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Vol. 16 (2024)

Durable Ru Nanocrystal with HfO2 Modification for Acidic Overall Water Splitting

https://doi.org/10.1007/s40820-024-01384-7
Xiangkai Kong
School of Materials and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu, People’s Republic of China
Jie Xu
Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, Huaibei Normal University, Huaibei 235000, Anhui, People’s Republic of China
Zhicheng Ju
School of Materials and Physics, China University of Mining and Technology, Xuzhou 221116, Jiangsu, People’s Republic of China
Changle Chen
School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, Anhui, People’s Republic of China

Corresponding Author: Changle Chen

changle@ustc.edu.cn

Nano-Micro Letters, Vol. 16 (2024), Article Number: 185

Abstract

Durable and efficient bi-functional catalyst, that is capable of both oxygen evolution reaction and hydrogen evolution reaction under acidic condition, are highly desired for the commercialization of proton exchange membrane water electrolysis. Herein, we report a robust L-Ru/HfO2 heterostructure constructed via confining crystalline Ru nanodomains by HfO2 matrix. When assembled with a proton exchange membrane, the bi-functional L-Ru/HfO2 catalyst-based electrolyzer presents a voltage of 1.57 and 1.67 V to reach 100 and 300 mA cm-2 current density, prevailing most of previously reported Ru-based materials as well as commercial Pt/C||RuO2 electrolyzer. It is revealed that the synergistic effect of HfO2 modification and small crystalline domain formation significantly alleviates the over-oxidation of Ru. More importantly, this synergistic effect facilitates a dual-site oxide path during the oxygen evolution procedure via optimization of the binding configurations of oxygenated adsorbates. As a result, the Ru active sites maintain the metallic state along with reduced energy barrier for the rate-determining step (*O→*OOH). Both of water adsorption and dissociation (Volmer step) are strengthened, while a moderate hydrogen binding is achieved to accelerate the hydrogen desorption procedure (Tafel step). Consequently, the activity and stability of acidic overall water splitting are simultaneously enhanced.


Highlights:
1 Heterostructure constructed via confining crystalline ruthenium nanodomains by hafnium dioxide matrix was fabricated through a two-step annealing method for overall water splitting.
2 The synergistic effect of hafnium dioxide modification and small crystalline domain formation significantly alleviates the over-oxidation of ruthenium.

