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Vol. 16 (2024)

Covalently Bonded Ni Sites in Black Phosphorene with Electron Redistribution for Efficient Metal-Lightweighted Water Electrolysis

https://doi.org/10.1007/s40820-024-01331-6
Wenfang Zhai
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Ya Chen
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Yaoda Liu
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Yuanyuan Ma
School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710072, People’s Republic of China
Paranthaman Vijayakumar
SSN Research Centre, SSN College of Engineering, Chennai, Tamil Nadu 603110, India
Yuanbin Qin
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
Yongquan Qu
School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi’an 710072, People’s Republic of China
Zhengfei Dai
State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China

Corresponding Author: Zhengfei Dai

sensdai@mail.xjtu.edu.cn

Nano-Micro Letters, Vol. 16 (2024), Article Number: 115

Abstract

The metal-lightweighted electrocatalysts for water splitting are highly desired for sustainable and economic hydrogen energy deployments, but challengeable. In this work, a low-content Ni-functionalized approach triggers the high capability of black phosphorene (BP) with hydrogen and oxygen evolution reaction (HER/OER) bifunctionality. Through a facile in situ electro-exfoliation route, the ionized Ni sites are covalently functionalized in BP nanosheets with electron redistribution and controllable metal contents. It is found that the as-fabricated Ni-BP electrocatalysts can drive the water splitting with much enhanced HER and OER activities. In 1.0 M KOH electrolyte, the optimized 1.5 wt% Ni-functionalized BP nanosheets have readily achieved low overpotentials of 136 mV for HER and 230 mV for OER at 10 mA cm−2. Moreover, the covalently bonding between Ni and P has also strengthened the catalytic stability of the Ni-functionalized BP electrocatalyst, stably delivering the overall water splitting for 50 h at 20 mA cm−2. Theoretical calculations have revealed that Ni–P covalent binding can regulate the electronic structure and optimize the reaction energy barrier to improve the catalytic activity effectively. This work confirms that Ni-functionalized BP is a suitable candidate for electrocatalytic overall water splitting, and provides effective strategies for constructing metal-lightweighted economic electrocatalysts.


Highlights:
1 Black phosphorene (BP) was functionalized by the ionized Ni through an in situ electrochemical exfoliation method.
2 Just 1.5 wt% Ni-functionalized BP can stably deliver the efficient alkaline H2/O2 evolution electrocatalysis.
3 Optimized intermediate chemisorption is enabled by Ni–P covalent bonding and electron redistributed surface.

