Citation: Zihou Zhang, Haozhe Xu, Yuxiang Wang, Pin Fang, Olga Demidenko, Yujing Li. Dynamically stabilized PtCuNi/C catalyst enabled by oxygen vacancies in WO_3-x[J]. Chinese Chemical Letters, ;2026, 37(5): 110889. doi: 10.1016/j.cclet.2025.110889 shu

Dynamically stabilized PtCuNi/C catalyst enabled by oxygen vacancies in WO_3-x

Zihou Zhang ^{a, 1} ,
Haozhe Xu ^{a, 1} ,
Yuxiang Wang ^a ,
Pin Fang ^a ,
Olga Demidenko ^b ,
Yujing Li ^{a, *,}

a.
Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
b.
Scientific-Practical Materials Research Centre, National Academy of Sciences of Belarus, Minsk 220072, Belarus

yjli@bit.edu.cn

Received Date: 11 December 2024
Revised Date: 11 January 2025
Accepted Date: 19 January 2025
Available Online: 20 January 2025

Figures(6)

The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO_3-x catalyst is designed employing non-stoichiometric WO_3-x with abundant oxygen vacancies (O_vac). The WO_3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO_3-x at the presence of O_vac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO_3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO_3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO_3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
- Tungsten oxide,
- Oxygen vacancies,
- PGM alloy,
- Stability,
- Oxygen reduction
1. [1]
  A. Rodríguez-Castellanos, J.L. Díaz-Bernabé, S. Citalán-Cigarroa, O. Solorza-Feria, 6 - Development and applications of portable systems based on conventional PEM fuel cells, in: P. Ferreira-Aparicio, A.M. Chaparro (Eds.), Portable Hydrogen Energy Systems, Academic Press, 2018, pp. 91–106.
2. [2]
  Y. Wang, D.F. Ruiz Diaz, K.S. Chen, et al., Mater. Today 32 (2020) 178–203. doi: 10.1016/j.mattod.2019.06.005
3. [3]
  R. Rath, P. Kumar, S. Mohanty, et al., Int. J. Energy Res. 43 (2019) 8931–8955. doi: 10.1002/er.4795
4. [4]
  F. Cai, S. Cai, Z. Tu, Energy Convers. Manage. 307 (2024) 118348. doi: 10.1016/j.enconman.2024.118348
5. [5]
  S. Hao, HSET 81 (2024) 607–614. doi: 10.54097/k3tbdx94
6. [6]
  S. Zhang, X. He, Y. Ding, et al., Renew. Sustain. Energy Rev. 204 (2024) 114821. doi: 10.1016/j.rser.2024.114821
7. [7]
  A. Kongkanand, M.F. Mathias, J. Phys. Chem. Lett. 7 (2016) 1127–1137. doi: 10.1021/acs.jpclett.6b00216
8. [8]
  A. Pavlets, E. Titskaya, A. Alekseenko, et al., Int. J. Hydrogen Energy 50 (2024) 458–470. doi: 10.1016/j.ijhydene.2023.07.028
9. [9]
  F. Zhu, A. Wu, L. Luo, et al., Fuel Cells 20 (2020) 196–202. doi: 10.1002/fuce.201900189
10. [10]
  Z. Zhao, Z. Liu, A. Zhang, et al., Nat. Nanotechnol. 17 (2022) 968–975. doi: 10.1038/s41565-022-01170-9
11. [11]
  C. Wang, J.S. Spendelow, Curr. Opin. Electrochem. 28 (2021) 100715. doi: 10.1016/j.coelec.2021.100715
12. [12]
