English

Electrochemical Synthesis for Metallic Nanocrystal Electrocatalysts: Principle, Application and Challenge

• Lutian Zhao ^1, ,
• Yangge Guo ^1, ,
• Liuxuan Luo ^1, ,
• Xiaohui Yan ^1, ,
• Shuiyun Shen ^{1, 2, ,} ,
• Junliang Zhang ^{1, 2,}

• 1.

  Institute of Fuel Cells, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

• 2.

  MOE Key Laboratory of Power & Machinery Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Corresponding author: Shuiyun Shen, Email: shuiyun_shen@sjtu.edu.cn

• Received Date: 14 June 2023
  Accepted Date: 23 August 2023
  Revised Date: 30 July 2023
  Available Online: 15 July 2024
• Fund Project:

  the National Key Research and Development Program of China 

  the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University 

Abstract: Nanoscale metallic catalysts are garnering increased attention in the advancement of electrochemical energy conversion technologies. The precise control of nanocrystal morphology, size, and crystalline structures offers the ability to manipulate electronic properties and enhance intrinsic catalytic performance. Consequently, a profound understanding of the nanocrystal growth mechanism becomes imperative for the design and production of highly active catalysts. However, mechanism studies in colloidal methods generally depend on operando technics and the development is hindered by expensive cost and limited resources. And high-temperature or high-pressure reaction conditions always bring trouble for the application of the equipment, so the in situ methods have been widely used. While ex situ methods need to detach the samples from the reaction environment, which might lose information about the process and thus fail to reflect the real situation. Furthermore, in conventional methods, the use of macromolecular organics to regulate crystal morphology results in intricate post-treatment processes, and any residual substances can adversely affect catalyst performance. Electrochemical synthesis offers a clean and controllable protocol for producing metallic nanocrystals and supported heterogeneous nanoparticle catalysts. In this review, building upon the classic principles of crystal growth in chemical colloidal methods and electrodeposition, it is proposed that the processes occurring during crystal formation could be visualized or monitored through electrochemical tests. By fine-tuning electrochemical parameters and refining deposition procedures, nucleation density and growth rates along specific facet orientations of nanocrystals can be precisely managed. Electrochemical signals provide insights into in situ reduction and deposition behaviors at the electrode-electrolyte interfaces through professional analysis. The direct loading of nanocrystals onto substrates amplifies their synergistic effects, mitigates exfoliation issues, and consequently enhances catalytic activity and stability. Additionally, due to its broader potential window compared to H₂O, non-aqueous liquids hold promise as a solution for preparing active metals and alloys that exhibit distinctive catalytic performance. Furthermore, electrochemical methods facilitate the synthesis of compounds composed of metallic and nonmetal elements, including metal oxides and phosphides. Thus, electrochemical techniques are poised to offer potential high-performance nanoscale metallic catalysts along with profound insights into the crystal growth mechanism. Nevertheless, a critical challenge hindering the application of electrochemical methods lies in bridging the considerable gap between catalysts and the preparation of electrode-level catalyst layers. The electrochemical signal proves highly sensitive to variations in the reaction environment, and discrepancies in electrode and system properties can lead to distinct electrochemical responses. Consequently, thorough investigations are imperative to address these issues.

Key words:
• Electrochemical energy conversion reaction
•  /  Nanoscale metallic electrocatalyst
•  /  High catalytic performance
•  /  Electrochemical synthesis
•  /  Crystal growth mechanism

• 1. [1]

     Yan, Y.; Chen, G.; She, P.; Zhong, G.; Yan, W.; Guan, B. Y.; Yamauchi, Y. Adv. Mater. 2020, 32, e2004654. doi: 10.1002/adma.202004654

  2. [2]

     Wang, J.; Dou, S.; Wang, X. Sci. Adv. 2021, 7, eabf3989. doi: 10.1126/sciadv.abf3989

  3. [3]

     Donaldson, L. Mater. Today 2020, 41, 8. doi: 10.1016/j.mattod.2020.09.024

  4. [4]

     Wu, H. B.; Lou, X. W. Sci. Adv. 2017, 3, eaap9252. doi: 10.1126/sciadv.aap9252

  5. [5]

     Wang, H.; Li, F.; Zhu, X. Fuel Cells 2021, 21, 2. doi: 10.1002/fuce.2021701012

  6. [6]

     Brinkert, K.; Mandin, P. NPJ Microgravity 2022, 8, 52. doi: 10.1038/s41526-022-00242-3

  7. [7]

     Li, M.; Irtem, E.; Iglesias van Montfort, H. P.; Abdinejad, M.; Burdyny, T. Nat. Commun. 2022, 13, 5398. doi: 10.1038/s41467-022-33145-8

  8. [8]

     Wu, Z. Y.; Karamad, M.; Yong, X.; Huang, Q.; Cullen, D. A.; Zhu, P.; Xia, C.; Xiao, Q.; Shakouri, M.; Chen, F. Y.; et al. Nat. Commun. 2021, 12, 2870. doi: 10.1038/s41467-021-23115-x

  9. [9]

     Leow, W. R.; Volker, S.; Meys, R.; Huang, J. E.; Jaffer, S. A.; Bardow, A.; Sargent, E. H. Nat. Commun. 2023, 14, 1954. doi: 10.1038/s41467-023-37382-3

  10. [10]

      Huang, Z.; Zhu, L.; Li, A.; Gao, Z. Front. Energy 2022, 16, 145. doi: 10.1007/s11708-022-0828-6

