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Vol. 16 (2024)

Achieving Negatively Charged Pt Single Atoms on Amorphous Ni(OH)2 Nanosheets with Promoted Hydrogen Absorption in Hydrogen Evolution

https://doi.org/10.1007/s40820-024-01420-6
Yue Liu
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology, Beihang University, Beijing 100191, People’s Republic of China
Gui Liu
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology, Beihang University, Beijing 100191, People’s Republic of China
Xiangyu Chen
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology, Beihang University, Beijing 100191, People’s Republic of China
Chuang Xue
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology, Beihang University, Beijing 100191, People’s Republic of China
Mingke Sun
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology, Beihang University, Beijing 100191, People’s Republic of China
Yifei Liu
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology, Beihang University, Beijing 100191, People’s Republic of China
Jianxin Kang
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology, Beihang University, Beijing 100191, People’s Republic of China
Xiujuan Sun
School of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Xiangtan 411105, Hunan, People’s Republic of China
Lin Guo
School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Key Laboratory of Bio‑inspired Smart Interfacial Science and Technology, Beihang University, Beijing 100191, People’s Republic of China

Corresponding Author: Lin Guo

guolin@buaa.edu.cn

Nano-Micro Letters, Vol. 16 (2024), Article Number: 202

Abstract

Single-atom (SA) catalysts with nearly 100% atom utilization have been widely employed in electrolysis for decades, due to the outperforming catalytic activity and selectivity. However, most of the reported SA catalysts are fixed through the strong bonding between the dispersed single metallic atoms with nonmetallic atoms of the substrates, which greatly limits the controllable regulation of electrocatalytic activity of SA catalysts. In this work, Pt–Ni bonded Pt SA catalyst with adjustable electronic states was successfully constructed through a controllable electrochemical reduction on the coordination unsaturated amorphous Ni(OH)2 nanosheet arrays. Based on the X-ray absorption fine structure analysis and first-principles calculations, Pt SA was bonded with Ni sites of amorphous Ni(OH)2, rather than conventional O sites, resulting in negatively charged Ptδ−. In situ Raman spectroscopy revealed that the changed configuration and electronic states greatly enhanced absorbability for activated hydrogen atoms, which were the essential intermediate for alkaline hydrogen evolution reaction. The hydrogen spillover process was revealed from amorphous Ni(OH)2 that effectively cleave the H–O–H bond of H2O and produce H atom to the Pt SA sites, leading to a low overpotential of 48 mV in alkaline electrolyte at −1000 mA cm−2 mg−1Pt, evidently better than commercial Pt/C catalysts. This work provided new strategy for the controllable modulation of the local structure of SA catalysts and the systematic regulation of the electronic states.


Highlights:
1 Pt–Ni bonded Pt single-atom (SA) catalyst, rather than classic Pt–O bonded SA catalyst, was successfully constructed.
2 The electronic states of Pt SA catalyst were deeply regulated and negatively charged Ptδ− was realized.
3 Pt–Ni bonded Pt SA catalyst-enhanced absorbability for activated hydrogen atoms and promoted hydrogen absorption.