Keywords

Ruthenium Hafnium dioxide Oxygen evolution catalysis Anti-oxidation
Kong, Xiangkai, Jie Xu, Zhicheng Ju, and Changle Chen. 2024. “Durable Ru Nanocrystal With HfO2 Modification for Acidic Overall Water Splitting”. Nano-Micro Letters 16 (April):185. https://doi.org/10.1007/s40820-024-01384-7.
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References
  1. J. Yang, A.R. Mohmad, Y. Wang, R. Fullon, X. Song et al., Ultrahigh-current-density niobium disulfide catalysts for hydrogen evolution. Nat. Mater. 18, 1309–1314 (2019). https://doi.org/10.1038/s41563-019-0463-8
  2. S. Liu, J. Liu, X. Liu, J. Shang, L. Xu et al., Hydrogen storage in incompletely etched multilayer Ti2CTx at room temperature. Nat. Nanotechnol. 16, 331–336 (2021). https://doi.org/10.1038/s41565-020-00818-8
  3. D. Yan, C. Mebrahtu, S. Wang, R. Palkovits, Innovative electrochemical strategies for hydrogen production: from electricity input to electricity output. Angew. Chem. Int. Ed. 62, e202214333 (2023). https://doi.org/10.1002/anie.202214333
  4. 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
  5. H. Song, M. Wu, Z. Tang, J.S. Tse, B. Yang et al., Single atom ruthenium-doped CoP/CDs nanosheets via splicing of carbon-dots for robust hydrogen production. Angew. Chem. Int. Ed. 60, 7234–7244 (2021). https://doi.org/10.1002/anie.202017102
  6. K. Yu, H. Yang, H. Zhang, H. Huang, Z. Wang et al., Immobilization of oxyanions on the reconstructed heterostructure evolved from a bimetallic oxysulfide for the promotion of oxygen evolution reaction. Nano-Micro Lett. 15, 186 (2023). https://doi.org/10.1007/s40820-023-01164-9
  7. D. Yan, C. Xia, W. Zhang, Q. Hu, C. He et al., Cation defect engineering of transition metal electrocatalysts for oxygen evolution reaction. Adv. Energy Mater. 12, 2202317 (2022). https://doi.org/10.1002/aenm.202202317
  8. C. Li, S.H. Kim, H.Y. Lim, Q. Sun, Y. Jiang et al., Self-accommodation induced electronic metal-support interaction on ruthenium site for alkaline hydrogen evolution reaction. Adv. Mater. 35, e2301369 (2023). https://doi.org/10.1002/adma.202301369
  9. J. Xu, Y. Feng, P. Wu, S. Tian, Z. Fang et al., Embedded ruthenium nanops within exfoliated nanosheets of Ti3C2Tx for hydrogen evolution. ACS Appl. Nano Mater. 5, 14241–14245 (2022). https://doi.org/10.1021/acsanm.2c03648
  10. B. Guo, Y. Ding, H. Huo, X. Wen, X. Ren et al., Recent advances of transition metal basic salts for electrocatalytic oxygen evolution reaction and overall water electrolysis. Nano-Micro Lett. 15, 57 (2023). https://doi.org/10.1007/s40820-023-01038-0
  11. X. Kong, C. Zhang, S.Y. Hwang, Q. Chen, Z. Peng, Free-standing holey Ni(OH)2 nanosheets with enhanced activity for water oxidation. Small 13, 1700334 (2017). https://doi.org/10.1002/smll.201700334
  12. H.N. Nong, T. Reier, H.-S. Oh, M. Gliech, P. Paciok et al., A unique oxygen ligand environment facilitates water oxidation in hole-doped IrNiOx core–shell electrocatalysts. Nat. Catal. 1, 841–851 (2018). https://doi.org/10.1038/s41929-018-0153-y
  13. T. Reier, H.N. Nong, D. Teschner, R. Schlögl, P. Strasser, Electrocatalytic oxygen evolution reaction in acidic environments–reaction mechanisms and catalysts. Adv. Energy Mater. 7, 1601275 (2017). https://doi.org/10.1002/aenm.201601275
  14. Y. Li, T. Xu, Q. Huang, L. Zhu, Y. Yan et al., C60 fullerenol to stabilize and activate Ru nanops for highly efficient hydrogen evolution reaction in alkaline media. ACS Catal. 13, 7597–7605 (2023). https://doi.org/10.1021/acscatal.3c01610
  15. H. Shi, H. Liang, F. Ming, Z. Wang, Efficient overall water-splitting electrocatalysis using lepidocrocite VOOH hollow nanospheres. Angew. Chem. Int. Ed. 56, 573–577 (2017). https://doi.org/10.1002/anie.201610211
  16. Q. Liang, Q. Li, L. Xie, H. Zeng, S. Zhou et al., Superassembly of surface-enriched Ru nanoclusters from trapping-bonding strategy for efficient hydrogen evolution. ACS Nano 16, 7993–8004 (2022). https://doi.org/10.1021/acsnano.2c00901
  17. L. Zhang, N. Jin, Y. Yang, X.-Y. Miao, H. Wang et al., Advances on axial coordination design of single-atom catalysts for energy electrocatalysis: a review. Nano-Micro Lett. 15, 228 (2023). https://doi.org/10.1007/s40820-023-01196-1
  18. C.-F. Li, T.-Y. Shuai, L.-R. Zheng, H.-B. Tang, J.-W. Zhao et al., The key role of carboxylate ligands in Ru@Ni-MOFs/NF in promoting water dissociation kinetics for effective hydrogen evolution in alkaline media. Chem. Eng. J. 451, 138618 (2023). https://doi.org/10.1016/j.cej.2022.138618