  11. [11]

      Ma, H.; Sun, Z.; Xue, Z.; Zhang, C.; Chen, Z. Front. Energy 2023, 17, 102. doi: 10.1007/s11708-023-0861-0

  12. [12]

      Davydova, E. S.; Mukerjee, S.; Jaouen, F.; Dekel, D. R. ACS Catal. 2018, 8, 6665. doi: 10.1021/acscatal.8b00689

  13. [13]

      Kulkarni, A.; Siahrostami, S.; Patel, A.; Norskov, J. K. Chem. Rev. 2018, 118, 2302. doi: 10.1021/acs.chemrev.7b00488

  14. [14]

      Liu, M.; Zhao, Z.; Duan, X.; Huang, Y. Adv. Mater. 2019, 31, e1802234. doi: 10.1002/adma.201802234

  15. [15]

      Wang, Y. J.; Long, W.; Wang, L.; Yuan, R.; Ignaszak, A.; Fang, B.; Wilkinson, D. P. Energy Environ. Sci. 2018, 11, 258. doi: 10.1039/c7ee02444d

  16. [16]

      Badreldin, A.; Youssef, E.; Djire, A.; Abdala, A.; Abdel-Wahab, A. Cell Rep. Phys. Sci. 2023, 4, 1011427. doi: 10.1016/j.xcrp.2023.101427

  17. [17]

      Mu, X.; Liu, S.; Chen, L.; Mu, S. Small Struct. 2023, 4, 2200281. doi: 10.1002/sstr.202200281

  18. [18]

      Sahoo, S.; Dekel, D. R.; Maric, R.; Alpay, S. P. ACS Catal. 2021, 11, 2561. doi: 10.1021/acscatal.0c04646

  19. [19]

      Luo, Z.; Zhang, H.; Yang, Y.; Wang, X.; Li, Y.; Jin, Z.; Jiang, Z.; Liu, C.; Xing, W.; Ge, J. Nat. Commun. 2020, 11, 1116. doi: 10.1038/s41467-020-14980-z

  20. [20]

      McCrum, I. T.; Koper, M. T. M. Nat. Energy 2020, 5, 891. doi: 10.1038/s41560-020-00710-8

  21. [21]

      Zheng, Y.; Jiao, Y.; Vasileff, A.; Qiao, S. Z. Angew. Chem. Int. Ed. 2018, 57, 7568. doi: 10.1002/anie.201710556

  22. [22]

      Zhu, J.; Hu, L.; Zhao, P.; Lee, L. Y. S.; Wong, K. Y. Chem. Rev. 2020, 120, 851. doi: 10.1021/acs.chemrev.9b00248

  23. [23]

      Chen, F.-Y.; Wu, Z.-Y.; Adler, Z.; Wang, H. Joule 2021, 5, 1704. doi: 10.1016/j.joule.2021.05.005

  24. [24]

      Fabbri, E.; Schmidt, T. J. ACS Catal. 2018, 8, 9765. doi: 10.1021/acscatal.8b02712

  25. [25]

      Kou, Z.; Li, X.; Zhang, L.; Zang, W.; Gao, X.; Wang, J. Small Sci. 2021, 1, 2100011. doi: 10.1002/smsc.202100011

  26. [26]

      Xie, X.; Du, L.; Yan, L.; Park, S.; Qiu, Y.; Sokolowski, J.; Wang, W.; Shao, Y. Adv. Funct. Mater. 2022, 32, 2110036. doi: 10.1002/adfm.202110036

  27. [27]

      Zhang, B.; Wang, L.; Cao, Z.; Kozlov, S. M.; García de Arquer, F. P.; Dinh, C. T.; Li, J.; Wang, Z.; Zheng, X.; Zhang, L.; et al. Nat. Catal. 2020, 3, 985. doi: 10.1038/s41929-020-00525-6

  28. [28]

      Matheu, R.; Garrido-Barros, P.; Gil-Sepulcre, M.; Ertem, M. Z.; Sala, X.; Gimbert-Suriñach, C.; Llobet, A. Nat. Rev. Chem. 2019, 3, 331. doi: 10.1038/s41570-019-0096-0

  29. [29]

      Todorova, T. K.; Schreiber, M. W.; Fontecave, M. ACS Catal. 2019, 10, 1754. doi: 10.1021/acscatal.9b04746

  30. [30]

      Woldu, A. R.; Huang, Z.; Zhao, P.; Hu, L.; Astruc, D. Coord. Chem. Rev. 2022, 454, 214340. doi: 10.1016/j.ccr.2021.214340

  31. [31]

      Xue, Y.; Guo, Y.; Cui, H.; Zhou, Z. Small Methods 2021, 5, e2100736. doi: 10.1002/smtd.202100736

  32. [32]

      Wang, C.; Zhang, Y.; Luo, H.; Zhang, H.; Li, W.; Zhang, W. X.; Yang, J. Small Methods 2022, 6, e2200790. doi: 10.1002/smtd.202200790

  33. [33]

      Han, S.; Li, H.; Li, T.; Chen, F.; Yang, R.; Yu, Y.; Zhang, B. Nat. Catal. 2023, 6, 402. doi: 10.1038/s41929-023-00951-2

  34. [34]

      Zhao, Y.; Liu, Y.; Zhang, Z.; Mo, Z.; Wang, C.; Gao, S. Nano Energy 2022, 97, 107124. doi: 10.1016/j.nanoen.2022.107124