Keywords

Black phosphorus Water electrolysis Electrocatalyst Electron redistribution Covalent functionalization
Zhai, Wenfang, Ya Chen, Yaoda Liu, Yuanyuan Ma, Paranthaman Vijayakumar, Yuanbin Qin, Yongquan Qu, and Zhengfei Dai. 2024. “Covalently Bonded Ni Sites in Black Phosphorene With Electron Redistribution for Efficient Metal-Lightweighted Water Electrolysis”. Nano-Micro Letters 16 (February):115. https://doi.org/10.1007/s40820-024-01331-6.
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References
  1. J.-W. Jiang, H.S. Park, Negative Poisson’s ratio in single-layer black phosphorus. Nat. Commun. 5, 4727 (2014). https://doi.org/10.1038/ncomms5727
  2. L. Li, Y. Yu, G.J. Ye, Q. Ge, X. Ou et al., Black phosphorus field-effect transistors. Nat. Nanotechnol. 9, 372–377 (2014). https://doi.org/10.1038/nnano.2014.35
  3. J. Qiao, X. Kong, Z.-X. Hu, F. Yang, W. Ji, High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus. Nat. Commun. 5, 4475 (2014). https://doi.org/10.1038/ncomms5475
  4. J. Zhu, G. Xiao, X. Zuo, Two-dimensional black phosphorus: an emerging anode material for lithium-ion batteries. Nano-Micro Lett. 12, 120 (2020). https://doi.org/10.1007/s40820-020-00453-x
  5. J. Cheng, L. Gao, T. Li, S. Mei, C. Wang et al., Two-dimensional black phosphorus nanomaterials: emerging advances in electrochemical energy storage science. Nano-Micro Lett. 12, 179 (2020). https://doi.org/10.1007/s40820-020-00510-5
  6. M. Fortin-Deschênes, F. Xia, Synthesis of black phosphorus films. Nat. Mater. 22, 681–682 (2023). https://doi.org/10.1038/s41563-023-01548-7
  7. Q. Jiang, L. Xu, N. Chen, H. Zhang, L. Dai et al., Facile synthesis of black phosphorus: an efficient electrocatalyst for the oxygen evolving reaction. Angew. Chem. Int. Ed. 55, 13849–13853 (2016). https://doi.org/10.1002/anie.201607393
  8. L. Zeng, X. Zhang, Y. Liu, X. Yang, J. Wang et al., Surface and interface control of black phosphorus. Chem 8, 632–662 (2022). https://doi.org/10.1016/j.chempr.2021.11.022
  9. Y. Zhang, C. Ma, J. Xie, H. Ågren, H. Zhang, Black phosphorus/polymers: status and challenges. Adv. Mater. 33, e2100113 (2021). https://doi.org/10.1002/adma.202100113
  10. X. Wang, R.K.M. Raghupathy, C.J. Querebillo, Z. Liao, D. Li et al., Interfacial covalent bonds regulated electron-deficient 2D black phosphorus for electrocatalytic oxygen reactions. Adv. Mater. 33, e2008752 (2021). https://doi.org/10.1002/adma.202008752
  11. J. Mei, T. He, J. Bai, D. Qi, A. Du et al., Surface-dependent intermediate adsorption modulation on iridium-modified black phosphorus electrocatalysts for efficient pH-universal water splitting. Adv. Mater. 33, e2104638 (2021). https://doi.org/10.1002/adma.202104638
  12. V.V. Kulish, O.I. Malyi, C. Persson, P. Wu, Adsorption of metal adatoms on single-layer phosphorene. Phys. Chem. Chem. Phys. 17, 992–1000 (2015). https://doi.org/10.1039/c4cp03890h
  13. J. Lu, X. Zhang, D. Liu, N. Yang, H. Huang et al., Modulation of phosphorene for optimal hydrogen evolution reaction. ACS Appl. Mater. Interfaces 11, 37787–37795 (2019). https://doi.org/10.1021/acsami.9b13666
  14. H. Qiao, H. Liu, Z. Huang, Q. Ma, S. Luo et al., Black phosphorus nanosheets modified with Au nanops as high conductivity and high activity electrocatalyst for oxygen evolution reaction. Adv. Energy Mater. 10, 2002424 (2020). https://doi.org/10.1002/aenm.202002424
  15. B. Yang, B. Wan, Q. Zhou, Y. Wang, W. Hu et al., Te-doped black phosphorus field-effect transistors. Adv. Mater. 28, 9408–9415 (2016). https://doi.org/10.1002/adma.201603723
  16. Y. Liu, P. Gao, T. Zhang, X. Zhu, M. Zhang et al., Azide passivation of black phosphorus nanosheets: covalent functionalization affords ambient stability enhancement. Angew. Chem. Int. Ed. 58, 1479–1483 (2019). https://doi.org/10.1002/anie.201813218
  17. Z. Sofer, J. Luxa, D. Bouša, D. Sedmidubský, P. Lazar et al., The covalent functionalization of layered black phosphorus by nucleophilic reagents. Angew. Chem. Int. Ed. 56, 9891–9896 (2017). https://doi.org/10.1002/anie.201705722
  18. M. Vanni, M. Bellini, S. Borsacchi, L. Calucci, M. Caporali et al., Interlayer coordination of Pd–Pd units in exfoliated black phosphorus. J. Am. Chem. Soc. 143, 10088–10098 (2021). https://doi.org/10.1021/jacs.1c01754