  19. P. Bhanja, Y. Kim, B. Paul, Y.V. Kaneti, A.A. Alothman et al., Microporous nickel phosphonate derived heteroatom doped nickel oxide and nickel phosphide: efficient electrocatalysts for oxygen evolution reaction. Chem. Eng. J. 405, 126803 (2021). https://doi.org/10.1016/j.cej.2020.126803
  20. N.L.W. Septiani, Y.V. Kaneti, Y. Guo, B. Yuliarto, X. Jiang et al., Holey assembly of two-dimensional iron-doped nickel-cobalt layered double hydroxide nanosheets for energy conversion application. ChemSusChem 13, 1645–1655 (2020). https://doi.org/10.1002/cssc.201901364
  21. Y. Guo, C. Zhang, J. Zhang, K. Dastafkan, K. Wang et al., Metal–organic framework-derived bimetallic NiFe selenide electrocatalysts with multiple phases for efficient oxygen evolution reaction. ACS Sustain. Chem. Eng. 9, 2047–2056 (2021). https://doi.org/10.1021/acssuschemeng.0c06969
  22. X. Gu, M. Yu, S. Chen, X. Mu, Z. Xu et al., Coordination environment of Ru clusters with in situ generated metastable symmetry-breaking centers for seawater electrolysis. Nano Energy 102, 107656 (2022). https://doi.org/10.1016/j.nanoen.2022.107656
  23. N. Han, W. Zhang, W. Guo, H. Pan, B. Jiang et al., Designing oxide catalysts for oxygen electrocatalysis: insights from mechanism to application. Nano-Micro Lett. 15, 185 (2023). https://doi.org/10.1007/s40820-023-01152-z
  24. D. Wu, D. Chen, J. Zhu, S. Mu, Ultralow Ru incorporated amorphous cobalt-based oxides for high-current-density overall water splitting in alkaline and seawater media. Small 17, e2102777 (2021). https://doi.org/10.1002/smll.202102777
  25. G. Li, H. Jang, S. Liu, Z. Li, M.G. Kim et al., The synergistic effect of Hf-O-Ru bonds and oxygen vacancies in Ru/HfO2 for enhanced hydrogen evolution. Nat. Commun. 13, 1270 (2022). https://doi.org/10.1038/s41467-022-28947-9
  26. J. Xu, S. Wang, C. Yang, T. Li, Q. Liu et al., Free-standing two-dimensional ruthenium-beryllium nanosheets for alkaline hydrogen evolution. Chem. Eng. J. 421, 129741 (2021). https://doi.org/10.1016/j.cej.2021.129741
  27. S. Li, D. Liu, G. Wang, P. Ma, X. Wang et al., Vertical 3D nanostructures boost efficient hydrogen production coupled with glycerol oxidation under alkaline conditions. Nano-Micro Lett. 15, 189 (2023). https://doi.org/10.1007/s40820-023-01150-1
  28. F. Bao, Z. Yang, Y. Yuan, P. Yu, G. Zeng et al., Synergistic cascade hydrogen evolution boosting via integrating surface oxophilicity modification with carbon layer confinement. Adv. Funct. Mater. 32, 2108991 (2022). https://doi.org/10.1002/adfm.202108991
  29. S. Hao, M. Liu, J. Pan, X. Liu, X. Tan et al., Dopants fixation of Ruthenium for boosting acidic oxygen evolution stability and activity. Nat. Commun. 11, 5368 (2020). https://doi.org/10.1038/s41467-020-19212-y
  30. A. Grimaud, O. Diaz-Morales, B. Han, W.T. Hong, Y.-L. Lee et al., Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution. Nat. Chem. 9, 457–465 (2017). https://doi.org/10.1038/nchem.2695
  31. P. Gayen, S. Saha, K. Bhattacharyya, V.K. Ramani, Oxidation state and oxygen-vacancy-induced work function controls bifunctional oxygen electrocatalytic activity. ACS Catal. 10, 7734–7746 (2020). https://doi.org/10.1021/acscatal.0c01541
  32. C. Roy, R.R. Rao, K.A. Stoerzinger, J. Hwang, J. Rossmeisl et al., Trends in activity and dissolution on RuO2 under oxygen evolution conditions: ps versus well-defined extended surfaces. ACS Energy Lett. 3, 2045–2051 (2018). https://doi.org/10.1021/acsenergylett.8b01178
  33. S. Chen, H. Huang, P. Jiang, K. Yang, J. Diao et al., Mn-doped RuO2 nanocrystals as highly active electrocatalysts for enhanced oxygen evolution in acidic media. ACS Catal. 10, 1152–1160 (2020). https://doi.org/10.1021/acscatal.9b04922
  34. J. Su, R. Ge, K. Jiang, Y. Dong, F. Hao et al., Assembling ultrasmall copper-doped ruthenium oxide nanocrystals into hollow porous polyhedra: highly robust electrocatalysts for oxygen evolution in acidic media. Adv. Mater., e1801351 (2018). https://doi.org/10.1002/adma.201801351
  35. X. Cui, P. Ren, C. Ma, J. Zhao, R. Chen et al., Robust interface Ru centers for high-performance acidic oxygen evolution. Adv. Mater. 32, e1908126 (2020). https://doi.org/10.1002/adma.201908126
  36. J. Wang, H. Yang, F. Li, L. Li, J. Wu et al., Single-site Pt-doped RuO2 hollow nanospheres with interstitial C for high-performance acidic overall water splitting. Sci. Adv. 8, eabl9271 (2022). https://doi.org/10.1126/sciadv.abl9271