  35. [35]

      Fang, L.; Wang, S.; Song, C.; Yang, X.; Li, Y.; Liu, H. J. Hazard. Mater. 2022, 421, 126628. doi: 10.1016/j.jhazmat.2021.126628

  36. [36]

      Liang, H. W.; Cao, X.; Zhou, F.; Cui, C. H.; Zhang, W. J.; Yu, S. H. Adv. Mater. 2011, 23, 1467. doi: 10.1002/adma.201004377

  37. [37]

      万昭敏, 魏星, 彭伟, 尹征磊, 肖丽, 庄林. 物理化学学报, 2016, 32, 1467. doi: 10.3866/PKU.WHXB201604144Wan, Z. M.; Wei, X.; Peng, W.; Yin, Z.-L.; Xiao, L.; Zhuang, L. Acta Phys. -Chim. Sin. 2016, 32, 1467. doi: 10.3866/PKU.WHXB201604144

  38. [38]

      Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Norskov, J. K.; Jaramillo, T. F. Science 2017, 355, eaad4998. doi: 10.1126/science.aad4998

  39. [39]

      Kwon, T.; Kim, T.; Son, Y.; Lee, K. Adv. Energy Mater. 2021, 11, 2100265. doi: 10.1002/aenm.202100265

  40. [40]

      Qin, R.; Zheng, N. Chem 2019, 5, 1935. doi: 10.1016/j.chempr.2019.07.011

  41. [41]

      Zhang, L.; Xie, Z.; Gong, J. Chem. Soc. Rev. 2016, 45, 3916. doi: 10.1039/c5cs00958h

  42. [42]

      Marinkovic, N. S.; Sasaki, K.; Adzic, R. R. Front. Energy 2017, 11, 236. doi: 10.1007/s11708-017-0487-1

  43. [43]

      Jin, R.; Zeng, C.; Zhou, M.; Chen, Y. Chem. Rev. 2016, 116, 10346. doi: 10.1021/acs.chemrev.5b00703

  44. [44]

      Kwon, S. G.; Hyeon, T. Small 2011, 7, 2685. doi: 10.1002/smll.201002022

  45. [45]

      Lee, H.; Habas, S. E.; Kweskin, S.; Butcher, D.; Somorjai, G. A.; Yang, P. Angew. Chem. Int. Ed. 2006, 118, 7988. doi: 10.1002/ange.200603068

  46. [46]

      Sun, Y. Chem. Soc. Rev. 2013, 42, 2497. doi: 10.1039/c2cs35289c

  47. [47]

      You, H.; Fang, J. Nano Today 2016, 11, 145. doi: 10.1016/j.nantod.2016.04.003

  48. [48]

      Peng, Z.; Yang, H. Nano Today 2009, 4, 143. doi: 10.1016/j.nantod.2008.10.010

  49. [49]

      Wang, Y.; He, J.; Liu, C.; Chong, W. H.; Chen, H. Angew. Chem. Int. Ed. 2015, 54, 2022. doi: 10.1002/anie.201402986

  50. [50]

      Xia, Y.; Xiong, Y.; Lim, B.; Skrabalak, S. E. Angew. Chem. Int. Ed. 2009, 48, 60. doi: 10.1002/anie.200802248

  51. [51]

      Habas, S. E.; Lee, H.; Radmilovic, V.; Somorjai, G. A.; Yang, P. Nat. Mater. 2007, 6, 692. doi: 10.1038/nmat1957

  52. [52]

      Gómez-Graña, S.; Goris, B.; Altantzis, T.; Fernández-López, C.; Carbó-Argibay, E.; Guerrero-Martínez, A.; Almora-Barrios, N.; López, N.; Pastoriza-Santos, I.; Pérez-Juste, J.; et al. J. Phys. Chem. Lett. 2013, 4, 2209. doi: 10.1021/jz401269w

  53. [53]

      Kamrani Moghaddam, L.; Ramezani Paschepari, S.; Zaimy, M. A.; Abdalaian, A.; Jebali, A. Cancer Gene Therapy 2016, 23, 321. doi: 10.1038/cgt.2016.38

  54. [54]

      Li, Q.; Rellan-Pineiro, M.; Almora-Barrios, N.; Garcia-Rates, M.; Remediakis, I. N.; Lopez, N. Nanoscale 2017, 9, 13089. doi: 10.1039/c7nr03889e

  55. [55]

      Chen, T.; Rodionov, V. O. ACS Catal. 2016, 6, 4025. doi: 10.1021/acscatal.6b00714

  56. [56]

      Li, Q.; Sun, S. Nano Energy 2016, 29, 178. doi: 10.1016/j.nanoen.2016.02.030

  57. [57]

      Tao, A. R.; Habas, S.; Yang, P. D. Small 2008, 4, 310. doi: 10.1002/smll.200701295

  58. [58]

      Zhao, Q.; Li, H.; Zhang, X.; Yu, S.; Wang, S.; Sun, G. J. Energy Chem. 2020, 41, 120. doi: 10.1016/j.jechem.2019.05.006

  59. [59]

      Dong, A.; Ye, X.; Chen, J.; Kang, Y.; Gordon, T.; Kikkawa, J. M.; Murray, C. B. J. Am. Chem. Soc. 2011, 133, 998. doi: 10.1021/ja108948z

  60. [60]

      Mamme, M. H.; Kohn, C.; Deconinck, J.; Ustarroz, J. Nanoscale 2018, 10, 7194. doi: 10.1039/c7nr08529j

