, Y. Zhao, G. Zhou, L. Shui, Y. Hu, M. Shakouri, X. Wang, Z. Chen, Energy Storage Mater., 2021, 41, 427-435.
[25]	W. Bi C,. Li D,. Yang Y.-Z., Zhang L,. Hu Q,. Gong J,. Zhang Y,. Zhang M,. Li J,. Wei Y,. Zhou D,. Zhou T,. Wu L.-F., Chen A. Cabot, Energy Environ. Sci., 2025, 18, 1929-1940.
[26]	G. Gao X,. Chen L,. Han G,. Zhu J,. Jia A,. Cabot Z. Sun, Coord. Chem. Rev., 2024, 503, 215639.
[27]	X. Wang, C. Xing, Z. Liang, P. Guardia, X. Han, Y. Zuo, J. Llorca, J. Arbiol, J. Li, A. Cabot, J. Mater. Chem. A, 2022, 10, 3659-3666.
[28]	X. Wang, X. Han, R. Du, Z. Liang, Y. Zuo, P. Guardia, J. Li, J. Llorca, J. Arbiol, R. Zheng, A. Cabot, Appl. Catal. B, 2023, 320, 121988.
[29]	X. Wang, J. Li, Q. Xue, X. Han, C. Xing, Z. Liang, P. Guardia, Y. Zuo, R. Du, L. Balcells, J. Arbiol, J. Llorca, X. Qi, A. Cabot, ACS Nano, 2023, 17, 825-836.
[30]	D. Yang, C. Zhang, J. J. Biendicho, X. Han, Z. Liang, R. Du, M. Li, J. Li, J. Arbiol, J. Llorca, Y. Zhou, J. R. Morante, A. Cabot, ACS Nano, 2020, 14, 15492-15504.
[31]	X. Wang, X. Han, R. Du, C. Xing, X. Qi, Z. Liang, P. Guardia, J. Arbiol, A. Cabot, J. Li, ACS Appl. Mater. Interfaces, 2022, 14, 41924-41933.
[32]	A. Cabot, M. Ibáñez, P. Guardia, A. P. Alivisatos, J. Am. Chem. Soc., 2009, 131, 11326-11328.
[33]	M. Ibáñez, J. Fan, W. Li, D. Cadavid, R. Nafria, A. Carrete, A. Cabot, Chem. Mater., 2011, 23, 3095-3104.
[34]	Y. Yin R. M., Rioux C. K., Erdonmez S,. Hughes G. A., Somorjai A. P. Alivisatos, Science, 2004, 304, 711-714.
[35]	Y. Yan M,. Wu L,. Zhou W,. Chen L,. Han G,. Gao Y,. Cui Z,. Sun A. Cabot, Adv. Funct. Mater., 2025, 35, 2419328.
[36]	X. Chen, Y. Cheng, Y. Wen, Y. Wang, X. Yan, J. Wei, S. He, J. Zhou, Adv. Sci., 2022, 9, 2204742.
[37]	X. Yu J,. Liu J,. Li Z,. Luo Y,. Zuo C,. Xing J,. Llorca D,. Nasiou J,. Arbiol K,. Pan T,. Kleinhanns Y,. Xie A. Cabot, Nano Energy, 2020, 77, 105116.
[38]	J. Liu Z,. Luo J,. Li X,. Yu J,. Llorca D,. Nasiou J,. Arbiol M,. Meyns A. Cabot, Appl. Catal. B, 2019, 242, 258-266.
[39]	X. Zhu X,. Yao X,. Lang J,. Liu C. V., Singh E,. Song Y,. Zhu Q. Jiang, Adv. Sci., 2023, 10, 2303682.
[40]	T. Hu Y,. Zhao Y,. Yang H,. Lv R,. Zhong F,. Ding F,. Mo H,. Hu C,. Zhi G. Liang, Adv. Mater., 2024, 36, 2312246.
[41]	C. Zhang, J. J. Biendicho, T. Zhang, R. Du, J. Li, X. Yang, J. Arbiol, Y. Zhou, J. R. Morante, A. Cabot, Adv. Funct. Mater., 2019, 29, 1903842.
[42]	J. Zhang, J. Li, W. Chen, Q. Zhang, J. Li, Y. Li, X. Ren, X. Ouyang, X. Meng, J. Qiu, J. Hu, S. Ye, J. Liu, Q. Zhang, Appl. Catal. B, 2025, 373, 125333.
[43]	L. Wang, H. Su, Z. Zhang, J. Xin, H. Liu, X. Wang, C. Yang, X. Liang, S. Wang, H. Liu, Y. Yin, T. Zhang, Y. Tian, Y. Li, Q. Liu, X. Sun, J. Sun, D. Wang, Y. Li, Angew. Chem. Int. Ed., 2023, 62, e202314185.
[44]	Y. Chang, Z. Ma, X. Lu, S. Wang, J. Bao, Y. Liu, C. Ma, Angew. Chem. Int. Ed., 2023, 62, e202310163.
[45]	S. Xue J,. Shang X,. Pu H,. Cheng L,. Zhang C,. Wang C.-S., Lee Y. Tang, Energy Storage Mater., 2023, 55, 33-41.
[46]	X. Wang, Y. Zuo, S. Horta, R. He, L. Yang, A. Ostovari Moghaddam, M. Ibáñez, X. Qi, A. Cabot, ACS Appl. Mater. Interfaces, 2022, 14, 48212-48219.
[47]	V. Mishra, A. E. Praveen, D. Raveendran, A. Chandrasekar, V. Mahalingam, Small, 2025, 21, 2412372.
[48]	L. Liu Y,. Chen Q,. Zhang Z,. Liu K,. Yue Y,. Cheng D,. Li Z,. Zhu J,. Li Y. Wang, Appl. Catal. B, 2024, 354, 124140.
[49]	X. Zhou, J. Li, G. Zhou, W. Huang, Y. Zhang, J. Yang, H. Pang, M. Zhang, D. Sun, Y. Tang, L. Xu, J. Energy Chem., 2024, 93, 592-600.
[50]	Y. Wang, Z. Meng, X. Gong, C. Jiang, C. Zhang, J. Xu, Y. Li, J. Bao, Y. Cui, H. Wang, Y. Zeng, X. Hu, S. Yu, H. Tian, Chem. Eng. J., 2022, 431, 133980.

