AI Chat Paper
Note: Please note that the following content is generated by AMiner AI. SciOpen does not take any responsibility related to this content.
{{lang === 'zh_CN' ? '文章概述' : 'Summary'}}
{{lang === 'en_US' ? '中' : 'Eng'}}
Chat more with AI
Powered by AMiner. Clicking this button will take you away from SciOpen.
Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Show full outline
Hide outline
Outline
Show full outline
Hide outline
Research Article

Micropore-confined Ru nanoclusters catalyst for efficient pH-universal hydrogen evolution reaction

Xiaoxiao Huang1,§, Ruihu Lu2,§, Yaping Cen1, Dunchao Wang1, Shao Jin1, Wenxing Chen3, Geoffrey I.1,2,3, N. Waterhouse2, Ziyun Wang2( ), Shubo Tian1( ), Xiaoming Sun1( )
State Key Laboratory of Chemical Resource Engineering College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China
School of Chemical Sciences, The University of Auckland, Auckland 1010, New Zealand
School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China

§ Xiaoxiao Huang and Ruihu Lu contributed equally to this work.

Show Author Information

Graphical Abstract

Through the interaction of Ru nanoclusters with an N-doped carbon support, both metal valence and local metal coordination can be manipulated, thus allowing the precise tailoring of metal electronic structures for optimal hydrogen evolution reaction (HER) performance.

Abstract

Pt-based catalysts are used commercially for the hydrogen evolution reaction (HER), even though the low earth abundance and high cost of platinum hinder scale-up applications. Ru metal is a promising alternative catalyst for HER owing to its lower cost but similar metal–hydrogen bond strength to Pt. However, designing an efficient and robust Ru-based electrocatalyst for pH-universal HER is challenging. Herein, we successfully synthesized N-doped carbon (NC) supported ruthenium catalysts with different Ru sizes (single-atoms, nanoclusters and nanoparticles), and then systematically evaluated their performance for HER. Among these catalysts, the Ru nanocluster catalyst (Ru NCs/NC) displayed optimal catalytic performance with overpotentials of only 14, 30, and 32 mV (at 10 mA·cm−2) in 1 M KOH, 1 M phosphate buffer saline (PBS), and 0.5 M H2SO4, respectively. The corresponding mass activities were 32.2, 12.1 and 8.1 times higher than those of 20 wt.% Pt/C, and also much better than those of the Ru single-atoms (Ru SAs/NC) and Ru nanoparticle (Ru NPs/NC) catalysts, at an overpotential of 100 mV under alkaline, neutral and acidic conditions, respectively. Density functional theory (DFT) calculations revealed that the outstanding HER performance of the Ru NCs/NC catalyst resulted from a strong interaction between the Ru nanoclusters and the N-doped carbon support, which downshifted the d-band center and thus weakened the *H adsorption ability of Ru sites.

Keywords

Ru nanoclustersRu single atomsRu nanoparticleshydrogen evolution reaction

Electronic Supplementary Material

Download File(s)
12274_2023_5711_MOESM1_ESM.pdf (2.9 MB)

References

[1]

Chu, S.; Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 2012, 488, 294–303.
Crossref Google Scholar
[2]

Turner, J. A. Sustainable hydrogen production. Science 2004, 305, 972–974.
Crossref Google Scholar
[3]

dos Santos, K. G.; Eckert, C. T.; De Rossi, E.; Bariccatti, R. A.; Frigo, E. P.; Lindino, C. A.; Alves, H. J. Hydrogen production in the electrolysis of water in Brazil, a review. Renew. Sustain. Energy Rev. 2017, 68, 563–571.
Crossref Google Scholar
[4]

Zou, X. X.; Zhang, Y. Noble metal-free hydrogen evolution catalysts for water splitting. Chem. Soc. Rev. 2015, 44, 5148–5180.
Crossref Google Scholar
[5]

Zhang, J. C.; Chen, G. B.; Liu, Q. C.; Fan, C.; Sun, D. M.; Tang, Y. W.; Sun, H. J.; Feng, X. L. Competitive adsorption: Reducing the poisoning effect of adsorbed hydroxyl on Ru single-atom site with SnO2 for efficient hydrogen evolution. Angew. Chem., Int. Ed. 2022, 61, e202209486.
Crossref Google Scholar
[6]