  61. [61]

      Lai, S. C. S.; Lazenby, R. A.; Kirkman, P. M.; Unwin, P. R. Chem. Sci. 2015, 6, 1126. doi: 10.1039/c4sc02792b

  62. [62]

      Scharifker, B. R.; Mostany, J. J. Electroanal. Chem. Interfacial Electrochem. 1984, 177, 13. doi: 10.1016/0022-0728(84)80207-7

  63. [63]

      Altimari, P.; Pagnanelli, F. Electrochim. Acta 2016, 206, 116. doi: 10.1016/j.electacta.2016.04.094

  64. [64]

      Mostany, J.; Mozota, J.; Scharifker, B. R. J. Electroanal. Chem. Interfacial Electrochem. 1984, 177, 25. doi: 10.1016/0022-0728(84)80208-9

  65. [65]

      Zhang, C.; Shen, X.; Pan, Y.; Peng, Z. Front. Energy 2017, 11, 268. doi: 10.1007/s11708-017-0466-6

  66. [66]

      Shen, S. Y.; Guo, Y. G.; Wei, G. H.; Luo, L. X.; Li, F.; Zhang, J. L. Front. Energy 2018, 12, 501. doi: 10.1007/s11708-018-0586-7

  67. [67]

      Chang, Q.; Xu, Y.; Zhu, S.; Xiao, F.; Shao, M. Front. Energy 2017, 11, 254. doi: 10.1007/s11708-017-0493-3

  68. [68]

      Peng, X.; Omasta, T. J.; Roller, J. M.; Mustain, W. E. Front. Energy 2017, 11, 299. doi: 10.1007/s11708-017-0495-1

  69. [69]

      Ye, R.; Liu, Y.; Peng, Z.; Wang, T.; Jalilov, A. S.; Yakobson, B. I.; Wei, S. H.; Tour, J. M. ACS Appl. Mater. Interfaces 2017, 9, 3785. doi: 10.1021/acsami.6b15725

  70. [70]

      Gloag, L.; Benedetti, T. M.; Cheong, S.; Li, Y.; Chan, X. H.; Lacroix, L. M.; Chang, S. L. Y.; Arenal, R.; Florea, I.; Barron, H.; et al. Angew. Chem. Int. Ed. 2018, 57, 10241. doi: 10.1002/anie.201806300

  71. [71]

      Liu, Z.; Zeng, L.; Yu, J.; Yang, L.; Zhang, J.; Zhang, X.; Han, F.; Zhao, L.; Li, X.; Liu, H.; et al. Nano Energy 2021, 85, 105940. doi: 10.1016/j.nanoen.2021.105940

  72. [72]

      Chen, W.; Tang, Y. W.; Lu, T. Electrochemistry 2008, 14, 235. doi: 10.1016/S1872-2067(08)60075-3

  73. [73]

      Visintin, A.; Triaca, W. E.; Arvia, A. J. J. Electroanal. Chem. 1987, 221, 239. doi: 10.1016/0022-0728(87)80260-7

  74. [74]

      Egli, W. A.; Visintin, A.; Triaca, W. E.; Arvia, A. J. Appl. Surf. Sci. 1993, 68, 583. doi: 10.1016/0169-4332(93)90240-C

  75. [75]

      Triaca, W. E.; Kessler, T.; Canullo, J. C.; Arvia, A. J. J. Electrochem. Soc. 1987, 134, 1165. doi: 10.1149/1.2100636

  76. [76]

      Zinola, C. F.; Castro Luna, A. M.; Triaca, W. E.; Arvia, A. J. J. Appl. Electrochem. 1994, 24, 119. doi: 10.1007/BF00247782

  77. [77]

      Tran, D. S.; Park, H.; Kim, H.; Kim, S. K. Int. J. Energy Res. 2020, 45, 5325. doi: 10.1002/er.6155

  78. [78]

      Chen, Y. N.; Zhang, X.; Zhou, Z. Small Methods 2019, 3, 1900050. doi: 10.1002/smtd.201900050

  79. [79]

      Vayssilov, G. N.; Lykhach, Y.; Migani, A.; Staudt, T.; Petrova, G. P.; Tsud, N.; Skala, T.; Bruix, A.; Illas, F.; Prince, K. C.; et al. Nat. Mater. 2011, 10, 310. doi: 10.1038/nmat2976

  80. [80]

      Xiao, F.; Wang, Q.; Xu, G.-L.; Qin, X.; Hwang, I.; Sun, C.-J.; Liu, M.; Hua, W.; Wu, H.-W.; Zhu, S.; et al. Nat. Catal. 2022, 5, 503. doi: 10.1038/s41929-022-00796-1

  81. [81]

      Campbell, C. T. Nat. Chem. 2012, 4, 597. doi: 10.1038/nchem.1412

  82. [82]

      Jackson, C.; Smith, G. T.; Inwood, D. W.; Leach, A. S.; Whalley, P. S.; Callisti, M.; Polcar, T.; Russell, A. E.; Levecque, P.; Kramer, D. Nat. Commun. 2017, 8, 15802. doi: 10.1038/ncomms15802

  83. [83]

      van Deelen, T. W.; Hernández Mejía, C.; de Jong, K. P. Nat. Catal. 2019, 2, 955. doi: 10.1038/s41929-019-0364-x

  84. [84]