Enhanced oxygen evolution and reduction by phosphorus-doped Co₉S₈ derived from MOFs: Toward high-performance zinc-air batteries

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 6

References

Related Articles 15

Recommended Articles

Metrics

[1]	Ping Li, Liang Wei, Wei Xia, Chengcheng Yuan, Chenbin Ai, Meng Li. Ultrafast electron transfer in 2D/2D g-C₃N₄/WO₃ S-scheme heterojunctions for enhanced H₂O₂ production [J]. Chinese Journal of Catalysis, 2026, 85(6): 333-345.
[2]	Kaiyang Zhang, Huihui Li, Shuhao Wang, Rui Yao, Jinping Li, Chuan Zhao, Guang Liu. Breaking the activity-stability trade-off of iridium-based catalysts for proton exchange membrane water electrolyzers [J]. Chinese Journal of Catalysis, 2026, 85(6): 193-203.
[3]	Liqing Wu, Wenxia Huang, Bingbing Zhao, Ping Cai, Wei Luo. Surface anions-mediated dynamic interfacial free water enriched microenvironment on RuO₂ for efficient acidic oxygen evolution [J]. Chinese Journal of Catalysis, 2026, 85(6): 237-246.
[4]	Qianqian Xu, Haihong Zhong, Chunli Li, Rong Jiang, Yongjun Feng, Luis Alberto Estudillo-Wong. O-bridged NiSe₂/CQDs composite synergistically triggers interfacial electrons transfer to promote H₂O₂ electrosynthesis [J]. Chinese Journal of Catalysis, 2026, 85(6): 258-271.
[5]	Wenning Liu, Li An, Jinming Wang, Ruyue Li, Jie Mu, Yongde Long, Dan Qu, Yichang Liu, Yuxiang Hu, Xiayan Wang, Ning Jiang, Zaicheng Sun. Group IIIA metals-induced p-d orbital hybridization enhances the oxygen reduction performance of Pd based metallene in zinc-air batteries [J]. Chinese Journal of Catalysis, 2026, 84(5): 144-158.
[6]	Jian Li, Zhenfa Wu, Xinru Zhang, Tongan Yan, Jin Luo, Wenjuan Xue, Zhaolin Lv, Hongliang Huang, Chongli Zhong. Dynamic coordination transformation from single-to dual-metal sites in MOFs for cascaded photoreforming of plastics into CO [J]. Chinese Journal of Catalysis, 2026, 84(5): 314-323.
[7]	Ran Sun, Yuqi Zhang, Kunge Hou, Yujie Tan, Xingang Liu, Jianyuan Hou, Weixuan Zhao, Andrew E. H. Wheatley, Renxi Zhang. Designing hydrogen-bonds in covalent organic frameworks: accelerating proton-coupled electron transfer for enhanced photocatalytic H₂O₂ synthesis [J]. Chinese Journal of Catalysis, 2026, 84(5): 274-287.
[8]	Hyunseok Yoon, Hee Jo Song, Yumin Park, Andi Haryanto, Dohun Kim, Kyuri Cho, Chanyeon Kim, Wooyul Kim, Chan Woo Lee, Dong-Wan Kim. Dynamic tuning of acidic oxygen evolution reaction pathways in Ru catalysts via Cu-induced surface restructuring [J]. Chinese Journal of Catalysis, 2026, 83(4): 363-375.
[9]	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.
[10]	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(4): 294-307.
[11]	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.
[12]	Yixin Li, Jianhao Qiu, Guanglu Xia, Qiying Liu, Biyao Fang, Meng Liu, Chen Chen, Jianfeng Yao. Hollow tubular In₂O₃ modified carbon nitride for photocatalytic high-yield cleavage of lignin C-C bonds under 395 nm light [J]. Chinese Journal of Catalysis, 2026, 83(4): 209-218.
[13]	Lin Liu, Jun Chen, Ailong Li, Shuang Kong, Ying Zhang, Yafei Qiao, Pengfei Zhang, Can Li, Hongxian Han. Harmonization of acidic OER activity and stability of ruthenium-manganese oxide by optimization of amorphous-crystalline heterostructure [J]. Chinese Journal of Catalysis, 2026, 82(3): 61-73.
[14]	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.
[15]	Xinran Sun, Mengtian Huo, Jianhang Sun, Yu Liang, Kaichi Qin, Haoyang Zhang, Zihao Xing, Jinfa Chang. Sacrificial conversion of metal sulfide precursors into active oxyhydroxide catalysts for enhanced oxygen evolution reaction [J]. Chinese Journal of Catalysis, 2026, 82(3): 84-91.