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Vol. 10 No. 4 (2018)

Heterostructured Electrocatalysts for Hydrogen Evolution Reaction Under Alkaline Conditions

https://doi.org/10.1007/s40820-018-0229-x
Jumeng Wei
College of Chemistry and Materials Engineering, Anhui Science and Technology University, Bengbu 233100, People’s Republic of China
Min Zhou
College of Physical Science and Technology, and Institute of Optoelectronic Technology, Yangzhou University, Yangzhou 225002, People’s Republic of China
Anchun Long
College of Physical Science and Technology, and Institute of Optoelectronic Technology, Yangzhou University, Yangzhou 225002, People’s Republic of China
Yanming Xue
School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300130, People’s Republic of China
Hanbin Liao
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
Chao Wei
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
Zhichuan J. Xu
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore

Corresponding Author: Zhichuan J. Xu

xuzc@ntu.edu.sg

Nano-Micro Letters, Vol. 10 No. 4 (2018), Article Number: 75

Abstract

The hydrogen evolution reaction (HER) is a half-cell reaction in water electrolysis for producing hydrogen gas. In industrial water electrolysis, the HER is often conducted in alkaline media to achieve higher stability of the electrode materials. However, the kinetics of the HER in alkaline medium is slow relative to that in acid because of the low concentration of protons in the former. Under the latter conditions, the entire HER process will require additional effort to obtain protons by water dissociation near or on the catalyst surface. Heterostructured catalysts, with fascinating synergistic effects derived from their heterogeneous interfaces, can provide multiple functional sites for the overall reaction process. At present, the activity of the most active known heterostructured catalysts surpasses (platinum-based heterostructures) or approaches (noble-metal-free heterostructures) that of the commercial Pt/C catalyst under alkaline conditions, demonstrating an infusive potential to break through the bottlenecks. This review summarizes the most representative and recent heterostructured HER catalysts for alkaline medium. The basics and principles of the HER under alkaline conditions are first introduced, followed by a discussion of the latest advances in heterostructured catalysts with/without noble-metal-based heterostructures. Special focus is placed on approaches for enhancing the reaction rate by accelerating the Volmer step. This review aims to provide an overview of the current developments in alkaline HER catalysts, as well as the design principles for the future development of heterostructured nano- or micro-sized electrocatalysts.


Highlights:


1 Heterostructured catalysts offer improved HER activities in alkaline solutions due to their fascinating synergistic effects on the heterogeneous interfaces.
2 Representative heterostructured HER catalysts for alkaline media are summarized.
3 Acceleration of the Volmer step, crucial for alkali-active catalysts, is highlighted.