      Sun, N.; Wang, M.; Chang, J.; Ge, J.; Xing, W.; Shao, G. Front. Energy 2017, 11, 310. doi: 10.1007/s11708-017-0491-5

  85. [85]

      Liu, Y.; You, H.; Kimmel, Y. C.; Esposito, D. V.; Chen, J. G.; Moffat, T. P. Chem. Mater. 2020, 504, 144472. doi: 10.1016/j.apsusc.2019.144472

  86. [86]

      Quinn, B. M.; Dekker, C.; Lemay, S. G. J. Am. Chem. Soc. 2005, 127, 6146. doi: 10.1021/ja0508828

  87. [87]

      Shinde, D. V.; Kokumai, T. M.; Buha, J.; Prato, M.; De Trizio, L.; Manna, L. J. Mater. Chem. A 2020, 8, 10787. doi: 10.1039/d0ta03475d

  88. [88]

      Mavrokefalos, C. K.; Hasan, M.; Khunsin, W.; Schmidt, M.; Maier, S. A.; Rohan, J. F.; Compton, R. G.; Foord, J. S. Electrochim. Acta 2017, 243, 310. doi: 10.1016/j.electacta.2017.05.039

  89. [89]

      Li, C.; Luo, M.; Xia, Z.; Guo, S. Nano Mater. Sci. 2020, 2, 309. doi: 10.1016/j.nanoms.2019.11.005

  90. [90]

      Tian, N.; Zhou, Z. Y.; Sun, S. G.; Ding, Y.; Wang, Z. L. Science 2007, 316, 732. doi: 10.1126/science.1140484

  91. [91]

      Xiao, C.; Lu, B. A.; Xue, P.; Tian, N.; Zhou, Z. Y.; Lin, X.; Lin, W. F.; Sun, S. G. Joule 2020, 4, 2562. doi: 10.1016/j.joule.2020.10.002

  92. [92]

      Yu, N. F.; Tian, N.; Zhou, Z. Y.; Huang, L.; Xiao, J.; Wen, Y. H.; Sun, S. G. Angew. Chem. Int. Ed. 2014, 53, 5097. doi: 10.1002/anie.201310597

  93. [93]

      Russell, A. E. Faraday Discuss 2008, 140, 9. doi: 10.1039/b814058h

  94. [94]

      Tian, N.; Zhou, Z. Y.; Yu, N. F.; Wang, L. Y.; Sun, S. G. J. Am. Chem. Soc. 2010, 132, 7580. doi: 10.1021/ja102177r

  95. [95]

      Tian, N.; Zhou, Z. Y.; Sun, S. G. Chem. Commun. 2009, 1502. doi: 10.1039/b819751b

  96. [96]

      Wei, L.; Mao, Y. J.; Wei, Y. S.; Li, J. W.; Nie, X. M.; Zhao, X. S.; Fan, Y. J.; Sun, S. G. Cryst. Growth Des. 2019, 19, 1532. doi: 10.1021/acs.cgd.8b00892

  97. [97]

      Cheng, Q.; Jiang, Y. X.; Tian, N.; Zhou, Z. Y.; Sun, S. G. Electrochim. Acta 2010, 55, 8273. doi: 10.1016/j.electacta.2010.06.045

  98. [98]

      Tian, N.; Zhou, Z. Y.; Sun, S. G.; Cui, L.; Ren, B.; Tian, Z. Q. Chem. Commun. 2006, 4090. doi: 10.1039/b609164d

  99. [99]

      Zhou, Z. Y.; Huang, Z. Z.; Chen, D. J.; Wang, Q.; Tian, N.; Sun, S. G. Angew. Chem. Int. Ed. 2010, 49, 411. doi: 10.1002/anie.200905413

  100. [100]

       Liu, S.; Tian, N.; Xie, A. Y.; Du, J. H.; Xiao, J.; Liu, L.; Sun, H. Y.; Cheng, Z. Y.; Zhou, Z. Y.; Sun, S. G. J. Am. Chem. Soc. 2016, 138, 5753. doi: 10.1021/jacs.5b13473

  101. [101]

       Chen, Q. S.; Zhou, Z. Y.; Vidal-Iglesias, F. J.; Solla-Gullon, J.; Feliu, J. M.; Sun, S. G. J. Am. Chem. Soc. 2011, 133, 12930. doi: 10.1021/ja2042029

  102. [102]

       Zhang, J.; Langille, M. R.; Personick, M. L.; Zhang, K.; Li, S.; Mirkin, C. A. J. Am. Chem. Soc. 2010, 132, 14012. doi: 10.1021/ja106394k

  103. [103]

       Wu, J.; Zhang, J.; Peng, Z.; Yang, S.; Wagner, F. T.; Yang, H. J. Am. Chem. Soc. 2010, 132, 4984. doi: 10.1021/ja100571h

  104. [104]

       Zhao, Q.; Martirez, J. M. P.; Carter, E. A. J. Am. Chem. Soc. 2021, 143, 6152. doi: 10.1021/jacs.1c00880

  105. [105]

       Wang, Z.; Yuan, Q.; Shan, J.; Jiang, Z.; Xu, P.; Hu, Y.; Zhou, J.; Wu, L.; Niu, Z.; Sun, J.; et al. J. Phys. Chem. Lett. 2020, 11, 7261. doi: 10.1021/acs.jpclett.0c01261

  106. [106]

       Xia, D.; Yu, H.; Xie, H.; Huang, P.; Menzel, R.; Titirici, M. M.; Chai, G. Nanoscale 2022, 14, 7957. doi: 10.1039/d2nr01900k