  37. M.A. Hubert, A.M. Patel, A. Gallo, Y. Liu, E. Valle et al., Acidic oxygen evolution reaction activity–stability relationships in Ru-based pyrochlores. ACS Catal. 10, 12182–12196 (2020). https://doi.org/10.1021/acscatal.0c02252
  38. D. Zhang, M. Li, X. Yong, H. Song, G.I.N. Waterhouse et al., Construction of Zn-doped RuO2 nanowires for efficient and stable water oxidation in acidic media. Nat. Commun. 14, 2517 (2023). https://doi.org/10.1038/s41467-023-38213-1
  39. A.M. Harzandi, S. Shadman, A.S. Nissimagoudar, D.Y. Kim, H.-D. Lim et al., Ruthenium core–shell engineering with nickel single atoms for selective oxygen evolution via nondestructive mechanism. Adv. Energy Mater. 11, 2003448 (2021). https://doi.org/10.1002/aenm.202003448
  40. Y. Zhang, G.-Q. Mao, X. Zhao, Y. Li, M. Zhang et al., Evolution of the conductive filament system in HfO2-based memristors observed by direct atomic-scale imaging. Nat. Commun. 12, 7232 (2021). https://doi.org/10.1038/s41467-021-27575-z
  41. D. Huang, K. Wang, L. Yu, T.H. Nguyen, S. Ikeda et al., Over 1% efficient unbiased stable solar water splitting based on a sprayed Cu2ZnSnS4 photocathode protected by a HfO2 photocorrosion-resistant film. ACS Energy Lett. 3, 1875–1881 (2018). https://doi.org/10.1021/acsenergylett.8b01005
  42. W. Banerjee, A. Kashir, S. Kamba, Hafnium oxide (HfO2) - A multifunctional oxide: a review on the prospect and challenges of hafnium oxide in resistive switching and ferroelectric memories. Small 18, e2107575 (2022). https://doi.org/10.1002/smll.202107575
  43. Y. Wang, Q. Lu, F. Li, D. Guan, Y. Bu, Atomic-scale configuration enables fast hydrogen migration for electrocatalysis of acidic hydrogen evolution. Adv. Funct. Mater. 33, 2213523 (2023). https://doi.org/10.1002/adfm.202213523
  44. J. Xu, C. Chen, X. Kong, Ru-O-Cu center constructed by catalytic growth of Ru for efficient hydrogen evolution. Nano Energy 111, 108403 (2023). https://doi.org/10.1016/j.nanoen.2023.108403
  45. J. Xu, X. Kong, Amorphous/crystalline heterophase ruthenium nanosheets for pH-universal hydrogen evolution. Small Methods 6, e2101432 (2022). https://doi.org/10.1002/smtd.202101432
  46. P. Wu, X. Kong, Y. Feng, W. Ding, Z. Sheng et al., Phase engineering on amorphous/crystalline γ-Fe2O3 nanosheets for boosting dielectric loss and high-performance microwave absorption. Adv. Funct. Mater., 34, 2311983 (2024). https://doi.org/10.1002/adfm.202311983
  47. G. Wu, X. Zheng, P. Cui, H. Jiang, X. Wang et al., A general synthesis approach for amorphous noble metal nanosheets. Nat. Commun. 10, 4855 (2019). https://doi.org/10.1038/s41467-019-12859-2
  48. G. Yan, Y. Wang, Z. Zhang, Y. Dong, J. Wang et al., Nanop-decorated ultrathin La2O3 nanosheets as an efficient electrocatalysis for oxygen evolution reactions. Nano-Micro Lett. 12, 49 (2020). https://doi.org/10.1007/s40820-020-0387-5
  49. M. Su, J. Shi, Q. Kang, D. Lai, Q. Lu et al., One-step multiple structure modulations on sodium vanadyl phosphate@carbon towards ultra-stable high rate sodium storage. Chem. Eng. J. 432, 134289 (2022). https://doi.org/10.1016/j.cej.2021.134289
  50. A. Pei, G. Li, L. Zhu, Z. Huang, J. Ye et al., Nickel hydroxide-supported Ru single atoms and Pd nanoclusters for enhanced electrocatalytic hydrogen evolution and ethanol oxidation. Adv. Funct. Mater. 32, 2208587 (2022). https://doi.org/10.1002/adfm.202208587
  51. L. Cao, Q. Luo, J. Chen, L. Wang, Y. Lin et al., Dynamic oxygen adsorption on single-atomic Ruthenium catalyst with high performance for acidic oxygen evolution reaction. Nat. Commun. 10, 4849 (2019). https://doi.org/10.1038/s41467-019-12886-z
  52. D. Majumdar, T. Maiyalagan, Z. Jiang, Recent progress in ruthenium oxide-based composites for supercapacitor applications. ChemElectroChem 6, 4343–4372 (2019). https://doi.org/10.1002/celc.201900668
  53. Y. Hu, C. Hu, A. Du, T. Xiao, L. Yu et al., Interfacial evolution on co-based oxygen evolution reaction electrocatalysts probed by using in situ surface-enhanced Raman spectroscopy. Anal. Chem. 95, 1703–1709 (2023). https://doi.org/10.1021/acs.analchem.2c04931
  54. J.C. Dong, M. Su, V. Briega-Martos, L. Li, J.B. Le et al., Direct in situ Raman spectroscopic evidence of oxygen reduction reaction intermediates at high-index Pt(hkl) surfaces. J. Am. Chem. Soc. 142, 715–719 (2020). https://doi.org/10.1021/jacs.9b12803
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