Keywords

Hybrid catalyst Hydrogen production Water splitting Interface engineering Synergistic effect
Wei, Jumeng, Min Zhou, Anchun Long, Yanming Xue, Hanbin Liao, Chao Wei, and Zhichuan J. Xu. 2018. “Heterostructured Electrocatalysts for Hydrogen Evolution Reaction Under Alkaline Conditions”. Nano-Micro Letters 10 (4):75. https://doi.org/10.1007/s40820-018-0229-x.
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References
  1. M.K. Debe, Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012). https://doi.org/10.1038/nature11115
  2. Y. Zheng, Y. Jiao, M. Jaroniec, S.Z. Qiao, Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory. Angew. Chem. Int. Ed. 54, 52–65 (2015). https://doi.org/10.1002/anie.201407031
  3. Y. Yan, T. He, B. Zhao, K. Qi, H. Liu, B.Y. Xia, Metal/covalent-organic frameworks-based electrocatalysts for water splitting. J. Mater. Chem. A 6, 15905 (2018). https://doi.org/10.1039/C8TA05985C
  4. J. Pan, Y.Y. Xu, H. Yang, Z. Dong, H. Liu, B.Y. Xia, Advanced architectures and relatives of air electrodes in Zn–air batteries. Adv. Sci. 5, 1700691 (2018). https://doi.org/10.1002/advs.201700691
  5. J. Zhang, H. Wang, Y. Tian, Y. Yan, Q. Xue et al., Anodic hydrazine oxidation assists energy-efficient hydrogen evolution over a bifunctional cobalt perselenide nanosheet electrode. Angew. Chem. Int. Ed. 57, 7649–7653 (2018). https://doi.org/10.1002/anie.201803543
  6. M. Miao, J. Pan, T. He, Y. Yan, B.Y. Xia, X. Wang, Molybdenum carbide-based electrocatalysts for hydrogen evolution reaction. Chem. Eur. J. 23, 10947–10961 (2017). https://doi.org/10.1002/chem.201701064
  7. L.M. Gandía, R. Oroz, A. Ursúa, P. Sanchis, P.M. Diéguez, Renewable hydrogen production: performance of an alkaline water electrolyzer working under emulated wind conditions. Energy Fuels 21, 1699–1706 (2007). https://doi.org/10.1021/ef060491u
  8. M. Zhou, Q. Weng, X. Zhang, X. Wang, Y. Xue, X. Zeng, Y. Bando, D. Golberg, In situ electrochemical formation of core-shell nickel-iron disulfide and oxyhydroxide heterostructured catalysts for a stable oxygen evolution reaction and the associated mechanisms. J. Mater. Chem. A 5, 4335–4342 (2017). https://doi.org/10.1039/C6TA09366C
  9. F. Safizadeh, E. Ghali, G. Houlachi, Electrocatalysis developments for hydrogen evolution reaction in alkaline solutions—a review. Int. J. Hydrogen Energy 40, 256–274 (2015). https://doi.org/10.1016/j.ijhydene.2014.10.109
  10. F. Lu, M. Zhou, Y. Zhou, X. Zeng, First-row transition metal based catalysts for the oxygen evolution reaction under alkaline conditions: basic principles and recent advances. Small 13, 1701931 (2017). https://doi.org/10.1002/smll.201701931
  11. N. Mahmood, Y. Yao, J.W. Zhang, L. Pan, X. Zhang, J.J. Zou, Electrocatalysts for hydrogen evolution in alkaline electrolytes: mechanisms, challenges, and prospective solutions. Adv. Sci. 5, 1700464 (2018). https://doi.org/10.1002/advs.201700464
  12. Z. Yao, J. Yan, V. Anthony, S.Z. Qiao, The hydrogen evolution reaction in alkaline solution: from theory, single crystal models, to practical electrocatalysts. Angew. Chem. Int. Ed. 57, 7568–7579 (2018). https://doi.org/10.1002/anie.201710556
  13. M. Gong, D.Y. Wang, C.C. Chen, B.J. Hwang, H. Dai, A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction. Nano Res. 9, 28–46 (2015). https://doi.org/10.1007/s12274-015-0965-x
  14. Z.W. Seh, J. Kibsgaard, C.F. Dickens, I. Chorkendorff, J.K. Nørskov, T.F. Jaramillo, Combining theory and experiment in electrocatalysis: Insights into materials design. Science 355, eaad4998 (2017). https://doi.org/10.1126/science.aad4998
  15. R. Subbaraman, D. Tripkovic, D. Strmcnik, K.C. Chang, M. Uchimura, A.P. Paulikas, V. Stamenkovic, N.M. Markovic, Enhancing hydrogen evolution activity in water splitting by tailoring Li+–Ni(OH)2–Pt interfaces. Science 334, 1256–1260 (2011). https://doi.org/10.1126/science.1211934