  107. [107]

       Wang, J.; Cheng, T.; Fenwick, A. Q.; Baroud, T. N.; Rosas-Hernandez, A.; Ko, J. H.; Gan, Q.; Goddard, W. A., III; Grubbs, R. H. J. Am. Chem. Soc. 2021, 143, 2857. doi: 10.1021/jacs.0c12478

  108. [108]

       Li, D.; Huang, L.; Tian, Y.; Liu, T.; Zhen, L.; Feng, Y. Appl. Catal. B 2021, 292, 120119. doi: 10.1016/j.apcatb.2021.120119

  109. [109]

       Hu, S.; Feng, C.; Wang, S.; Liu, J.; Wu, H.; Zhang, L.; Zhang, J. ACS Appl. Mater. Interfaces 2019, 11, 13168. doi: 10.1021/acsami.8b19052

  110. [110]

       Shin, H. C.; Liu, M. Chem. Mater. 2004, 16, 5460. doi: 10.1021/cm048887b

  111. [111]

       Huan, T. N.; Simon, P.; Rousse, G.; Genois, I.; Artero, V.; Fontecave, M. Chem. Sci. 2017, 8, 742. doi: 10.1039/c6sc03194c

  112. [112]

       Zhang, K.; Zou, R. Small 2021, 17, e2100129. doi: 10.1002/smll.202100129

  113. [113]

       Tong, Y.; Chen, P.; Zhou, T.; Xu, K.; Chu, W.; Wu, C.; Xie, Y. Angew. Chem. Int. Ed. 2017, 56, 7121. doi: 10.1002/anie.201702430

  114. [114]

       Tian, T.; Gao, H.; Zhou, X.; Zheng, L.; Wu, J.; Li, K.; Ding, Y. ACS Energy Lett. 2018, 3, 2150. doi: 10.1021/acsenergylett.8b01206

  115. [115]

       Tao, S.; Yang, F.; Schuch, J.; Jaegermann, W.; Kaiser, B. ChemSusChem 2018, 11, 948. doi: 10.1002/cssc.201702138

  116. [116]

       Li, X.; Wang, Y.; Wang, J.; Da, Y.; Zhang, J.; Li, L.; Zhong, C.; Deng, Y.; Han, X.; Hu, W. Adv. Mater. 2020, 32, e2003414. doi: 10.1002/adma.202003414

  117. [117]

       Huan, T. N.; Rousse, G.; Zanna, S.; Lucas, I. T.; Xu, X.; Menguy, N.; Mougel, V.; Fontecave, M. Angew. Chem. Int. Ed. 2017, 56, 4792. doi: 10.1002/anie.201700388

  118. [118]

       Cao, Y.; Chen, Z.; Ye, F.; Yang, Y.; Wang, K.; Wang, Z.; Yin, L.; Xu, C. J. Alloys Compd. 2022, 896, 163103. doi: 10.1016/j.jallcom.2021.163103

  119. [119]

       Liu, Q.; Gu, S.; Li, C. M. J. Power Sources 2015, 299, 342. doi: 10.1016/j.jpowsour.2015.09.027

  120. [120]

       Sun, Y.; Huang, C.; Shen, J.; Zhong, Y.; Ning, J.; Hu, Y. J. Colloid Interface Sci. 2020, 558, 1. doi: 10.1016/j.jcis.2019.09.090

  121. [121]

       Gao, S.; Zavabeti, A.; Wang, B.; Ren, R.; Yang, C.; Liu, Z.; Wang, Y. ACS Appl. Nano Mater. 2021, 4, 4542. doi: 10.1021/acsanm.1c00134

  122. [122]

       Liu, M.; Yang, L.; Liu, T.; Tang, Y.; Luo, S.; Liu, C.; Zeng, Y. J. Mater. Chem. A 2017, 5, 8608. doi: 10.1039/c7ta01791j

  123. [123]

       Chen, Y. X.; Chen, S. P.; Chen, Q. S.; Zhou, Z. Y.; Sun, S. G. Electrochim. Acta 2008, 53, 6938. doi: 10.1016/j.electacta.2008.02.024

  124. [124]

       Chen, Y. X.; Chen, S. P.; Zhou, Z. Y.; Tian, N.; Jiang, Y. X.; Sun, S. G.; Ding, Y.; Wang, Z. L. J. Am. Chem. Soc. 2009, 131, 10860. doi: 10.1021/ja904225q

  125. [125]

       Chen, L. F.; Xie, A. Y.; Lou, Y. Y.; Tian, N.; Zhou, Z. Y.; Sun, S. G. J. Electroanal. Chem. 2022, 907, 116022. doi: 10.1016/j.jelechem.2022.116022

  126. [126]

       Li, X. Curr. Opin Electrochem. 2023, 39, 101289. doi: 10.1016/j.coelec.2023.101289

  127. [127]

       Wu, W.; Eliaz, N.; Gileadi, E. J. Electrochem. Soc. 2014, 162, D20. doi: 10.1149/2.0281501jes

  128. [128]

       Heusler, K. E. Electrochim. Acta 1996, 41, 411. doi: 10.1016/0013-4686(95)00321-5

  129. [129]

       Beermann, V.; Gocyla, M.; Kuhl, S.; Padgett, E.; Schmies, H.; Goerlin, M.; Erini, N.; Shviro, M.; Heggen, M.; Dunin-Borkowski, R. E.; et al. J. Am. Chem. Soc. 2017, 139, 16536. doi: 10.1021/jacs.7b06846