Zheng, Y.; Jiao, Y.; Zhu, Y. H.; Li, L. H.; Han, Y.; Chen, Y.; Jaroniec, M.; Qiao, S. Z. High electrocatalytic hydrogen evolution activity of an anomalous ruthenium catalyst. J. Am. Chem. Soc. 2016, 138, 16174–16181.
Crossref Google Scholar
[7]

Song, H. Q.; Wu, M.; Tang, Z. Y.; Tse, J. S.; Yang, B.; Lu, S. Y. Single atom ruthenium-doped CoP/CDs nanosheets via splicing of carbon-dots for robust hydrogen production. Angew. Chem., Int. Ed. 2021, 60, 7234–7244.
Crossref Google Scholar
[8]

Yang, Q.; Liu, H. X.; Yuan, P.; Jia, Y.; Zhuang, L. Z.; Zhang, H. W.; Yan, X. C.; Liu, G. H.; Zhao, Y. F.; Liu, J. Z. et al. Single carbon vacancy traps atomic platinum for hydrogen evolution catalysis. J. Am. Chem. Soc. 2022, 144, 2171–2178.
Crossref Google Scholar
[9]

Ryu, J.; Wuttig, A.; Surendranath, Y. Quantification of interfacial pH variation at molecular length scales using a concurrent non-faradaic reaction. Angew. Chem., Int. Ed. 2018, 57, 9300–9304.
Crossref Google Scholar
[10]

Zhu, S. Q.; Shao, M. H. Electrolyte pH-dependent hydrogen binding energies and coverages on platinum, iridium, rhodium, and ruthenium surfaces. Catal. Sci. Technol. 2022, 12, 3228–3233.
Crossref Google Scholar
[11]

Lai, W. H.; Zhang, L. F.; Hua, W. B.; Indris, S.; Yan, Z. C.; Hu, Z.; Zhang, B. W.; Liu, Y. N.; Wang, L.; Liu, M. et al. General π-electron-assisted strategy for Ir, Pt, Ru, Pd, Fe, Ni single-atom electrocatalysts with bifunctional active sites for highly efficient water splitting. Angew. Chem., Int. Ed. 2019, 58, 11868–11873.
Crossref Google Scholar
[12]

Li, P. S.; Duan, X. X.; Wang, S. Y.; Zheng, L. R.; Li, Y. P.; Duan, H. H.; Kuang, Y.; Sun, X. M. Amorphous ruthenium-sulfide with isolated catalytic sites for Pt-like electrocatalytic hydrogen production over whole pH range. Small 2019, 15, 1904043.
Crossref Google Scholar
[13]

Chen, H.; Ai, X.; Liu, W.; Xie, Z. B.; Feng, W. Q.; Chen, W.; Zou, X. X. Promoting subordinate, efficient ruthenium sites with interstitial silicon for Pt-like electrocatalytic activity. Angew. Chem., Int. Ed. 2019, 58, 11409–11413.
Crossref Google Scholar
[14]

Yang, Y. J.; Yu, Y. H.; Li, J.; Chen, Q. R.; Du, Y. L.; Rao, P.; Li, R. S.; Jia, C. M.; Kang, Z. Y.; Deng, P. L. et al. Engineering ruthenium-based electrocatalysts for effective hydrogen evolution reaction. Nano-Micro Lett. 2021, 13, 160.
Crossref Google Scholar
[15]

Wang, J.; Wei, Z. Z.; Mao, S. J.; Li, H. R.; Wang, Y. Highly uniform Ru nanoparticles over N-doped carbon: pH and temperature-universal hydrogen release from water reduction. Energy Environ. Sci. 2018, 11, 800–806.
Crossref Google Scholar
[16]

Yang, Z. P.; Yang, D. D.; Wang, Y.; Long, Y.; Huang, W. C.; Fan, G. Y. Strong electrostatic adsorption-engaged fabrication of sub-3.0 nm PtRu alloy nanoparticles as synergistic electrocatalysts toward hydrogen evolution. Nanoscale 2021, 13, 10044–10050.
Crossref Google Scholar
[17]