  19. P. Zhou, M. Luo, S. Guo, Optimizing the semiconductor–metal-single-atom interaction for photocatalytic reactivity. Nat. Rev. Chem. 6, 823–838 (2022). https://doi.org/10.1038/s41570-022-00434-1
  20. Q. Zhou, C. Xu, J. Hou, W. Ma, T. Jian et al., Duplex interpenetrating-phase FeNiZn and FeNi3 heterostructure with low-gibbs free energy interface coupling for highly efficient overall water splitting. Nano-Micro Lett. 15, 95 (2023). https://doi.org/10.1007/s40820-023-01066-w
  21. B. Singh, M.B. Gawande, A.D. Kute, R.S. Varma, P. Fornasiero et al., Single-atom (iron-based) catalysts: synthesis and applications. Chem. Rev. 121, 13620–13697 (2021). https://doi.org/10.1021/acs.chemrev.1c00158
  22. R.G. Kadam, T. Zhang, D. Zaoralová, M. Medveď, A. Bakandritsos et al., Single co-atoms as electrocatalysts for efficient hydrazine oxidation reaction. Small 17, e2006477 (2021). https://doi.org/10.1002/smll.202006477
  23. E. Khare, N. Holten-Andersen, M.J. Buehler, Transition-metal coordinate bonds for bioinspired macromolecules with tunable mechanical properties. Nat. Rev. Mater. 6, 421–436 (2021). https://doi.org/10.1038/s41578-020-00270-z
  24. P. Vishnoi, A. Saraswat, C.N.R. Rao, Chemically functionalized phosphorenes and their use in the water splitting reaction. J. Mater. Chem. A 10, 19534–19551 (2022). https://doi.org/10.1039/D2TA01932A
  25. W. Fu, J. Wan, H. Zhang, J. Li, W. Chen et al., Photoinduced loading of electron-rich Cu single atoms by moderate coordination for hydrogen evolution. Nat. Commun. 13, 5496 (2022). https://doi.org/10.1038/s41467-022-33275-z
  26. L. Zeng, Z. Zhao, F. Lv, Z. Xia, S.-Y. Lu et al., Anti-dissolution Pt single site with Pt(OH)(O3)/Co(P) coordination for efficient alkaline water splitting electrolyzer. Nat. Commun. 13, 3822 (2022). https://doi.org/10.1038/s41467-022-31406-0
  27. S. Li, B. Chen, Y. Wang, M.Y. Ye, P.A. van Aken et al., Oxygen-evolving catalytic atoms on metal carbides. Nat. Mater. 20, 1240–1247 (2021). https://doi.org/10.1038/s41563-021-01006-2
  28. H. Liu, J. Cheng, W. He, Y. Li, J. Mao et al., Interfacial electronic modulation of Ni3S2 nanosheet arrays decorated with Au nanops boosts overall water splitting. Appl. Catal. B Environ. 304, 120935 (2022). https://doi.org/10.1016/j.apcatb.2021.120935
  29. T. Liang, S. Lenus, Y. Liu, Y. Chen, T. Sakthivel et al., Interface and M3+/M2+ valence dual-engineering on nickel cobalt sulfoselenide/black phosphorus heterostructure for efficient water splitting electrocatalysis. Energy Environ. Mater. 6, 12332 (2023). https://doi.org/10.1002/eem2.12332
  30. C. Wang, Q. He, U. Halim, Y. Liu, E. Zhu et al., Monolayer atomic crystal molecular superlattices. Nature 555, 231–236 (2018). https://doi.org/10.1038/nature25774
  31. J. Li, J. Li, J. Ren, H. Hong, D. Liu et al., Electric-field-treated Ni/Co3O4 film as high-performance bifunctional electrocatalysts for efficient overall water splitting. Nano-Micro Lett. 14, 148 (2022). https://doi.org/10.1007/s40820-022-00889-3
  32. X. Wang, Q. Li, P. Shi, J. Fan, Y. Min et al., Nickel nitride ps supported on 2D activated graphene-black phosphorus heterostructure: an efficient electrocatalyst for the oxygen evolution reaction. Small 15, e1901530 (2019). https://doi.org/10.1002/smll.201901530
  33. W. Yang, B. Ling, B. Hu, H. Yin, J. Mao et al., Synergistic N-heterocyclic carbene/palladium-catalyzed umpolung 1, 4-addition of aryl iodides to enals. Angew. Chem. Int. Ed. 59, 161–166 (2020). https://doi.org/10.1002/anie.201912584
  34. S.J. Song, I.S. Raja, Y.B. Lee, M.S. Kang, H.J. Seo et al., Comparison of cytotoxicity of black phosphorus nanosheets in different types of fibroblasts. Biomater. Res. 23, 23 (2019). https://doi.org/10.1186/s40824-019-0174-x
  35. Y. Liu, Y. Chen, Y. Tian, T. Sakthivel, H. Liu et al., Synergizing hydrogen spillover and deprotonation by the internal polarization field in a MoS2/NiPS3 vertical heterostructure for boosted water electrolysis. Adv. Mater. 34, e2203615 (2022). https://doi.org/10.1002/adma.202203615
  36. Y. Wang, X. Li, Z. Huang, H. Wang, Z. Chen et al., Amorphous Mo-doped NiS0.5 Se0.5 Nanosheets@Crystalline NiS0.5 Se0.5 nanorods for high current-density electrocatalytic water splitting in neutral media. Angew. Chem. Int. Ed. 62, e202215256 (2023). https://doi.org/10.1002/anie.202215256