  16. H. Yang, C. Wang, F. Hu, Y. Zhang, H. Lu, Q. Wang, Atomic-scale Pt clusters decorated on porous α-Ni(OH)2 nanowires as highly efficient electrocatalyst for hydrogen evolution reaction. Sci. China Mater. 60, 1121–1128 (2017). https://doi.org/10.1007/s40843-017-9035-8
  17. J. Mahmood, F. Li, S.M. Jung, M.S. Okyay, I. Ahmad, S.J. Kim, N. Park, H.Y. Jeong, J.B. Baek, An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction. Nat. Nanotechnol. 12, 441 (2017). https://doi.org/10.1038/nnano.2016.304
  18. L. Wang, Y. Zhu, Z. Zeng, C. Lin, M. Giroux et al., Platinum–nickel hydroxide nanocomposites for electrocatalytic reduction of water. Nano Energy 31, 456–461 (2017). https://doi.org/10.1016/j.nanoen.2016.11.048
  19. B. Zhang, J. Liu, J. Wang, Y. Ruan, X. Ji et al., Interface engineering: the Ni(OH)2/MoS2 heterostructure for highly efficient alkaline hydrogen evolution. Nano Energy 37, 74–80 (2017). https://doi.org/10.1016/j.nanoen.2017.05.011
  20. Z. Zeng, K.C. Chang, J. Kubal, N.M. Markovic, J. Greeley, Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion. Nat. Energy 2, 17070 (2017). https://doi.org/10.1038/nenergy.2017.70
  21. B.E. Conway, L. Bai, Determination of adsorption of OPD H species in the cathodic hydrogen evolution reaction at Pt in relation to electrocatalysis. J. Electroanal. Chem. 198, 149–175 (1986). https://doi.org/10.1016/0022-0728(86)90033-1
  22. B.E. Conway, G. Jerkiewicz, Relation of energies and coverages of underpotential and overpotential deposited H at Pt and other metals to the ‘volcano curve’ for cathodic H2 evolution kinetics. Electrochim. Acta 45, 4075–4083 (2000). https://doi.org/10.1016/S0013-4686(00)00523-5
  23. W. Sheng, M. Myint, J.G. Chen, Y. Yan, Correlating the hydrogen evolution reaction activity in alkaline electrolytes with the hydrogen binding energy on monometallic surfaces. Energy Environ. Sci. 6, 1509 (2013). https://doi.org/10.1039/c3ee00045a
  24. I. Ledezma-Yanez, W.D.Z. Wallace, P. Sebastián-Pascual, V. Climent, J.M. Feliu, M.T.M. Koper, Interfacial water reorganization as a pH-dependent descriptor of the hydrogen evolution rate on platinum electrodes. Nat. Energy 2, 17031 (2017). https://doi.org/10.1038/nenergy.2017.31
  25. R. Subbaraman, D. Tripkovic, K.C. Chang, D. Strmcnik, A.P. Paulikas et al., Trends in activity for the water electrolyser reactions on 3d M(Ni Co, Fe, Mn) hydr(oxy)oxide catalysts. Nat. Mater. 11, 550 (2012). https://doi.org/10.1038/nmat3313
  26. T. Bligaard, J.K. Nørskov, S. Dahl, J. Matthiesen, C.H. Christensen, J. Sehested, The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis. J. Catal. 224, 206–217 (2004). https://doi.org/10.1016/j.jcat.2004.02.034
  27. G.S. Karlberg, Adsorption trends for water, hydroxyl, oxygen, and hydrogen on transition-metal and platinum-skin surfaces. Phys. Rev. B 74, 153414 (2006). https://doi.org/10.1103/PhysRevB.74.153414
  28. D.E. Brown, M.N. Mahmood, M.C.M. Man, A.K. Turner, Preparation and characterization of low overvoltage transition metal alloy electrocatalysts for hydrogen evolution in alkaline solutions. Electrochim. Acta 29, 1551–1556 (1984). https://doi.org/10.1016/0013-4686(84)85008-2
  29. I.A. Raj, K.I. Vasu, Transition metal-based hydrogen electrodes in alkaline solution-electrocatalysis on nickel based binary alloy coatings. J. Appl. Electrochem. 20, 32–38 (1990). https://doi.org/10.1007/BF01012468
  30. Y.Y. Chen, Y. Zhang, X. Zhang, T. Tang, H. Luo, S. Niu, Z.H. Dai, L.J. Wan, J.S. Hu, Self-templated fabrication of MoNi4/MoO3−x nanorod arrays with dual active components for highly efficient hydrogen evolution. Adv. Mater. 29, 1703311 (2017). https://doi.org/10.1002/adma.201703311
  31. J. Zhang, T. Wang, P. Liu, Z. Liao, S. Liu, X. Zhuang, M. Chen, E. Zschech, X. Feng, Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics. Nat. Commun. 8, 15437 (2017). https://doi.org/10.1038/ncomms15437
  32. P.M. Csernica, J.R. McKone, C.R. Mulzer, W.R. Dichtel, H.D. Abruña, F.J. DiSalvo, Electrochemical hydrogen evolution at ordered Mo7Ni7. ACS Catal. 7, 3375–3383 (2017). https://doi.org/10.1021/acscatal.7b00344