Li, J. S.; Huang, M. J.; Zhou, Y. W.; Chen, X. N.; Yang, S.; Zhu, J. Y.; Liu, G. D.; Ma, L. J.; Cai, S. H.; Han, J. Y. RuP2-based hybrids derived from MOFs: Highly efficient pH-universal electrocatalysts for the hydrogen evolution reaction. J. Mater. Chem. A 2021, 9, 12276–12282.
Crossref Google Scholar
[18]

Liu, Y.; Liu, S. L.; Wang, Y.; Zhang, Q. H.; Gu, L.; Zhao, S. C.; Xu, D. D.; Li, Y. F.; Bao, J. C.; Dai, Z. H. Ru modulation effects in the synthesis of unique rod-like Ni@Ni2P-Ru heterostructures and their remarkable electrocatalytic hydrogen evolution performance. J. Am. Chem. Soc. 2018, 140, 2731–2734.
Crossref Google Scholar
[19]

Lu, B. Z.; Guo, L.; Wu, F.; Peng, Y.; Lu, J. E.; Smart, T. J.; Wang, N.; Finfrock, Y. Z.; Morris, D.; Zhang, P. et al. Ruthenium atomically dispersed in carbon outperforms platinum toward hydrogen evolution in alkaline media. Nat. Commun. 2019, 10, 631.
Crossref Google Scholar
[20]

Su, P. P.; Pei, W.; Wang, X. W.; Ma, Y. F.; Jiang, Q. K.; Liang, J.; Zhou, S.; Zhao, J. J.; Liu, J.; Lu, G. Q. Exceptional electrochemical HER performance with enhanced electron transfer between Ru nanoparticles and single atoms dispersed on a carbon substrate. Angew. Chem., Int. Ed. 2021, 60, 16044–16050.
Crossref Google Scholar
[21]

Hu, C.; Song, E. H.; Wang, M. Y.; Chen, W.; Huang, F. Q.; Feng, Z. X.; Liu, J. J.; Wang, J. C. Partial-single-atom, partial-nanoparticle composites enhance water dissociation for hydrogen evolution. Adv. Sci. 2021, 8, 2001881.
Crossref Google Scholar
[22]

Zhu, Q. Y.; Huang, X. X.; Zeng, Y. C.; Sun, K.; Zhou, L. L.; Liu, Y. Y.; Luo, L.; Tian, S. B.; Sun, X. M. Controllable synthesis and electrocatalytic applications of atomically precise gold nanoclusters. Nanoscale Adv. 2021, 3, 6330–6341.
Crossref Google Scholar
[23]

Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981–5079.
Crossref Google Scholar
[24]

Yang, J. R.; Li, W. H.; Xu, K. N.; Tan, S. D.; Wang, D. S.; Li, Y. D. Regulating the tip effect on single-atom and cluster catalysts: Forming reversible oxygen species with high efficiency in chlorine evolution reaction. Angew. Chem., Int. Ed. 2022, 61, e202200366.
Crossref Google Scholar
[25]

Yan, L.; Li, P. P.; Zhu, Q. Y.; Kumar, A.; Sun, K.; Tian, S. B.; Sun, X. M. Atomically precise electrocatalysts for oxygen reduction reaction. Chem 2023, 9, 280–342.
Crossref Google Scholar
[26]

Kumar, A.; Sun, K.; Duan, X. X.; Tian, S. B.; Sun, X. M. Construction of dual-atom Fe via face-to-face assembly of molecular phthalocyanine for superior oxygen reduction reaction. Chem. Mater. 2022, 34, 5598–5606.
Crossref Google Scholar
[27]

Jiang, Z. L.; Song, S. J.; Zheng, X. B.; Liang, X.; Li, Z. X.; Gu, H. F.; Li, Z.; Wang, Y.; Liu, S. H.; Chen, W. X. et al. Lattice strain and schottky junction dual regulation boosts ultrafine ruthenium nanoparticles anchored on a N-modified carbon catalyst for H2 production. J. Am. Chem. Soc. 2022, 144, 19619–19626.
Crossref Google Scholar
[28]