  130. [130]

       Gan, L.; Rudi, S.; Cui, C.; Heggen, M.; Strasser, P. Small 2016, 12, 3189. doi: 10.1002/smll.201600027

  131. [131]

       Wang, S.; Xiong, L.; Bi, J.; Zhang, X.; Yang, G.; Yang, S. ACS Appl. Mater. Interfaces 2018, 10, 27009. doi: 10.1021/acsami.8b07742

  132. [132]

       Zhu, H.; Zhang, S.; Guo, S.; Su, D.; Sun, S. J. Am. Chem. Soc. 2013, 135, 7130. doi: 10.1021/ja403041g

  133. [133]

       Carpenter, M. K.; Moylan, T. E.; Kukreja, R. S.; Atwan, M. H.; Tessema, M. M. J. Am. Chem. Soc. 2012, 134, 8535. doi: 10.1021/ja300756y

  134. [134]

       Chang, Q.; Xu, Y.; Duan, Z.; Xiao, F.; Fu, F.; Hong, Y.; Kim, J.; Choi, S. I.; Su, D.; Shao, M. Nano Lett. 2017, 17, 3926. doi: 10.1021/acs.nanolett.7b01510

  135. [135]

       Zhang, C.; Hwang, S. Y.; Trout, A.; Peng, Z. J. Am. Chem. Soc. 2014, 136, 7805. doi: 10.1021/ja501293x

  136. [136]

       Bu, L.; Ding, J.; Guo, S.; Zhang, X.; Su, D.; Zhu, X.; Yao, J.; Guo, J.; Lu, G.; Huang, X. Adv. Mater. 2015, 27, 7204. doi: 10.1002/adma.201502725

  137. [137]

       Wang, C.; Chi, M.; Wang, G.; van der Vliet, D.; Li, D.; More, K.; Wang, H.-H.; Schlueter, J. A.; Markovic, N. M.; Stamenkovic, V. R. Adv. Funct. Mater. 2011, 21, 147. doi: 10.1002/adfm.201001138

  138. [138]

       Matsuda, Y.; Imahashi, K.; Yoshimoto, N.; Morita, M.; Haga, M. J. Alloys Compd. 1993, 193, 277. doi: 10.1016/0925-8388(93)90370-3

  139. [139]

       Liu, P.; Yang, Q.; Tong, Y.; Yang, Y. Electrochim. Acta 2000, 45, 2147. doi: 10.1016/S0013-4686(99)00434-X

  140. [140]

       Yang, Q.; Liu, P.; Yang, Y.; Tong, Y. J. Electroanal. Chem. 1998, 456, 223. doi: 10.1016/S0022-0728(98)00283-6

  141. [141]

       Monnens, W.; Deferm, C.; Binnemans, K.; Fransaer, J. Phys. Chem. Chem. Phys. 2020, 22, 24526. doi: 10.1039/d0cp03277h

  142. [142]

       Shen, Q.; Xue, J.; Liu, X.; Jia, H.; Yang, X.; Xu, B. J. Solid State Electrochem. 2016, 21, 19. doi: 10.1007/s10008-016-3314-4

  143. [143]

       Li, G. R.; Zhang, Z. S.; Su, C. Y.; Tong, Y. X. J. Phys. Chem. C 2009, 113, 1227. doi: 10.1021/jp805051p

  144. [144]

       Tauster, S. J.; Fung, S. C.; Garten, R. L. J. Am. Chem. Soc. 1978, 100, 170. doi: 10.1021/ja00469a029‚

  145. [145]

       Farmer, J. A.; Campbell, C. T. Science 2010, 329, 933. doi: 10.1126/science.1191778

  146. [146]

       Rao, R. G.; Blume, R.; Hansen, T. W.; Fuentes, E.; Dreyer, K.; Moldovan, S.; Ersen, O.; Hibbitts, D. D.; Chabal, Y. J.; Schlogl, R.; et al. Nat. Commun. 2017, 8, 340. doi: 10.1038/s41467-017-00421-x

  147. [147]

       Yan, Q. Q.; Wu, D. X.; Chu, S. Q.; Chen, Z. Q.; Lin, Y.; Chen, M. X.; Zhang, J.; Wu, X. J.; Liang, H. W. Nat. Commun. 2019, 10, 4977. doi: 10.1038/s41467-019-12851-w

  148. [148]

       Zhao, L.; Guo, Y.; Fu, C.; Luo, L.; Wei, G.; Shen, S.; Zhang, J. Chin. J. Catal. 2021, 42, 2068. doi: 10.1016/s1872-2067(21)63860-3

  149. [149]

       Zhao, L.; Fu, C.; Luo, L.; You, J.; An, L.; Yan, X.; Shen, S.; Zhang, J. Appl. Catal. B 2022, 318, 121831. doi: 10.1016/j.apcatb.2022.121831

  150. [150]

       Liu, F.; Deng, Y.; Han, X.; Hu, W.; Zhong, C. J. Alloys Compd. 2016, 654, 163. doi: 10.1016/j.jallcom.2015.09.137

  151. [151]

       Hallett, J. P.; Welton, T. Chem. Rev. 2011, 111, 3508. doi: 10.1021/cr1003248

  152. [152]

       Singh, S. K.; Savoy, A. W. J. Mol. Liq. 2020, 297, 112038. doi: 10.1016/j.molliq.2019.112038