  P. Mardle, G. Thirunavukkarasu, S. Guan, et al., ACS Appl. Mater. Interfaces 12 (2020) 42832–42841. doi: 10.1021/acsami.0c11531
13. [13]
  X. Zhao, C. Xi, R. Zhang, et al., ACS Catal. 10 (2020) 10637–10645. doi: 10.1021/acscatal.0c03036
14. [14]
  G. Fisseha, Y. Hu, Y. Yu, et al., Chin. Chem. Lett. 35 (2024) 108445. doi: 10.1016/j.cclet.2023.108445
15. [15]
  Q. Wang, H. Tao, Z. Li, et al., J. Alloys Compd. 814 (2020) 152212. doi: 10.1016/j.jallcom.2019.152212
16. [16]
  T. Yu, Y. Chen, Y. Li, et al., J. Mater. Sci. : Mater. Electron. 33 (2022) 12713–12725. doi: 10.1007/s10854-022-08218-5
17. [17]
  M. Ma, L. Shen, Z. Zhao, et al., eScience 4 (2024) 100254. doi: 10.1016/j.esci.2024.100254
18. [18]
  Y. Wang, D. Wang, Y. Li, SmartMat 2 (2021) 56–75. doi: 10.1002/smm2.1023
19. [19]
  Z. Zhou, H.J. Zhang, X. Feng, et al., J. Electroanal. Chem. 959 (2024) 118165. doi: 10.1016/j.jelechem.2024.118165
20. [20]
  R.L. Borup, A. Kusoglu, K.C. Neyerlin, et al., Curr. Opin. Electrochem. 21 (2020) 192–200. doi: 10.1016/j.coelec.2020.02.007
21. [21]
  M. Prokop, M. Drakselova, K. Bouzek, Curr. Opin. Electrochem. 20 (2020) 20–27. doi: 10.1016/j.coelec.2020.01.016
22. [22]
  Q. Zhuo, M. Luo, Q. Guo, et al., Electrochim. Acta 213 (2016) 358–367. doi: 10.1016/j.electacta.2016.07.005
23. [23]
  F. Xiao, Y.C. Wang, Z.P. Wu, et al., Adv. Mater. 33 (2021) 2006292. doi: 10.1002/adma.202006292
24. [24]
  X. Liu, S. Chen, Z. Xiong, et al., Prog. Mater. Sci. 130 (2022) 100978. doi: 10.1016/j.pmatsci.2022.100978
25. [25]
  H. -Z. Xu, D. Li, Y. Chen, et al., Tungsten 6 (2024) 293–303. doi: 10.1007/s42864-023-00226-0
26. [26]
  S. Kumar, S.N. Bhange, R. Soni, et al., ACS Appl. Energy Mater. 3 (2020) 1908–1921. doi: 10.1021/acsaem.9b02333
27. [27]
  M. Babu Poudel, P. Chandra Lohani, A.A. Kim, Chem. Phys. Lett. 804 (2022) 139884. doi: 10.1016/j.cplett.2022.139884
28. [28]
  Y. Liu, S. Shrestha, W.E. Mustain, ACS Catal. 2 (2012) 456–463. doi: 10.1021/cs200657w
29. [29]
  C. Ma, Y. Jin, M. Shi, et al., J. Electrochem. Soc. 161 (2013) F246.
30. [30]
  W. Tu, K. Chen, L. Zhu, et al., Adv. Funct. Mater. 29 (2019) 1807070. doi: 10.1002/adfm.201807070
31. [31]
  H. Wang, J. Gao, C. Chen, et al., Nano-Micro Lett. 15 (2023) 143. doi: 10.1201/9781003272601-7
32. [32]
  G.Y. Kim, K.R. Yoon, K. Shin, et al., Small 17 (2021) 2103755. doi: 10.1002/smll.202103755
33. [33]
  Q. Wang, Y. Cheng, H.B. Tao, et al., Angew. Chem. 135 (2023) e202216645. doi: 10.1002/ange.202216645
34. [34]
  K.J. May, C.E. Carlton, K.A. Stoerzinger, et al., J. Phys. Chem. Lett. 3 (2012) 3264–3270. doi: 10.1021/jz301414z
35. [35]
  J. Zhu, S. Wang, S. Xie, et al., Chem. Commun. 47 (2011) 4403–4405. doi: 10.1039/c1cc00064k
36. [36]
  S.K. Cui, D.J. Guo, J. Alloys Compd. 874 (2021) 159869. doi: 10.1016/j.jallcom.2021.159869
37. [37]