  33. P. Wang, K. Jiang, G. Wang, J. Yao, X. Huang, Phase and interface engineering of platinum–nickel nanowires for efficient electrochemical hydrogen evolution. Angew. Chem. Int. Ed. 55, 12859–12863 (2016). https://doi.org/10.1002/anie.201606290
  34. P. Wang, X. Zhang, J. Zhang, S. Wan, S. Guo, G. Lu, J. Yao, X. Huang, Precise tuning in platinum–nickel/nickel sulfide interface nanowires for synergistic hydrogen evolution catalysis. Nat. Commun. 8, 14580 (2017). https://doi.org/10.1038/ncomms14580
  35. H. Yin, S. Zhao, K. Zhao, A. Muqsit, H. Tang, L. Chang, H. Zhao, Y. Gao, Z. Tang, Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity. Nat. Commun. 6, 6430 (2015). https://doi.org/10.1038/ncomms7430
  36. L. Wang, C. Lin, D. Huang, J. Chen, L. Jiang, M. Wang, L. Chi, L. Shi, J. Jin, Optimizing the Volmer step by single-layer nickel hydroxide nanosheets in hydrogen evolution reaction of platinum. ACS Catal. 5, 3801–3806 (2015). https://doi.org/10.1021/cs501835c
  37. N. Cheng, S. Stambula, D. Wang, M.N. Banis, J. Liu et al., Platinum single-atom and cluster catalysis of the hydrogen evolution reaction. Nat. Commun. 7, 13638 (2016). https://doi.org/10.1038/ncomms13638
  38. J. Deng, H. Li, J. Xiao, Y. Tu, D. Deng et al., Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS2 surface via single-atom metal doping. Energy Environ. Sci. 8, 1594 (2015). https://doi.org/10.1039/C5EE00751H
  39. Y. Wang, L. Chen, X. Yu, Y. Wang, G. Zheng, Superb alkaline hydrogen evolution and simultaneous electricity generation by Pt-decorated Ni3N nanosheets. Adv. Energy Mater. 7, 1601390 (2017). https://doi.org/10.1002/aenm.201601390
  40. H. Liao, C. Wei, J. Wang, A. Fisher, T. Sritharan, Z. Feng, Z.J. Xu, A multisite strategy for enhancing the hydrogen evolution reaction on a nano-Pd surface in alkaline media. Adv. Energy Mater. 7, 1701129 (2017). https://doi.org/10.1002/aenm.201701129
  41. J. Xu, T. Liu, J. Li, B. Li, Y. Liu et al., Boosting the hydrogen evolution performance of ruthenium clusters through synergistic coupling with cobalt phosphide. Energy Environ. Sci. 11, 1819–1827 (2018). https://doi.org/10.1039/C7EE03603E
  42. M. Gong, W. Zhou, M.C. Tsai, J. Zhou, M. Guan et al., Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis. Nat. Commun. 5, 4695 (2014). https://doi.org/10.1038/ncomms5695
  43. T.F. Jaramillo, K.P. Jørgensen, J. Bonde, J.H. Nielsen, S. Horch, I. Chorkendorff, Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts. Science 317, 100–102 (2007). https://doi.org/10.1126/science.1141483
  44. J. Hu, C. Zhang, L. Jiang, H. Lin, Y. An, D. Zhou, M.K.H. Leung, S. Yang, Nanohybridization of MoS2 with layered double hydroxides efficiently synergizes the hydrogen evolution in alkaline media. Joule 1, 383–393 (2017). https://doi.org/10.1016/j.joule.2017.07.011
  45. Y. Luo, X. Li, X. Cai, X. Zou, F. Kang, H.M. Cheng, B. Liu, Two-dimensional MoS2 confined Co(OH)2 electrocatalysts for hydrogen evolution in alkaline electrolytes. ACS Nano 12, 4565–4573 (2018). https://doi.org/10.1021/acsnano.8b00942
  46. X. Zhang, Y. Liang, Nickel hydr(oxy)oxide nanoparticles on metallic MoS2 nanosheets: a synergistic electrocatalyst for hydrogen evolution reaction. Adv. Sci. 5, 1700644 (2018). https://doi.org/10.1002/advs.201700644
  47. J. Zhang, T. Wang, D. Pohl, B. Rellinghaus, R. Dong, S. Liu, X. Zhuang, X. Feng, Interface engineering of MoS2/Ni3S2 heterostructures for highly enhanced electrochemical overall-water-splitting activity. Angew. Chem. Int. Ed. 55, 6702–6707 (2016). https://doi.org/10.1002/anie.201602237
  48. P. Kuang, T. Tong, K. Fan, J. Yu, In situ fabrication of Ni–Mo bimetal sulfide hybrid as an efficient electrocatalyst for hydrogen evolution over a wide pH range. ACS Catal. 7, 6179–6187 (2017). https://doi.org/10.1021/acscatal.7b02225