  37. Y. Wang, X. Li, M. Zhang, J. Zhang, Z. Chen et al., Highly active and durable single-atom tungsten-doped NiS0.5 Se0.5 nanosheet @ NiS0.5 Se0.5 nanorod heterostructures for water splitting. Adv. Mater. 34, e2107053 (2022). https://doi.org/10.1002/adma.202107053
  38. L. Su, D. Gong, N. Yao, Y. Li, Z. Li et al., Modification of the intermediate binding energies on Ni/Ni3N heterostructure for enhanced alkaline hydrogen oxidation reaction. Adv. Funct. Mater. 31, 2106156 (2021). https://doi.org/10.1002/adfm.202106156
  39. Y. Bai, Y. Wu, X. Zhou, Y. Ye, K. Nie et al., Promoting nickel oxidation state transitions in single-layer NiFeB hydroxide nanosheets for efficient oxygen evolution. Nat. Commun. 13, 6094 (2022). https://doi.org/10.1038/s41467-022-33846-0
  40. X. Wang, S. Xi, P. Huang, Y. Du, H. Zhong et al., Pivotal role of reversible NiO6 geometric conversion in oxygen evolution. Nature 611, 702–708 (2022). https://doi.org/10.1038/s41586-022-05296-7
  41. Y. Lin, H. Wang, C.-K. Peng, L. Bu, C.-L. Chiang et al., Co-induced electronic optimization of hierarchical NiFe LDH for oxygen evolution. Small 16, e2002426 (2020). https://doi.org/10.1002/smll.202002426
  42. L. Li, L. Wang, X. Peng, S. Tao, M.-H. Zeng, Nickel–salen as a model for bifunctional OER/UOR electrocatalysts: pyrolysis temperature–electrochemical activity interconnection. Inorg. Chem. Front. 9, 1973–1983 (2022). https://doi.org/10.1039/d2qi00226d
  43. P.F. Liu, X. Li, S. Yang, M.Y. Zu, P. Liu et al., Ni2P(O)/Fe2P(O) interface can boost oxygen evolution electrocatalysis. ACS Energy Lett. 2, 2257–2263 (2017). https://doi.org/10.1021/acsenergylett.7b00638
  44. W. Zhai, Y. Chen, Y. Liu, T. Sakthivel, Y. Ma et al., Bimetal-incorporated black phosphorene with surface electron deficiency for efficient anti-reconstruction water electrolysis. Adv. Funct. Mater. 33, 2301565 (2023). https://doi.org/10.1002/adfm.202301565
  45. W. Ni, T. Wang, F. Héroguel, A. Krammer, S. Lee et al., An efficient nickel hydrogen oxidation catalyst for hydroxide exchange membrane fuel cells. Nat. Mater. 21, 804–810 (2022). https://doi.org/10.1038/s41563-022-01221-5
  46. J. Wang, J. Yu, J. Wang, K. Wang, L. Yu et al., Adsorbed p-aminothiophenol molecules on platinum nanops improve electrocatalytic hydrogen evolution. Small 19, e2207135 (2023). https://doi.org/10.1002/smll.202207135
  47. J. Wang, S.-J. Kim, J. Liu, Y. Gao, S. Choi et al., Redirecting dynamic surface restructuring of a layered transition metal oxide catalyst for superior water oxidation. Nat. Catal. 4, 212–222 (2021). https://doi.org/10.1038/s41929-021-00578-1
  48. H. Lei, L. Ma, Q. Wan, S. Tan, B. Yang et al., Promoting surface reconstruction of NiFe layered double hydroxide for enhanced oxygen evolution. Adv. Energy Mater. 12, 2202522 (2022). https://doi.org/10.1002/aenm.202202522
  49. J. Mei, J. Shang, T. He, D. Qi, L. Kou et al., 2D/2D black phosphorus/nickel hydroxide heterostructures for promoting oxygen evolution via electronic structure modulation and surface reconstruction. Adv. Energy Mater. 12, 2270104 (2022). https://doi.org/10.1002/aenm.202270104
  50. T. Wu, S. Xu, Z. Zhang, M. Luo, R. Wang et al., Bimetal modulation stabilizing a metallic heterostructure for efficient overall water splitting at large current density. Adv. Sci. 9, e2202750 (2022). https://doi.org/10.1002/advs.202202750
  51. D. S. Hongzhiwei Technology, Version 2021A, China. https://iresearch.net.cn/cloudSoftware. Accessed Oct 2022
  52. Y. Liu, P. Vijayakumar, Q. Liu, T. Sakthivel, F. Chen et al., Shining light on anion-mixed nanocatalysts for efficient water electrolysis: fundamentals, progress, and perspectives. Nano-Micro Lett. 14, 43 (2022). https://doi.org/10.1007/s40820-021-00785-2
  53. B. Zhang, Y. Chen, J. Wang, H. Pan, W. Sun, Supported sub-nanometer clusters for electrocatalysis applications. Adv. Funct. Mater. 32, 2202227 (2022). https://doi.org/10.1002/adfm.202202227
  54. Z. Yuan, J. Li, M. Yang, Z. Fang, J. Jian et al., Ultrathin black phosphorus-on-nitrogen doped graphene for efficient overall water splitting: dual modulation roles of directional interfacial charge transfer. J. Am. Chem. Soc. 141, 4972–4979 (2019). https://doi.org/10.1021/jacs.9b00154
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