  H.Q. Pham, T.T. Huynh, A.C.S. Appl, ACS Appl. Nano Mater. 4 (2021) 4983–4993. doi: 10.1021/acsanm.1c00506
38. [38]
  M. Bao, I.S. Amiinu, T. Peng, et al., ACS Energy Lett. 3 (2018) 940–945. doi: 10.1021/acsenergylett.8b00330
39. [39]
  X. Wang, L. Zhang, F. Wang, et al., Prog. Nat. Sci. : Mater. Int. 30 (2020) 905–911. doi: 10.1016/j.pnsc.2020.10.017
40. [40]
  Q. Wu, X. Huang, T. Wan, et al., Inorg. Chem. 61 (2022) 2612–2618. doi: 10.1021/acs.inorgchem.1c03664
41. [41]
  N.T.T. Thao, K. Kim, J.H. Ryu, et al., Adv. Sci. 10 (2023) 2207695. doi: 10.1002/advs.202207695
42. [42]
  G. Liu, H.G. Yang, X. Wang, et al., J. Phys. Chem. C 113 (2009) 21784–21788. doi: 10.1021/jp907749r
43. [43]
  J. Diao, W. Yuan, Y. Qiu, et al., J. Mater. Chem. A 7 (2019) 6730–6739. doi: 10.1039/c9ta01044k
44. [44]
  C. Guillén, J. Herrero, J. Mater. Sci. Technol. 78 (2021) 223–228. doi: 10.1016/j.jmst.2020.11.036
45. [45]
  S. Poongodi, P.S. Kumar, Y. Masuda, et al., RSC Adv. 5 (2015) 96416–96427. doi: 10.1039/C5RA19177G
46. [46]
  J.J. Li, M. Zhang, B. Weng, et al., Appl. Surf. Sci. 507 (2020) 145133. doi: 10.1016/j.apsusc.2019.145133
47. [47]
  J. Di, C. Zhu, M. Ji, et al., Angew. Chem. Int. Ed. 57 (2018) 14847–14851. doi: 10.1002/anie.201809492
48. [48]
  X. Jiao, Z. Chen, X. Li, et al., J. Am. Chem. Soc. 139 (2017) 7586–7594. doi: 10.1021/jacs.7b02290
49. [49]
  R.M. Castagna, J.M. Sieben, A.E. Alvarez, et al., Int. J. Hydrogen Energy 44 (2019) 5970–5982. doi: 10.1016/j.ijhydene.2019.01.090
50. [50]
  J. Bentley, S. Desai, B.P. Bastakoti, Chem. Eur. J. 27 (2021) 9241–9252. doi: 10.1002/chem.202100649
51. [51]
  J. Shim, C.R. Lee, H.K. Lee, et al., J. Power Sources 102 (2001) 172–177. doi: 10.1016/S0378-7753(01)00817-5
52. [52]
  Y. Zhu, Z. Qu, G. Zhang, et al., Electrochim. Acta 475 (2024) 143590. doi: 10.1016/j.electacta.2023.143590
1. [1]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
2. [2]
  Jincheng Zhang , Mengjie Sun , Jiali Ren , Rui Zhang , Min Ma , Qingzhong Xue , Jian Tian . Oxygen vacancies-rich molybdenum tungsten oxide nanowires as a highly active nitrogen fixation electrocatalyst. Chinese Chemical Letters, 2025, 36(1): 110491-. doi: 10.1016/j.cclet.2024.110491
3. [3]
  Qiyan Wu , Ruixin Zhou , Zhangyi Yao , Tanyuan Wang , Qing Li . Effective approaches for enhancing the stability of ruthenium-based electrocatalysts towards acidic oxygen evolution reaction. Chinese Chemical Letters, 2024, 35(10): 109416-. doi: 10.1016/j.cclet.2023.109416
4. [4]
  Xiaoyu Zhao , Kai Gao , Sen Xue , Wei Ran , Rui Liu . Synergistic effects of oxygen vacancies and Pd single atoms on Pd@TiO_2−x for efficient HER catalysis. Chinese Chemical Letters, 2025, 36(6): 110309-. doi: 10.1016/j.cclet.2024.110309
5. [5]