Keywords

Hydrogen evolution reaction Amorphous Pt single atoms Hydrogen spillover
Liu, Yue, Gui Liu, Xiangyu Chen, Chuang Xue, Mingke Sun, Yifei Liu, Jianxin Kang, Xiujuan Sun, and Lin Guo. 2024. “Achieving Negatively Charged Pt Single Atoms on Amorphous Ni(OH)2 Nanosheets With Promoted Hydrogen Absorption in Hydrogen Evolution”. Nano-Micro Letters 16 (May):202. https://doi.org/10.1007/s40820-024-01420-6.
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References
  1. Y. Hu, T. Chao, Y. Li, P. Liu, T. Zhao et al., Cooperative Ni(Co)–Ru–P Sites activate dehydrogenation for hydrazine oxidation assisting self-powered H2 production. Angew. Chem. Int. Ed. 62(35), e202308800 (2023). https://doi.org/10.1002/anie.202308800
  2. J. Park, S. Lee, H. Kim, A. Cho, S. Kim et al., Investigation of the support effect in atomically dispersed Pt on WO3−x for utilization of Pt in the hydrogen evolution reaction. Angew. Chem. Int. Ed. 58(45), 16038–16042 (2019). https://doi.org/10.1002/anie.201908122
  3. H. Gu, J. Li, X. Niu, J. Lin, L. Chen et al., Symmetry-breaking p-block antimony single atoms trigger N-bridged titanium sites for electrocatalytic nitrogen reduction with high efficiency. ACS Nano 17(21), 21838–21849 (2023). https://doi.org/10.1021/acsnano.3c07857
  4. H. Gu, W. Yue, J. Hu, X. Niu, H. Tang et al., Asymmetrically coordinated Cu–N1C2 single-atom catalyst immobilized on Ti3C2Tx MXene as separator coating for lithium-sulfur batteries. Adv. Energy Mater. 13(20), 2204014 (2023). https://doi.org/10.1002/aenm.202204014
  5. Q. Li, Q. Zhang, W. Xu, R. Zhao, M. Jiang et al., Sowing single atom seeds: a versatile strategy for hyper-low noble metal loading to boost hydrogen evolution reaction. Adv. Energy Mater. 13(10), 2203955 (2023). https://doi.org/10.1002/aenm.202203955
  6. C. Ye, J. Shan, C. Zhu, W. Xu, L. Song et al., Spatial structure engineering of interactive single platinum sites toward enhanced electrocatalytic hydrogen evolution. Adv. Energy Mater. 13(45), 2302190 (2023). https://doi.org/10.1002/aenm.202302190
  7. C. Wang, L. Kuai, W. Cao, H. Singh, A. Zakharov et al., Highly dispersed Cu atoms in MOF-derived N-doped porous carbon inducing Pt loads for superior oxygen reduction and hydrogen evolution. Chem. Eng. J. 426(15), 130749 (2021). https://doi.org/10.1016/j.cej.2021.130749
  8. Z. Chen, X. Li, J. Zhao, S. Zhang, J. Wang et al., Stabilizing Pt single atoms through Pt–Se electron bridges on vacancy-enriched nickel selenide for efficient electrocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 62(39), e202308686 (2023). https://doi.org/10.1002/anie.202308686
  9. R. Li, D. Wu, P. Rao, P. Deng, J. Li et al., General approach for atomically dispersed precious metal catalysts toward hydrogen reaction. Carbon Energy 5(7), e294 (2023). https://doi.org/10.1002/cey2.294
  10. K. Chen, N. Zhang, F. Wang, J. Kang, K. Chu, Main-group indium single-atom catalysts for electrocatalytic NO reduction to NH3. J. Mater. Chem. A 11(13), 6814–6819 (2023). https://doi.org/10.1039/d3ta00606a
  11. X. Cheng, B. Xiao, Y. Chen, Y. Wang, L. Zheng et al., Ligand charge donation-acquisition balance: a unique strategy to boost single pt atom catalyst mass activity toward the hydrogen evolution reaction. ACS Catal. 12(10), 5970–5978 (2022). https://doi.org/10.1021/acscatal.2c00891
  12. P. Kuang, Y. Wang, B. Zhu, F. Xia, C. Tung et al., Pt single atoms supported on N-doped mesoporous hollow carbon spheres with enhanced electrocatalytic H2-evolution activity. Adv. Mater. 33(18), 2008599 (2021). https://doi.org/10.1002/adma.202008599
  13. H. Yang, Y. Ji, Q. Shao, W. Zhu, M. Fang et al., Metastable-phase platinum oxide for clarifying the Pt–O active site for the hydrogen evolution reaction. Energy Environ. Sci. 16(2), 574–583 (2023). https://doi.org/10.1039/D2EE03351H
  14. W. Chen, Y. Ma, F. Li, L. Pan, W. Gao et al., Strong electronic interaction of amorphous Fe2O3 nanosheets with single-atom Pt toward enhanced carbon monoxide oxidation. Adv. Funct. Mater. 29(42), 1904278 (2019). https://doi.org/10.1002/adfm.201904278
