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CVD-grown three-dimensional sulfur-doped graphene as a binder-free electrocatalytic electrode for highly effective and stable hydrogen evolution reaction

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Abstract

Three-dimensional sulfur-doped graphene (3DSG) with high sulfur-doping content (2.9%) was synthesized on nickel foam by chemical vapor deposition using solid organic source of thianthrene as both the carbon source and sulfur dopant. The 3DSG further treated by Ar plasma (3DSG-Ar) was demonstrated as a free-standing and binder-free electrocatalyst without any polymeric binders for electrode fabrication. Particularly, 3DSG-Ar can be used as highly effective and stable electrocatalyst for hydrogen evolution reaction (HER). It delivers a very low Tafel slope of 64 mV dec−1, which is superior or comparable to most metal-free carbon-based electrocatalysts ever reported; moreover, it shows superior long-term electrocatalytic stability even after 2000 cycles. The excellent HER performances of 3DSG-Ar can be attributed to its well-designed porous, conductive and flexible 3D sulfur-doped graphene structure. Sulfur doping combing with plasma treatment cause a synergistic effect to effectively provide many more electrocatalytic active sites, resulting in significantly improved HER performance. In addition, the conductive, porous and flexible 3D graphene skeleton can not only act as free-standing and binder-free electrocatalytic electrode, but also guarantee the interconnected conductive paths in the whole electrode, leading to facilitate the charge transportation between the electrocatalyst and electrolyte and thus enhance its HER performances.

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References

  1. Fei H, Dong J, Arellano-Jimenez MJ, Ye G, Kim ND, Samuel ELG, Peng Z, Zhu Z, Qin F, Bao J, Yacaman MJ, Ajayan PM, Chen D, Tour JM (2015) Atomic cobalt on nitrogen-doped graphene for hydrogen generation. Nat Commun 6:9668–9676

    Google Scholar 

  2. Liu X, Dai L (2016) Carbon-based metal-free catalysts. Nat Rev Mater 1:16064–16076

    Article  Google Scholar 

  3. Gong M, Wang D, Chen C, Hwang B, Dai H (2016) A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction. Nano Res 9:28–46

    Article  Google Scholar 

  4. Shi Y, Zhang B (2016) Recent advances in transition metal phosphide nanomaterials: synthesis and applications in hydrogen evolution reaction. Chem Soc Rev 45:1529–1541

    Article  Google Scholar 

  5. Jamesh MI (2016) Recent progress on earth abundant hydrogen evolution reaction and oxygen evolution reaction bifunctional electrocatalyst for overall water splitting in alkaline media. J Power Sources 333:213–236

    Article  Google Scholar 

  6. Safizadeh F, Ghali E, Houlachi G (2015) Electrocatalysis developments for hydrogen evolution reaction in alkaline solutions—a review. Int J Hydrogen Energy 40:256–274

    Article  Google Scholar 

  7. Zeng M, Li Y (2015) Recent advances in heterogeneous electrocatalysts for the hydrogen evolution reaction. J Mater Chem A 3:14942–14962

    Article  Google Scholar 

  8. Yan Y, Xia B, Xu Z, Wang X (2014) Recent development of molybdenum sulfides as advanced electrocatalysts for hydrogen evolution reaction. Acs Catal 4:1693–1705

    Article  Google Scholar 

  9. Wang X, Chen Y, Zheng B, Qi F, He J, Li Q, Li P, Zhang W (2017) Graphene-like WSe2 nanosheets for efficient and stable hydrogen evolution. J Alloys Compd 691:698–704

    Article  Google Scholar 

  10. Qi F, Wang X, Zheng B, Chen Y, Yu B, Zhou J, He J, Li P, Zhang W, Li Y (2017) Self-assembled chrysanthemum-like microspheres constructed by few-layer ReSe2 nanosheets as a highly efficient and stable electrocatalyst for hydrogen evolution reaction. Electrochim Acta 224:593–599

    Article  Google Scholar 

  11. Yu B, Wang X, Qi F, Zheng B, He J, Lin J, Zhang W, Li Y, Chen Y (2017) Self-assembled coral-like hierarchical architecture constructed by NiSe2 nanocrystals with comparable hydrogen-evolution performance of precious platinum catalyst. ACS Appl Mater Interfaces 9:7154–7159