  Fengchen Wang , Yujia Xiang , Yuqi Zhang , Xin Zhou , Jing Zhang , Chuanshu He , Heng Zhang , Zhaokun Xiong , Peng Zhou , Hongyu Zhou , Yang Liu , Bo Lai . A comprehensive review on oxygen vacancies modified catalysts: Synthesis, characterization, and crucial role in catalytic ozonation. Chinese Chemical Letters, 2026, 37(2): 111315-. doi: 10.1016/j.cclet.2025.111315
6. [6]
  Mengxiang Zhu , Tao Ding , Yunzhang Li , Yuanjie Peng , Ruiping Liu , Quan Zou , Leilei Yang , Shenglei Sun , Pin Zhou , Guosheng Shi , Dongting Yue . Graphene controlled solid-state growth of oxygen vacancies riched V₂O₅ catalyst to highly activate Fenton-like reaction. Chinese Chemical Letters, 2024, 35(12): 109833-. doi: 10.1016/j.cclet.2024.109833
7. [7]
  Jinli Chen , Shouquan Feng , Tianqi Yu , Yongjin Zou , Huan Wen , Shibin Yin . Modulating Metal-Support Interaction Between Pt3Ni and Unsaturated WOx to Selectively Regulate the ORR Performance. Chinese Journal of Structural Chemistry, 2023, 42(10): 100168-100168. doi: 10.1016/j.cjsc.2023.100168
8. [8]
  Jinqiang Gao , Haifeng Yuan , Xinjuan Du , Feng Dong , Yu Zhou , Shengnan Na , Yanpeng Chen , Mingyu Hu , Mei Hong , Shihe Yang . Methanol steam mediated corrosion engineering towards high-entropy NiFe layered double hydroxide for ultra-stable oxygen evolution. Chinese Chemical Letters, 2025, 36(1): 110232-. doi: 10.1016/j.cclet.2024.110232
9. [9]
  Xia Gao , Shuaikang Sang , Enquan Zhu , Lihua Cai , Chang Liu , Ferdi Karadas , Chao Zhang , Jingxiang Low , Yujie Xiong . Highly dispersed Ni–O site on Ni catalysts for efficient and durable light-driven dry reforming of CH4 at ambient conditions. Chinese Journal of Structural Chemistry, 2025, 44(5): 100570-100570. doi: 10.1016/j.cjsc.2025.100570
10. [10]
  Doudou Liu , Weiwei Guo , Guoliang Mei , Youpeng Dan , Rong Yang , Chao Huang , Yanling Zhai , Xiaoquan Lu . Application of catalyst Cu-t-ZrO₂ based on the electronic metal-support interaction in electrocatalytic nitrate reduction. Chinese Chemical Letters, 2025, 36(8): 110578-. doi: 10.1016/j.cclet.2024.110578
11. [11]
  Yan-Kai Zhang , Yong-Zheng Zhang , Chun-Xiao Jia , Fang Wang , Xiuling Zhang , Yuhang Wu , Zhongmin Liu , Hui Hu , Da-Shuai Zhang , Longlong Geng , Jing Xu , Hongliang Huang . A stable Zn-MOF with anthracene-based linker for Cr(VI) photocatalytic reduction under sunlight irradiation. Chinese Chemical Letters, 2024, 35(12): 109756-. doi: 10.1016/j.cclet.2024.109756
12. [12]
  Jingyuan Yang , Xinyu Tian , Liuzhong Yuan , Yu Liu , Yue Wang , Chuandong Dou . Enhancing stability of diradical polycyclic hydrocarbons via P=O-attaching. Chinese Chemical Letters, 2024, 35(8): 109745-. doi: 10.1016/j.cclet.2024.109745
13. [13]
  Ting Wang , Xin Yu , Yaqiang Xie . Unlocking stability: Preserving activity of biomimetic catalysts with covalent organic framework cladding. Chinese Chemical Letters, 2024, 35(6): 109320-. doi: 10.1016/j.cclet.2023.109320