  153. [153]

       Rogers, R. D.; Voth, G. A. Acc. Chem. Res. 2007, 40, 1077. doi: 10.1021/ar700221n

  154. [154]

       Zhang, Q.; Hua, Y.; Xu, C.; Li, Y.; Li, J.; Dong, P. J. Rare Earths 2015, 33, 1017. doi: 10.1016/s1002-0721(14)60520-2

  155. [155]

       Zhang, Q.; Wang, Q.; Zhang, S.; Lu, X.; Zhang, X. ChemPhysChem 2016, 17, 335. doi: 10.1002/cphc.201500713

  156. [156]

       Wallace, A. G.; Symes, M. D. Trends Chem. 2019, 1, 247. doi: 10.1016/j.trechm.2019.03.003

  157. [157]

       Gao, M. Y.; Yang, C.; Zhang, Q. B.; Zeng, J. R.; Li, X. T.; Hua, Y. X.; Xu, C. Y.; Li, Y. J. Electrochem. Soc. 2017, 164, D778. doi: 10.1149/2.1751712jes

  158. [158]

       Zhang, Q.; De Oliveira Vigier, K.; Royer, S.; Jerome, F. Chem. Soc. Rev. 2012, 41, 7108. doi: 10.1039/c2cs35178a

  159. [159]

       Wu, J.; Liang, Q.; Yu, X.; Lü, Q. F.; Ma, L.; Qin, X.; Chen, G.; Li, B. Adv. Funct. Mater. 2021, 31, 2011102. doi: 10.1002/adfm.202011102

  160. [160]

       Cojocaru, P.; Magagnin, L.; Gomez, E.; Vallés, E. Mater. Lett. 2011, 65, 3597. doi: 10.1016/j.matlet.2011.08.003

  161. [161]

       Yang, H.; Guo, X.; Birbilis, N.; Wu, G.; Ding, W. Appl. Surf. Sci. 2011, 257, 9094. doi: 10.1016/j.apsusc.2011.05.106

  162. [162]

       Abbott, A. P.; Boothby, D.; Capper, G.; Davies, D. L.; Rasheed, R. K. J. Am. Chem. Soc. 2004, 126, 9142. doi: 10.1021/ja048266j

  163. [163]

       Renjith, A.; Lakshminarayanan, V. J. Mater. Chem. A 2015, 3, 3019. doi: 10.1039/c4ta05302h

  164. [164]

       Sebastian, P.; Giannotti, M. I.; Gómez, E.; Feliu, J. M. ACS Appl. Energy Mater. 2018, 1, 1016. doi: 10.1021/acsaem.7b00177

  165. [165]

       Zhang, J. M.; He, J. J.; Wang, X. Q.; Fan, Y. J.; Zhang, X. J.; Zhong, J. P.; Chen, W.; Sun, S. G. Int. J. Hydrogen Energy 2019, 44, 28709. doi: 10.1016/j.ijhydene.2019.09.104

  166. [166]

       Gao, M. Y.; Yang, C.; Zhang, Q. B.; Zeng, J. R.; Li, X. T.; Hua, Y. X.; Xu, C. Y.; Dong, P. J. Mater. Chem. A 2017, 5, 5797. doi: 10.1039/c6ta10812a

  167. [167]

       Mao, Y. J.; Liu, F.; Chen, Y. H.; Jiang, X.; Zhao, X. S.; Sheng, T.; Ye, J. Y.; Liao, H. G.; Wei, L.; Sun, S. G. J. Mater. Chem. A 2021, 9, 26277. doi: 10.1039/d1ta05515a

  168. [168]

       Abbott, A. P.; El Ttaib, K.; Ryder, K. S.; Smith, E. L. Trans. IMF 2013, 86, 234. doi: 10.1179/174591908x327581

  169. [169]

       Li, R.; Hou, Y.; Liu, B.; Wang, D.; Liang, J. Electrochim. Acta 2016, 222, 1272. doi: 10.1016/j.electacta.2016.11.101

  170. [170]

       Wei, L.; Xu, C. D.; Huang, L.; Zhou, Z. Y.; Chen, S. P.; Sun, S. G. J. Phys. Chem. C 2015, 120, 15569. doi: 10.1021/acs.jpcc.5b03580

  171. [171]

       Wei, L.; Fan, Y. J.; Tian, N.; Zhou, Z. Y.; Zhao, X. Q.; Mao, B. W.; Sun, S. G. J. Phys. Chem. C 2011, 116, 2040. doi: 10.1021/jp209743h

  172. [172]

       Zhong, J.; Li, L.; Waqas, M.; Wang, X.; Fan, Y.; Qi, J.; Yang, B.; Rong, C.; Chen, W.; Sun, S. Electrochim. Acta 2019, 322, 134677. doi: 10.1016/j.electacta.2019.134677

  173. [173]

       Xiang, S.; Wang, L.; Huang, C. C.; Fan, Y. J.; Tang, H. G.; Wei, L.; Sun, S. G. J. Power Sources 2018, 399, 422. doi: 10.1016/j.jpowsour.2018.07.102

  174. [174]

       Wang, S.; Zou, X.; Lu, Y.; Rao, S.; Xie, X.; Pang, Z.; Lu, X.; Xu, Q.; Zhou, Z. Int. J. Hydrogen Energy 2018, 43, 15673. doi: 10.1016/j.ijhydene.2018.06.188

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