    Article  Google Scholar 

  12. Wang X, Chen Y, Qi F, Zheng B, He J, Li Q, Li P, Zhang W, Li Y (2016) InterwovenWSe2/CNTs hybrid network: a highly efficient and stable electrocatalyst for hydrogen evolution. Electrochem Commun 72:74–78

    Article  Google Scholar 

  13. Wang X, Chen Y, Zheng B, Qi F, He J, Li P, Zhang W (2016) Few-layered WSe2 nanoflowers anchored on graphene nanosheets: a highly efficient and stable electrocatalyst for hydrogen evolution. Electrochim Acta 222:1293–1299

    Article  Google Scholar 

  14. Qi F, Li P, Chen Y, Zheng B, Liu J, Zhou J, He J, Hao X, Zhang W (2017) Three-dimensional structure of WS2/graphene/Ni as a binder-free electrocatalytic electrode for highly effective and stable hydrogen evolution reaction. Int J Hydrogen Energy 42:7811–7819

    Article  Google Scholar 

  15. Hu C, Dai L (2016) Carbon-based metal-free catalysts for electrocatalysis beyond the ORR. Angew Chem Int Ed 55:11736–11758

    Article  Google Scholar 

  16. Zhou W, Jia J, Lu J, Yang L, Hou D, Li G, Chen S (2016) Recent developments of carbon-based electrocatalysts for hydrogen evolution reaction. Nano Energy 28:29–43

    Article  Google Scholar 

  17. Duan J, Chen S, Jaroniec M, Qiao SZ (2015) Heteroatom-doped graphene-based materials for energy-relevant electrocatalytic processes. Acs Catal 5:5207–5234

    Article  Google Scholar 

  18. Wang Z, Chen Y, Li P, He J, Zhang W, Guo Z, Li Y, Dong M (2016) Synthesis of silicon-doped reduced graphene oxide and its applications in dye-sensitive solar cells and supercapacitors. Rsc Adv 6:15080–15086

    Article  Google Scholar 

  19. Wang Z, Chen Y, Li P, Zhou J, He J, Zhang W, Guo Z, Li Y, Dong M (2016) Modulation of N-bonding configurations and their influence on the electrical properties of nitrogen-doped graphene. Rsc Adv 6:92682–92687

    Article  Google Scholar 

  20. Wang Z, Li P, Chen Y, He J, Liu J, Zhang W, Li Y (2014) Phosphorus-doped reduced graphene oxide as an electrocatalyst counter electrode in dye-sensitized solar cells. J Power Sources 263:246–251

    Article  Google Scholar 

  21. Wang Z, Li P, Chen Y, He J, Zhang W, Schmidt OG, Li Y (2014) Pure thiophene–sulfur doped reduced graphene oxide: synthesis, structure, and electrical properties. Nanoscale 6:7281–7287

    Article  Google Scholar 

  22. Wang Z, Li P, Chen Y, Liu J, Tian H, Zhou J, Zhang W, Li Y (2014) Synthesis of nitrogen-doped graphene by chemical vapour deposition using melamine as the sole solid source of carbon and nitrogen. J Mater Chem C 2:7396–7401

    Article  Google Scholar 

  23. Wang Z, Li P, Chen Y, Liu J, Zhang W, Guo Z, Dong M, Li Y (2015) Synthesis, characterization and electrical properties of silicon-doped graphene films. J Mater Chem C 3:6301–6306

    Article  Google Scholar 

  24. Zheng B, Chen Y, Li P, Wang Z, Cao B, Qi F, Liu J, Qiu Z, Zhang W (2017) Ultrafast ammonia-driven, microwave-assisted synthesis of nitrogen-doped graphene quantum dots and their optical properties. Nanophotonics 6:259–267

    Google Scholar 

  25. Zhou J, Wang Z, Chen Y, Liu J, Zheng B, Zhang W, Li Y (2017) Growth and properties of large-area sulfur-doped graphene films. J Mater Chem C 5:7944–7949

    Article  Google Scholar 

  26. Sathe BR, Zou X, Asefa T (2014) Metal-free B-doped graphene with efficient electrocatalytic activity for hydrogen evolution reaction. Catal Sci Technol 4:2023–2030

    Article  Google Scholar 

  27. Huang X, Zhao Y, Ao Z, Wang G (2014) Micelle-template synthesis of nitrogen-doped mesoporous graphene as an efficient metal-free electrocatalyst for hydrogen production. Sci Rep 4:7557–7563