Yang, J. R.; Li, W. H.; Tan, S. D.; Xu, K. N.; Wang, Y.; Wang, D. S.; Li, Y. D. The electronic metal–support interaction directing the design of single atomic site catalysts: Achieving high efficiency towards hydrogen evolution. Angew. Chem., Int. Ed. 2021, 60, 19085–19091.
Crossref Google Scholar
[29]

Luo, Z. X.; Zhao, G. Q.; Pan, H. G.; Sun, W. P. Strong metal–support interaction in heterogeneous catalysts. Adv. Energy Mater. 2022, 12, 2201395.
Crossref Google Scholar
[30]

Zhu, P.; Xiong, X.; Wang, D. S. Regulations of active moiety in single atom catalysts for electrochemical hydrogen evolution reaction. Nano Res. 2022, 15, 5792–5815.
Crossref Google Scholar
[31]

Tang, J. L.; Xu, S. H.; Sun, K.; Gao, X. Q.; Chen, A. B.; Tian, S. B.; Zhou, D. J.; Sun, X. M. Recycling synthesis of single-atom Zn-nitrogen-carbon catalyst for electrocatalytic reduction of O2 to H2O2. Sci. China Mater. 2022, 65, 3490–3496.
Crossref Google Scholar
[32]

Liu, J. L.; Zheng, Y.; Zhu, D. D.; Vasileff, A.; Ling, T.; Qiao, S. Z. Identification of pH-dependent synergy on Ru/MoS2 interface: A comparison of alkaline and acidic hydrogen evolution. Nanoscale 2017, 9, 16616–16621.
Crossref Google Scholar
[33]

Zhao, Z. L.; Wang, Q.; Huang, X.; Feng, Q.; Gu, S.; Zhang, Z.; Xu, H.; Zeng, L.; Gu, M.; Li, H. Boosting the oxygen evolution reaction using defect-rich ultra-thin ruthenium oxide nanosheets in acidic media. Energy Environ. Sci. 2020, 13, 5143–5151.
Crossref Google Scholar
[34]

Dong, C. Y.; Li, Y. L.; Cheng, D. Y.; Zhang, M. T.; Liu, J. J.; Wang, Y. G.; Xiao, D. Q.; Ma, D. Supported metal clusters: Fabrication and application in heterogeneous catalysis. ACS Catal. 2020, 10, 11011–11045.
Crossref Google Scholar
[35]

Liu, D. Q.; Luo, Z. X.; Zhang, B. X.; Zhao, G. Q.; Guo, W.; Chen, J.; Gao, M. X.; Liu, Y. F.; Pan, H. G.; Sun, W. P. Tailoring interfacial charge transfer of epitaxially grown Ir clusters for boosting hydrogen oxidation reaction. Adv. Energy Mater. 2023, 13, 2202913.
Crossref Google Scholar
[36]

Li, R. Z.; Wang, D. S. Understanding the structure–performance relationship of active sites at atomic scale. Nano Res. 2022, 15, 6888–6923.
Crossref Google Scholar
[37]

Deng, D. H.; Yu, L.; Chen, X. Q.; Wang, G. X.; Jin, L.; Pan, X. L.; Deng, J.; Sun, G. Q.; Bao, X. H. Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction. Angew. Chem., Int. Ed. 2013, 52, 371–375.
Crossref Google Scholar
[38]

Liu, Y.; Zhang, T.; Deng, C.; Cao, S. X.; Dai, X.; Guo, S. W.; Chen, Y. Z.; Tan, Q.; Zhu, H. Y.; Zhang, S. et al. Ordered mesoporous carbon spheres assisted Ru nanoclusters/RuO2 with redistribution of charge density for efficient CO2 methanation in a novel H2/CO2 fuel cell. J. Energy Chem. 2022, 72, 116–124.
Crossref Google Scholar
[39]

Hu, Q.; Wang, Z. Y.; Huang, X. W.; Qin, Y. J.; Yang, H. P.; Ren, X. Z.; Zhang, Q. L.; Liu, J. H.; He, C. X. A unique space confined strategy to construct defective metal oxides within porous nanofibers for electrocatalysis. Energy Environ. Sci. 2020, 13, 5097–5103.
Crossref Google Scholar
[40]