14. [14]
  Xingang Kong , Yabei Su , Cuijuan Xing , Weijie Cheng , Jianfeng Huang , Lifeng Zhang , Haibo Ouyang , Qi Feng . Facile synthesis of porous TiO₂/SnO₂ nanocomposite as lithium ion battery anode with enhanced cycling stability via nanoconfinement effect. Chinese Chemical Letters, 2024, 35(11): 109428-. doi: 10.1016/j.cclet.2023.109428
15. [15]
  Xinpin Pan , Yongjian Cui , Zhe Wang , Bowen Li , Hailong Wang , Jian Hao , Feng Li , Jing Li . Robust chemo-mechanical stability of additives-free SiO₂ anode realized by honeycomb nanolattice for high performance Li-ion batteries. Chinese Chemical Letters, 2024, 35(10): 109567-. doi: 10.1016/j.cclet.2024.109567
16. [16]
  Ziling Jiang , Chen Liu , Jie Yang , Xia Li , Chaochao Wei , Qiyue Luo , Zhongkai Wu , Lin Li , Liping Li , Shijie Cheng , Chuang Yu . Designing F-doped Li₃InCl₆ electrolyte with enhanced stability for all-solid-state lithium batteries in a wide voltage window. Chinese Chemical Letters, 2025, 36(6): 109741-. doi: 10.1016/j.cclet.2024.109741
17. [17]
  Xiaodan Wang , Yingnan Liu , Zhibin Liu , Zhongjian Li , Tao Zhang , Yi Cheng , Lecheng Lei , Bin Yang , Yang Hou . Highly efficient electrosynthesis of H₂O₂ in acidic electrolyte on metal-free heteroatoms co-doped carbon nanosheets and simultaneously promoting Fenton process. Chinese Chemical Letters, 2024, 35(7): 108926-. doi: 10.1016/j.cclet.2023.108926
18. [18]
  Wenxuan Yang , Long Shang , Xiaomeng Liu , Sihan Zhang , Haixia Li , Zhenhua Yan , Jun Chen . Ultrafast synthesis of nanocrystalline spinel oxides by Joule-heating method. Chinese Chemical Letters, 2024, 35(11): 109501-. doi: 10.1016/j.cclet.2024.109501
19. [19]
  Huizhong Wu , Ruiheng Liang , Ge Song , Zhongzheng Hu , Xuyang Zhang , Minghua Zhou . Enhanced interfacial charge transfer on Bi metal@defective Bi₂Sn₂O₇ quantum dots towards improved full-spectrum photocatalysis: A combined experimental and theoretical investigation. Chinese Chemical Letters, 2024, 35(6): 109131-. doi: 10.1016/j.cclet.2023.109131
20. [20]
  Jianing He , Xiao Wang , Zijian Wang , Ruize Jiang , Ke Wang , Rui Zhang , Huilin Wang , Baokang Geng , Hongyi Gao , Shuyan Song , Hongjie Zhang . Investigation on Cu promotion effect on Ce-based solid solution-anchored Rh single atoms for three-way catalysis. Chinese Chemical Letters, 2025, 36(2): 109640-. doi: 10.1016/j.cclet.2024.109640

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(7)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Dynamically stabilized PtCuNi/C catalyst enabled by oxygen vacancies in WO3-x

Metrics

通讯作者: 陈斌, bchen63@163.com

Dynamically stabilized PtCuNi/C catalyst enabled by oxygen vacancies in WO_3-x