    Article  Google Scholar 

  28. Jiang H, Zhu Y, Su Y, Yao Y, Liu Y, Yang X, Li C (2015) Highly dual-doped multilayer nanoporous graphene: efficient metal-free electrocatalysts for the hydrogen evolution reaction. J Mater Chem A 3:12642–12645

    Article  Google Scholar 

  29. Zheng Y, Jiao Y, Li LH, Xing T, Chen Y, Jaroniec M, Qiao SZ (2014) Toward design of synergistically active carbon-based catalysts for electrocatalytic hydrogen evolution. ACS Nano 8:5290–5296

    Article  Google Scholar 

  30. Shervedani RK, Amini A (2015) Sulfur-doped graphene as a catalyst support: influences of carbon black and ruthenium nanoparticles on the hydrogen evolution reaction performance. Carbon 93:762–773

    Article  Google Scholar 

  31. Hou D, Zhou W, Zhou K, Zhou Y, Zhong J, Yang L, Lu J, Li G, Chen S (2015) Flexible and porous catalyst electrodes constructed by co nanoparticles@nitrogen-doped graphene films for highly efficient hydrogen evolution. J Mater Chem A 3:15962–15968

    Article  Google Scholar 

  32. Hou D, Zhou W, Liu X, Zhou K, Xie J, Li G, Chen S (2015) Pt nanoparticles/MoS2 nanosheets/carbon fibers as efficient catalyst for the hydrogen evolution reaction. Electrochim Acta 166:26–31

    Article  Google Scholar 

  33. Tian Y, Wei Z, Wang X, Peng S, Zhang X, Liu WM (2016) Plasma-etched, S-doped graphene for effective hydrogen evolution reaction. Int J Hydrogen Energy 7:4184–4192

    Google Scholar 

  34. He J, Chen Y, Lv W, Wen K, Li P, Qi F, Wang Z, Zhang W, Li Y, Qin W, He W (2016) Highly-flexible 3D Li2S/graphene cathode for high-performance lithium sulfur batteries. J Power Sources 327:474–480

    Article  Google Scholar 

  35. Zhou J, Yue H, Qi F, Wang H, Chen Y (2017) Significantly enhanced electrocatalytic properties of three-dimensional graphene foam via Ar plasma pretreatment and N, S co-doping. Int J Hydrogen Energ 42:27004–27012

    Article  Google Scholar 

  36. Zhou H, Yu F, Huang Y, Sun J, Zhu Z, Nielsen RJ, He R, Bao J, Goddard WA III, Chen S, Ren Z (2016) Efficient hydrogen evolution by ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. Nat Commun 7:12765–12772

    Article  Google Scholar 

  37. Lu Q, Hutchings GS, Yu W, Zhou Y, Forest RV, Tao R, Rosen J, Yonemoto BT, Cao Z, Zheng H, Xiao JQ, Jiao F, Chen JG (2015) Highly porous non-precious bimetallic electrocatalysts for efficient hydrogen evolution. Nat Commun 6:6567–6575

    Article  Google Scholar 

  38. Qiu HJ, Ito Y, Cong W, Tan Y, Liu P, Hirata A, Fujita T, Tang Z, Chen M (2015) Nanoporous graphene with single-atom nickel dopants: an efficient and stable catalyst for electrochemical hydrogen production. Angew Chem Int Edit 54:14031–14035

    Article  Google Scholar 

  39. Hassani F, Tavakol H, Keshavarzipour F, Javaheri A (2016) A simple synthesis of sulfur-doped graphene using sulfur powder by chemical vapor deposition. RSC Adv 6:27158–27163

    Article  Google Scholar 

  40. Ferrari AC, Basko DM (2013) Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat Nanotechnol 8:235–247

    Article  Google Scholar 

  41. Wei D, Liu Y, Wang Y, Zhang H, Huang L, Yu G (2009) Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett 9:1752–1758

    Article  Google Scholar 

  42. Soin N, Sinha Roy S, Roy S, Hazra KS, Misra DS, Lim TH, Hetherington CJ, McLaughlin JA (2011) Enhanced and stable field emission from in situ nitrogen-doped few-layered graphene nanoflakes. J Phys Chem C 115:5366–5372