Ohyama, J.; Sato, T.; Yamamoto, Y.; Arai, S.; Satsuma, A. Size specifically high activity of Ru nanoparticles for hydrogen oxidation reaction in alkaline electrolyte. J. Am. Chem. Soc. 2013, 135, 8016–8021.
Crossref Google Scholar
[41]

Li, T. Y.; Zhang, X. Y.; Chen, Y. L.; Zhong, L. X.; Li, S. Z.; Zhang, P. X.; Zhao, C. Y. Boosting the water dissociation kinetics via charge redistribution of ruthenium decorated on S, N-codoped carbon. J. Mater. Chem. A 2021, 9, 16967–16973.
Crossref Google Scholar
[42]

Li, C. F.; Zhao, J. W.; Xie, L. J.; Wang, Y.; Tang, H. B.; Zheng, L. R.; Li, G. R. N coupling with S-coordinated Ru nanoclusters for highly efficient hydrogen evolution in alkaline media. J. Mater. Chem. A 2021, 9, 12659–12669.
Crossref Google Scholar
[43]

Yang, J.; Chen, B. X.; Liu, X. K.; Liu, W.; Li, Z. J.; Dong, J. C.; Chen, W. X.; Yan, W. S.; Yao, T.; Duan, X. Z. et al. Efficient and robust hydrogen evolution: Phosphorus nitride imide nanotubes as supports for anchoring single ruthenium sites. Angew. Chem., Int. Ed. 2018, 57, 9495–9500.
Crossref Google Scholar
[44]

Liu, Y.; Li, X.; Zhang, Q. H.; Li, W. D.; Xie, Y.; Liu, H. Y.; Shang, L.; Liu, Z. Y.; Chen, Z. M.; Gu, L. et al. A general route to prepare low-ruthenium-content bimetallic electrocatalysts for pH-universal hydrogen evolution reaction by using carbon quantum dots. Angew. Chem., Int. Ed. 2020, 59, 1718–1726.
Crossref Google Scholar
[45]

Wang, Y. J.; Luo, W. J.; Li, H. J.; Cheng, C. W. Ultrafine Ru nanoclusters supported on N/S doped macroporous carbon spheres for efficient hydrogen evolution reaction. Nanoscale Adv. 2021, 3, 5068–5074.
Crossref Google Scholar
[46]

Xie, Q. J.; Wang, Z.; Lin, L. K.; Shu, Y.; Zhang, J. J.; Li, C.; Shen, Y. H.; Uyama, H. Nanoscaled and atomic ruthenium electrocatalysts confined inside super-hydrophilic carbon nanofibers for efficient hydrogen evolution reaction. Small 2021, 17, 2102160.
Crossref Google Scholar
[47]

Ji, S. F.; Chen, Y. J.; Zhao, S.; Chen, W. X.; Shi, L. J.; Wang, Y.; Dong, J. C.; Li, Z.; Li, F. W.; Chen, C. et al. Atomically dispersed ruthenium species inside metal-organic frameworks: Combining the high activity of atomic sites and the molecular sieving effect of MOFs. Angew. Chem., Int. Ed. 2019, 58, 4271–4275.
Crossref Google Scholar
[48]

Lin, J. F.; Ding, J. N.; Wang, H. Z.; Yang, X. Y.; Zheng, X. R.; Huang, Z. C.; Song, W. Q.; Ding, J.; Han, X. P.; Hu, W. B. Boosting energy efficiency and stability of Li-CO2 batteries via synergy between Ru atom clusters and single-atom Ru-N4 sites in the electrocatalyst cathode. Adv. Mater. 2022, 34, 2200559.
Crossref Google Scholar
[49]

Funke, H.; Scheinost, A. C.; Chukalina, M. Wavelet analysis of extended X-ray absorption fine structure data. Phys. Rev. B 2005, 71, 094110.
Crossref Google Scholar
[50]

Wu, Y. C.; Wei, W.; Yu, R. H.; Xia, L. X.; Hong, X. F.; Zhu, J. X.; Li, J. T.; Lv, L.; Chen, W.; Zhao, Y. et al. Anchoring sub-nanometer Pt clusters on crumpled paper-like MXene enables high hydrogen evolution mass activity. Adv. Funct. Mater. 2022, 32, 2110910.
Crossref Google Scholar
[51]