  15. Q. Fu, L. Wong, F. Zheng, X. Zheng, C.S. Tsang et al., Unraveling and leveraging in situ surface amorphization for enhanced hydrogen evolution reaction in alkaline media. Nat. Commun. 14(1), 6462 (2023). https://doi.org/10.1038/s41467-023-42221-6
  16. J. Nai, H. Yin, T. You, L. Zheng, J. Zhang et al., Efficient electrocatalytic water oxidation by using amorphous Ni–Co double hydroxides nanocages. Adv. Energy Mater. 5(10), 1401880 (2015). https://doi.org/10.1002/aenm.201401880
  17. X. Chen, S. Lv, J. Kang, Z. Wang, T. Guo et al., Efficient C–N coupling in the direct synthesis of urea from CO2 and N2 by amorphous SbxBi1−xOy clusters. Proc. Natl. Acad. Sci. U.S.A. 120(39), e2306841120 (2023). https://doi.org/10.1073/pnas.2306841120
  18. J. Kang, X. Chen, R. Si, X. Gao, S. Zhang et al., Activating Bi p-orbitals in dispersed clusters of amorphous BiOx for electrocatalytic nitrogen reduction. Angew. Chem. Int. Ed. 62(15), e202217428 (2023). https://doi.org/10.1002/anie.202217428
  19. Y. Zhao, Z. Huang, L. Wang, X. Chen, Y. Zhang et al., Highly efficient and recyclable amorphous Pd(II)/crystal Pd(0) catalyst for boosting Suzuki reaction in aqueous solution. Nano Res. 15(2), 1193–1198 (2022). https://doi.org/10.1007/s12274-021-3623-5
  20. J. Du, Y. Huang, Z. Huang, G. Wu, B. Wu et al., Reversing the catalytic selectivity of single-atom Ru via support amorphization. JACS Au 2(5), 1078–1083 (2022). https://doi.org/10.1021/jacsau.2c00192
  21. Y. Liu, X. Liu, A.R. Jadhav, T. Yang, Y. Hwang et al., Unraveling the function of metal-amorphous support interactions in single-atom electrocatalytic hydrogen evolution. Angew. Chem. Int. Ed. 61(9), e202114160 (2022). https://doi.org/10.1002/anie.202114160
  22. D. Feng, P. Wang, R. Qin, W. Shi, L. Gong et al., Flower-like amorphous MoO3−x stabilized Ru single atoms for efficient overall water/seawater splitting. Adv. Sci. 10(18), 2300342 (2023). https://doi.org/10.1002/advs.202300342
  23. Y. Hu, G. Luo, L. Wang, X. Liu, Y. Qu et al., Single Ru atoms stabilized by hybrid amorphous/crystalline FeCoNi layered double hydroxide for ultraefficient oxygen evolution. Adv. Energy Mater. 11(1), 2002816 (2021). https://doi.org/10.1002/aenm.202002816
  24. K. Chen, Y. Zhang, J. Xiang, X. Zhao, X. Li et al., p-Block antimony single-atom catalysts for nitric oxide electroreduction to ammonia. ACS Energy Lett. 8(3), 1281–1288 (2023). https://doi.org/10.1021/acsenergylett.2c02882
  25. L. Zeng, Z. Zhao, Q. Huang, C. Zhou, W. Chen et al., Single-atom Cr–N4 sites with high oxophilicity interfaced with Pt atomic clusters for practical alkaline hydrogen evolution catalysis. J. Am. Chem. Soc. 145(39), 21432–21441 (2023). https://doi.org/10.1021/jacs.3c06863
  26. J. Kang, Y. Xue, J. Yang, Q. Hu, Q. Zhang et al., Realizing two-electron transfer in Ni(OH)2 nanosheets for energy storage. J. Am. Chem. Soc. 144(20), 8969–8976 (2022). https://doi.org/10.1021/jacs.1c13523
  27. J. Kang, X. Qiu, Q. Hu, J. Zhong, X. Gao et al., Valence oscillation and dynamic active sites in monolayer NiCo hydroxides for water oxidation. Nat. Catal. 4(12), 1050–1058 (2021). https://doi.org/10.1038/s41929-021-00715-w
  28. J. Kang, G. Liu, Q. Hu, Y. Huang, L.M. Liu et al., Parallel nanosheet arrays for industrial oxygen production. J. Am. Chem. Soc. 145(46), 25143–25149 (2023). https://doi.org/10.1021/jacs.3c05688
  29. W. Guo, X. Gao, M. Zhu, C. Xu, X. Zhu et al., A closely packed Pt1.5Ni1−x/Ni–N–C hybrid for relay catalysis towards oxygen reduction. Energy Environ. Sci. 16(1), 148–156 (2023). https://doi.org/10.1039/D2EE02381D
  30. M. Wang, Y. Xu, C.K. Peng, S.Y. Chen, Y.G. Lin et al., Site-specified two-dimensional heterojunction of Pt nanops/metal-organic frameworks for enhanced hydrogen evolution. J. Am. Chem. Soc. 143(40), 16512–16518 (2021). https://doi.org/10.1021/jacs.1c06006
  31. T. Zhang, Z. Zhao, D. Zhang, X. Liu, P. Wang et al., Superexchange-induced Pt–O–Ti3+ site on single photocatalyst for efficient H2 production with organics degradation in wastewater. Proc. Natl. Acad. Sci. U.S.A. 120(23), e2302873120 (2023). https://doi.org/10.1073/pnas.2302873120
  32. Y. Li, A.I. Frenkel, Deciphering the local environment of single-atom catalysts with X-ray absorption spectroscopy. Acc. Chem. Res. 54(11), 2660–2669 (2021). https://doi.org/10.1021/acs.accounts.1c00180