    Article  Google Scholar 

  43. Wang Z, Cao X, Ping J, Wang Y, Lin T, Huang X, Ma Q, Wang F, He C, Zhang H (2015) Electrochemical doping of three-dimensional graphene networks used as efficient electrocatalysts for oxygen reduction reaction. Nanoscale 7:9394–9398

    Article  Google Scholar 

  44. Wang G, Zhang M, Zhu Y, Ding G, Jiang D, Guo Q, Liu S, Xie X, Chu PK, Di Z, Wang X (2013) Direct growth of graphene film on germanium substrate. Sci Rep 3:2465–2471

    Article  Google Scholar 

  45. Tian Y, Mei R, Xue D, Zhang X, Peng W (2016) Enhanced electrocatalytic hydrogen evolution in graphene via defect engineering and heteroatoms co-doping. Electrochim Acta 219:781–789

    Article  Google Scholar 

  46. Liu X, Zhou W, Yang L, Li L, Zhang Z, Ke Y, Chen S (2015) Nitrogen and sulfur co-doped porous carbon derived from human hair as highly efficient metal-free electrocatalysts for hydrogen evolution reactions. J Mater Chem A 3:10135–10135

    Article  Google Scholar 

  47. Yu X, Zhang M, Chen J, Li Y, Shi G (2016) Nitrogen and sulfur co-doped graphite foam as a self-supported metal-free electrocatalytic electrode for water oxidation. Adv Energy Mater 6:1501492–1501501

    Article  Google Scholar 

  48. Jeon I, Zhang S, Zhang L, Choi H, Seo J, Xia Z, Dai L, Baek J (2013) Edge-selectively sulfurized graphene nanoplatelets as efficient metal-free electrocatalysts for oxygen reduction reaction: the electron spin effect. Adv Mater 25:6138–6145

    Article  Google Scholar 

  49. Islam MM, Subramaniyam CM, Akhter T, Faisal SN, Minett AI, Liu HK, Konstantinov K, Dou SX (2017) Three dimensional cellular architecture of sulfur doped graphene: self-standing electrode for flexible supercapacitors, lithium ion and sodium ion batteries. J Mater Chem A 5:5290–5302

    Article  Google Scholar 

  50. Lu Y, Chen J, Wang A, Bao N, Feng J, Wang W, Shao L (2015) Facile synthesis of oxygen and sulfur co-doped graphitic carbon nitride fluorescent quantum dots and their application for mercury(II) detection and bioimaging. J Mater Chem C 3:73–78

    Article  Google Scholar 

  51. Ge J, Zhang B, Lv L, Wang H, Ye T, Wei X, Su J, Wang K, Li X, Chen J (2015) Constructing holey graphene monoliths via supramolecular assembly: enriching nitrogen heteroatoms up to the theoretical limit for hydrogen evolution reaction. Nano Energy 15:567–575

    Article  Google Scholar 

  52. Zhang J, Qu L, Shi G, Liu J, Chen J, Dai L (2016) N, P-codoped carbon networks as efficient metal-free bifunctional catalysts for oxygen reduction and hydrogen evolution reactions. Angew Chem Int Ed 55:2230–2234

    Article  Google Scholar 

  53. Zhou Y, Leng Y, Zhou W, Huang J, Zhao M, Zhan J, Feng C, Tang Z, Chen S, Liu H (2015) Sulfur and nitrogen self-doped carbon nanosheets derived from peanut root nodules as high-efficiency non-metal electrocatalyst for hydrogen evolution reaction. Nano Energy 16:357–366

    Article  Google Scholar 

  54. Wei L, Karahan HE, Goh K, Jiang W, Yu D, Birer Ö, Jiang R, Chen Y (2015) A high-performance metal-free hydrogen-evolution reaction electrocatalyst from bacterium derived carbon. J Mater Chem A 3:7210–7214

    Article  Google Scholar 

  55. Ito Y, Cong W, Fujita T, Tang Z, Chen M (2015) High catalytic activity of nitrogen and sulfur co-doped nanoporous graphene in the hydrogen evolution reaction. Angew Chem Int Ed 54:2131–2136

    Article  Google Scholar 

  56. Wang Z, Zuo P, Fan L, Han J, Xiong Y, Yin G (2016) Facile electrospinning preparation of phosphorus and nitrogen dual-doped cobalt-based carbon nanofibers as bifunctional electrocatalyst. J Power Sources 311:68–80