Li, L.; Zhang, G. W.; Wang, B.; Yang, T.; Yang, S. C. Electrochemical formation of PtRu bimetallic nanoparticles for highly efficient and pH-universal hydrogen evolution reaction. J. Mater. Chem. A 2020, 8, 2090–2098.
Crossref Google Scholar
[52]

Liu, Z. H.; Du, Y.; Yu, R. H.; Zheng, M. B.; Hu, R.; Wu, J. S.; Xia, Y. Y.; Zhuang, Z. C.; Wang, D. S. Tuning mass transport in electrocatalysis down to sub-5 nm through nanoscale grade separation. Angew. Chem., Int. Ed. 2023, 62, e202212653.
Crossref Google Scholar
[53]

Ma, M.; Li, G.; Yan, W.; Wu, Z. Z.; Zheng, Z. P.; Zhang, X. B.; Wang, Q. X.; Du, G. F.; Liu, D. Y.; Xie, Z. X. et al. Single-atom molybdenum engineered platinum nanocatalyst for boosted alkaline hydrogen oxidation. Adv. Energy Mater. 2022, 12, 2103336.
Crossref Google Scholar
[54]

Strmcnik, D.; Lopes, P. P.; Genorio, B.; Stamenkovic, V. R.; Markovic, N. M. Design principles for hydrogen evolution reaction catalyst materials. Nano Energy 2016, 29, 29–36.
Crossref Google Scholar
[55]

Durst, J.; Siebel, A.; Simon, C.; Hasché, F.; Herranz, J.; Gasteiger, H. A. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ. Sci. 2014, 7, 2255–2260.
Crossref Google Scholar
[56]

Zhuang, Z. W.; Wang, Y.; Xu, C. Q.; Liu, S. J.; Chen, C.; Peng, Q.; Zhuang, Z. B.; Xiao, H.; Pan, Y.; Lu, S. Q. et al. Three-dimensional open nano-netcage electrocatalysts for efficient pH-universal overall water splitting. Nat. Commun. 2019, 10, 4875.
Crossref Google Scholar
[57]

Yao, Q.; Huang, B. L.; Zhang, N.; Sun, M. Z.; Shao, Q.; Huang, X. Q. Channel-rich RuCu nanosheets for pH-universal overall water splitting electrocatalysis. Angew. Chem., Int. Ed. 2019, 58, 13983–13988.
Crossref Google Scholar
[58]

Moussallem, I.; Jörissen, J.; Kunz, U.; Pinnow, S.; Turek, T. Chlor-alkali electrolysis with oxygen depolarized cathodes: History, present status and future prospects. J. Appl. Electrochem. 2008, 38, 1177–1194.
Crossref Google Scholar
[59]

Pu, Z. H.; Amiinu, I. S.; Kou, Z. K.; Li, W. Q.; Mu, S. C. RuP2-based catalysts with platinum-like activity and higher durability for the hydrogen evolution reaction at all pH values. Angew. Chem., Int. Ed. 2017, 56, 11559–11564.
Crossref Google Scholar
[60]

Anantharaj, S.; Noda, S.; Jothi, V. R.; Yi, S.;Driess, M.; Menezes, P. W. Strategies and perspectives to catch the missing pieces in energy-efficient hydrogen evolution reaction in alkaline media. Angew. Chem., Int. Ed. 2021, 60, 18981–19006.
Crossref Google Scholar
Nano Research
Volume 16 Issue 7,
July 2023
Pages 9073-9080
DOI: 10.1007/s12274-023-5711-1
Cite this article:
Huang X, Lu R, Cen Y, et al. Micropore-confined Ru nanoclusters catalyst for efficient pH-universal hydrogen evolution reaction. Nano Research, 2023, 16(7): 9073-9080. https://doi.org/10.1007/s12274-023-5711-1
Topics:
Hydrogen evolution reaction Nanoclusters

1239

Views

28

Crossref

30

Web of Science

29

Scopus

0

CSCD

Altmetrics
Received: 20 February 2023
Revised: 03 April 2023
Accepted: 07 April 2023
Published: 25 May 2023
© Tsinghua University Press 2023
Return