  49. K. Xu, H. Ding, M. Zhang, M. Chen, Z. Hao, L. Zhang, C. Wu, Y. Xie, Regulating water-reduction kinetics in cobalt phosphide for enhancing her catalytic activity in alkaline solution. Adv. Mater. 29, 1606980 (2017). https://doi.org/10.1002/adma.201606980
  50. J. Zhang, T. Wang, P. Liu, S. Liu, R. Dong, X. Zhuang, M. Chen, X. Feng, Engineering water dissociation sites in MoS2 nanosheets for accelerated electrocatalytic hydrogen production. Energy Environ. Sci. 9, 2789–2793 (2016). https://doi.org/10.1039/C6EE01786J
  51. Z. Weng, W. Liu, L.C. Yin, R. Fang, M. Li et al., Metal/oxide interface nanostructures generated by surface segregation for electrocatalysis. Nano Lett. 15, 7704–7710 (2015). https://doi.org/10.1021/acs.nanolett.5b03709
  52. Z. Zhu, H. Yin, C.T. He, M. Al-Mamun, P. Liu et al., Ultrathin transition metal dichalcogenide/3d metal hydroxide hybridized nanosheets to enhance hydrogen evolution activity. Adv. Mater. (2018). https://doi.org/10.1002/adma.201801171
  53. X. Yu, J. Zhao, L.R. Zheng, Y. Tong, M. Zhang, G. Xu, C. Li, J. Ma, G. Shi, Hydrogen evolution reaction in alkaline media: alpha- or beta-nickel hydroxide on the surface of platinum? ACS Energy Lett. 3, 237–244 (2018). https://doi.org/10.1021/acsenergylett.7b01103
  54. M. Zhou, Q. Weng, Z.I. Popov, Y. Yang, L.Y. Antipina, P.B. Sorokin, X. Wang, Y. Bando, D. Golberg, Construction of polarized carbon–nickel catalytic surfaces for potent, durable, and economic hydrogen evolution reactions. ACS Nano 12, 4148–4155 (2018). https://doi.org/10.1021/acsnano.7b08724
  55. Y. Liu, Q. Li, R. Si, G.D. Li, W. Li et al., Coupling sub-nanometric copper clusters with quasi-amorphous cobalt sulfide yields efficient and robust electrocatalysts for water splitting reaction. Adv. Mater. 29, 1606200 (2017). https://doi.org/10.1002/adma.201606200
  56. J.X. Feng, J.Q. Wu, Y.X. Tong, G.R. Li, Efficient hydrogen evolution on Cu nanodots-decorated Ni3S2 nanotubes by optimizing atomic hydrogen adsorption and desorption. J. Am. Chem. Soc. 140, 610–617 (2018). https://doi.org/10.1021/jacs.7b08521
  57. C. Wei, Z.J. Xu, The Comprehensive understanding of 10 mA cm −2geo as an evaluation parameter for electrochemical water splitting. Small Methods (2018). https://doi.org/10.1002/smtd.201800168
  58. S. Sun, H. Li, Z.J. Xu, Impact of surface area in evaluation of catalyst activity. Joule 2, 1019–1027 (2018). https://doi.org/10.1016/j.joule.2018.05.003
  59. Z. Li, D. Wang, Y. Wu, Y. Li, Recent advances in the precise control of isolated single site catalysts by chemical methods. Natl. Sci. Rev. 5(5), 673–689 (2018). https://doi.org/10.1093/nsr/nwy056
  60. Y.P. Zhu, C. Guo, Y. Zheng, S.Z. Qiao, Surface and interface engineering of noble-metal-free electrocatalysts for efficient energy conversion processes. Acc. Chem. Res. 50, 915–923 (2017). https://doi.org/10.1021/acs.accounts.6b00635
  61. Z. Xing, C. Han, D. Wang, Q. Li, X. Yang, Ultrafine Pt nanoparticle-decorated Co(OH)2 nanosheet arrays with enhanced catalytic activity toward hydrogen evolution. ACS Catal. 7, 7131–7135 (2017). https://doi.org/10.1021/acscatal.7b01994
  62. Z. Wang, Z. Liu, G. Du, A.M. Asiri, L. Wang et al., Ultrafine PtO2 nanoparticles coupled with a Co(OH)F nanowire array for enhanced hydrogen evolution. Chem. Commun. 54, 810–813 (2018). https://doi.org/10.1039/C7CC08870A
  63. Z. Wang, X. Ren, X. Shi, A. Asiri, L. Wang, X. Li, X. Sun, Q. Zhang, H. Wang, A platinum oxide decorated amorphous cobalt oxide hydroxide nanosheet array towards alkaline hydrogen evolution. J. Mater. Chem. A 6, 3864–3868 (2018). https://doi.org/10.1039/C8TA00241J
  64. C. Wang, P. Zhang, J. Lei, W. Dong, J. Wang, Integrated 3d MoSe2@Ni0.85Se nanowire network with synergistic cooperation as highly efficient electrocatalysts for hydrogen evolution reaction in alkaline medium. Electrochim. Acta 246, 712–719 (2017). https://doi.org/10.1016/j.electacta.2017.06.028
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