    Article  Google Scholar 

  57. Zhang H, Ma Z, Duan J, Liu H, Liu G, Wang T, Chang K, Li M, Shi L, Meng X (2016) Active sites implanted carbon cages in core-shell architecture: highly active and durable electrocatalyst for hydrogen evolution reaction. ACS Nano 10:684–694

    Article  Google Scholar 

  58. Yang Y, Lun Z, Xia G, Zheng F, He M, Chen Q (2015) Non-precious alloy encapsulated in nitrogen-doped graphene layers derived from MOFs as an active and durable hydrogen evolution reaction catalyst. Energy Environ Sci 8:3563–3571

    Article  Google Scholar 

  59. Zhuang M, Ou X, Dou Y, Zhang L, Zhang Q, Wu R, Ding Y, Shao M, Luo Z (2016) Polymer-embedded fabrication of Co2P nanoparticles encapsulated in N, P-doped graphene for hydrogen generation. Nano Lett 16:4691–4698

    Article  Google Scholar 

  60. Youn DH, Han S, Kim JY, Kim JY, Park H, Sun HC, Lee JS (2014) Highly active and stable hydrogen evolution electrocatalysts based on molybdenum compounds on carbon nanotube-graphene hybrid support. ACS Nano 8:5164–5173

    Article  Google Scholar 

  61. Duan J, Chen S, Chambers BA, Andersson GG, Qiao SZ (2015) 3D WS2 nanolayers@heteroatom-doped graphene films as hydrogen evolution catalyst electrodes. Adv Mater 27:4234–4241

    Article  Google Scholar 

  62. Chen S, Duan J, Tang Y, Jin B, Zhang Qiao S (2015) Molybdenum sulfide clusters-nitrogen-doped graphene hybrid hydrogel film as an efficient three-dimensional hydrogen evolution electrocatalyst. Nano Energy 11:11–18

    Article  Google Scholar 

  63. Cruz-Silva E, López-Urías F, Munoz-Sandoval E, Sumpter BG, Terrones H, Charlier J, Meunier V, Terrones M (2009) Electronic transport and mechanical properties of phosphorus-and phosphorus-nitrogen-doped carbon nanotubes. ACS Nano 3:1913–1921

    Article  Google Scholar 

  64. Zhao L, He R, Rim KT, Schiros T, Kim KS, Zhou H, Gutiérrez C, Chockalingam SP, Arguello CJ, Pálová L (2011) Visualizing individual nitrogen dopants in monolayer graphene. Science 333:999–1003

    Article  Google Scholar 

  65. Kong X, Chen C, Chen Q (2014) Doped graphene for metal-free catalysis. Chem Soc Rev 43:2841–2857

    Article  Google Scholar 

  66. Carr LD, Lusk MT (2010) Defect engineering: graphene gets designer defects. Nat Nanotechnol 5:316–317

    Article  Google Scholar 

  67. Tang C, Wang HF, Chen X, Li BQ, Hou TZ, Zhang B, Zhang Q, Titirici MM, Wei F (2016) Oxygen electrocatalysis: topological defects in metal-free nanocarbon for oxygen electrocatalysis (Adv. Mater. 32/2016). Adv Mater 28:7030

    Article  Google Scholar 

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Acknowledgments

The research was supported by the National Natural Science Foundation of China (Grant Nos. 21773024, 51372033) and National High Technology Research and Development Program of China (Grant No. 2015AA034202).

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Authors and Affiliations

  1. State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu, 610054, People’s Republic of China

    Jinhao Zhou, Fei Qi, Yuanfu Chen, Binjie Zheng & Xinqiang Wang

  2. Interdisciplinary Nanoscience Center (iNANO), Aarhus University, 8000, Aarhus C, Denmark

    Zegao Wang

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  1. Jinhao Zhou
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  2. Fei Qi
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  3. Yuanfu Chen
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  4. Zegao Wang
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  5. Binjie Zheng
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Correspondence to Yuanfu Chen or Zegao Wang.

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Zhou, J., Qi, F., Chen, Y. et al. CVD-grown three-dimensional sulfur-doped graphene as a binder-free electrocatalytic electrode for highly effective and stable hydrogen evolution reaction. J Mater Sci 53, 7767–7777 (2018). https://doi.org/10.1007/s10853-018-2118-6

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