  33. M. Zhou, H. Li, A. Long, B. Zhou, F. Lu et al., Modulating 3D orbitals of Ni atoms on Ni–Pt edge sites enables highly-efficient alkaline hydrogen evolution. Adv. Energy Mater. 11(36), 2101789 (2021). https://doi.org/10.1002/aenm.202101789
  34. K. Zhou, Z. Wang, C. Han, X. Ke, C. Wang et al., Platinum single-atom catalyst coupled with transition metal/metal oxide heterostructure for accelerating alkaline hydrogen evolution reaction. Nat. Commun. 12(1), 3783 (2021). https://doi.org/10.1038/s41467-021-24079-8
  35. X. Xiao, Z. Li, Y. Xiong, Y.W. Yang, IrMo nanocluster-doped porous carbon electrocatalysts derived from cucurbit[6]uril boost efficient alkaline hydrogen evolution. J. Am. Chem. Soc. 145(30), 16548–16556 (2023). https://doi.org/10.1021/jacs.3c03489
  36. X. Liu, Y. Jiang, J. Huang, W. Zhong, B. He et al., Bifunctional PdPt bimetallenes for formate oxidation-boosted water electrolysis. Carbon Energy 5(12), e367 (2023). https://doi.org/10.1002/cey2.367
  37. J. Chen, C. Chen, M. Qin, B. Li, B. Lin et al., Reversible hydrogen spillover in Ru–WO3−x enhances hydrogen evolution activity in neutral pH water splitting. Nat. Commun. 13(1), 5382 (2022). https://doi.org/10.1038/s41467-022-33007-3
  38. X. Chen, X.T. Wang, J.B. Le, S.M. Li, X. Wang et al., Revealing the role of interfacial water and key intermediates at ruthenium surfaces in the alkaline hydrogen evolution reaction. Nat. Commun. 14(1), 5289 (2023). https://doi.org/10.1038/s41467-023-41030-1
  39. C. Wan, Z. Zhang, J. Dong, M. Xu, H. Pu et al., Amorphous nickel hydroxide shell tailors local chemical environment on platinum surface for alkaline hydrogen evolution reaction. Nat. Mater. 22(8), 1022–1029 (2023). https://doi.org/10.1038/s41563-023-01584-3
  40. X. Wang, C. Xu, M. Jaroniec, Y. Zheng, S.Z. Qiao, Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions. Nat. Commun. 10(1), 4876 (2019). https://doi.org/10.1038/s41467-019-12773-7
  41. T. Zhang, J. Jin, J. Chen, Y. Fang, X. Han et al., Pinpointing the axial ligand effect on platinum single-atom-catalyst towards efficient alkaline hydrogen evolution reaction. Nat. Commun. 13(1), 6875 (2022). https://doi.org/10.1038/s41467-022-34619-5
  42. R. Subbaraman, D. Tripkovic, D. Strmcnik, K.C. Chang, M. Uchimura et al., Enhancing hydrogen evolution activity in water splitting by tailoring Li+–Ni(OH)2–Pt interfaces. Science 334(6060), 1256–1260 (2011). https://doi.org/10.1126/science.1211934
  43. Q. Xu, Heterogeneous interface engineered atomic configuration on ultrathin Ni(OH)2/Ni3S2 nanoforests for efficient water splitting. Appl. Catal. B 242, 60–66 (2019). https://doi.org/10.1016/j.apcatb.2018.09.064
  44. A. Mahdavi-Shakib, T.N. Whittaker, T.Y. Yun, K.B. Sravan Kumar, L.C. Rich et al., The role of surface hydroxyls in the entropy-driven adsorption and spillover of H2 on Au/TiO2 catalysts. Nat. Catal. 6(1), 710–719 (2023). https://doi.org/10.1038/s41929-023-00996-3
  45. J.K. Nørskov, T. Bligaard, A. Logadottir, J.R. Kitchin, J.G. Chen et al., Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152(3), J23 (2005). https://doi.org/10.1149/1.1856988
  46. Q. Yang, H. Liu, P. Yuan, Y. Jia, L. Zhuang et al., Single carbon vacancy traps atomic platinum for hydrogen evolution catalysis. J. Am. Chem. Soc. 144(5), 2171–2178 (2022). https://doi.org/10.1021/jacs.1c10814
  47. H. Zhang, P. An, W. Zhou, B. Guan, P. Zhang et al., Dynamic traction of lattice-confined platinum atoms into mesoporous carbon matrix for hydrogen evolution reaction. Sci. Adv. 4(1), eaao6657 (2018). https://doi.org/10.1126/sciadv.aao6657
  48. Y. Tian, M. Wen, A. Huang, Q. Wu, Z. Wang et al., Significantly stabilizing hydrogen evolution reaction induced by Nb-doping Pt/Co(OH)2 nanosheets. Small 19(20), 2207569 (2023). https://doi.org/10.1002/smll.202207569
  49. X. Wan, H. Wu, B. Guan, D. Luan, X. Lou, Confining sub-nanometer Pt clusters in hollow mesoporous carbon spheres for boosting hydrogen evolution activity. Adv. Mater. 32(7), 1901349 (2020). https://doi.org/10.1002/adma.201901349
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