Skip to main content

Advertisement

SpringerLink
Log in

As a highly efficient reduced graphene oxide-supported ternary catalysts for the fast hydrogen release from NaBH4

  • Original Article
  • Published:
Graphene Technology Aims and scope Submit manuscript

Abstract

In this study, reduced graphene oxide (rGO)-based Co–Cu–B nanocatalysts were produced to catalytic efficiency of hydrogen (H2) generation from sodium borohydride (NaBH4) hydrolysis reaction. The characterization was achieved by X-ray diffraction, field emission scanning electron microscope (S-4800) and energy-dispersive X-ray spectroscopy, inductively coupled plasma-optical emission spectroscopy. Co–Cu–B(5%(wt))/rGO trimetallic nanoparticles provide an initial H2 production rate of 13,000 mL g−1 min−1 (3%(wt) NaBH4), turnover frequency 4013 h−1 and activation energy (Ea) 36.76 kJ mol−1 at room temperature that shows higher catalytic activity than most of the recently reported noble metal based on a heterogeneous catalyst that is used in the reaction of hydrolytic dehydrogenation of NaBH4. The excellent hydrolysis performance of Co–Cu–B(5%(wt))/rGO can be attributed to both synergistic effect and high surface area of rGO. The improvement of effective and inexpensive Co–Cu–B(5%(wt))/rGO catalysts enhances the applicability of NaBH4 as chemical H2 safekeeping equipment that can be used in the H2 fuel cell industry.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Manoharan Y, Hosseini SE, Butler B, Alzhahrani H, Fou BT, Ashuri T, Krohn J (2019) Hydrogen fuel cell vehicles; current status and future prospect. Appl Sci Basel 9(11):2296

    CAS  Google Scholar 

  2. Granovskii M, Dincer I, Rosen MA (2007) Greenhouse gas emissions reduction by use of wind and solar energies for hydrogen and electricity production: economic factors. Int J Hydrogen Energy 32(8):927–931

    CAS  Google Scholar 

  3. Cakanyildirim C, Guru M (2010) Supported CoCl2 catalyst for NaBH4 dehydrogenation. Renew Energy 35(4):839–844

    CAS  Google Scholar 

  4. Sahin O, Kilinc D, Saka C (2016) Bimetallic Co–Ni based complex catalyst for hydrogen production by catalytic hydrolysis of sodium borohydride with an alternative approach. J Energy Inst 89(4):617–626

    CAS  Google Scholar 

  5. Kojima Y, Suzuki K, Fukumoto K, Sasaki M, Yamamoto T, Kawai Y, Hayashi H (2002) Hydrogen generation using sodium borohydride solution and metal catalyst coated on metal oxide. Int J Hydrogen Energy 27(10):1029–1034

    CAS  Google Scholar 

  6. Sun HM, Meng J, Jiao LF, Cheng FY, Chen J (2018) A review of transition-metal boride/phosphide-based materials for catalytic hydrogen generation from hydrolysis of boron-hydrides. Inorg Chem Front 5(4):760–772

    CAS  Google Scholar 

  7. Sahin O, Izgi MS, Onat E, Saka C (2016) Influence of the using of methanol instead of water in the preparation of Co–B–TiO2 catalyst for hydrogen production by NaBH4 hydrolysis and plasma treatment effect on the Co–B–TiO2 catalyst. Int J Hydrogen Energy 41(4):2539–2546

    CAS  Google Scholar 

  8. Jiang HL, Umegaki T, Akita T, Zhang XB, Haruta M, Xu Q (2010) Bimetallic Au–Ni nanoparticles embedded in SiO2 nanospheres: synergetic catalysis in hydrolytic dehydrogenation of ammonia borane. Chem Eur J 16(10):3132–3137

    CAS  Google Scholar 

  9. Xu DY, Dai P, Liu XM, Cao CQ, Guo QJ (2008) Carbon-supported cobalt catalyst for hydrogen generation from alkaline sodium borohydride solution. J Power Sources 182(2):616–620

    CAS  Google Scholar 

  10. Huang YQ, Wang Y, Zhao RX, Shen PK, Wei ZD (2008) Accurately measuring the hydrogen generation rate for hydrolysis of sodium borohydride on multiwalled carbon nanotubes/Co–B catalysts. Int J Hydrogen Energy 33(23):7110–7115

    CAS  Google Scholar 

  11. Ingersoll JC, Mani N, Thenmozhiyal JC, Muthaiah A (2007) Catalytic hydrolysis of sodium borohydride by a novel nickel–cobalt–boride catalyst. J Power Sources 173(1):450–457

    CAS  Google Scholar 

  12. Li F, Li Q, Kim H (2012) CoB/open-CNTs catalysts for hydrogen generation from alkaline NaBH4 solution. Chem Eng J 210:316–324

    CAS  Google Scholar 

  13. Krishnan P, Advani SG, Prasad AK (2008) Cobalt oxides as Co2B catalyst precursors for the hydrolysis of sodium borohydride solutions to generate hydrogen for PEM fuel cells. Int J Hydrogen Energy 33(23):7095–7102

    CAS  Google Scholar 

  14. Demirci UB, Miele P (2014) Cobalt-based catalysts for the hydrolysis of NaBH4 and NH3BH3. Phys Chem Chem Phys 16(15):6872–6885

    CAS  Google Scholar 

  15. Bandal HA, Jadhav AR, Kim H (2017) Cobalt impregnated magnetite-multiwalled carbon nanotube nanocomposite as magnetically separable efficient catalyst for hydrogen generation by NaBH4 hydrolysis. J Alloy Compd 699:1057–1067

    CAS  Google Scholar 

  16. Liang ZH, Li QN, Li F, Zhao SD, Xia X (2017) Hydrogen generation from hydrolysis of NaBH4 based on high stable NiB/NiFe2O4 catalyst. Int J Hydrogen Energy 42(7):3971–3980

    CAS  Google Scholar 

  17. Cakanyildirim C, Guru M (2017) Decomposition of NaBH4 with self-regeneration of carbon-supported CoCl2 catalyst. Int J Green Energy 14(12):1005–1010

    CAS  Google Scholar 

  18. İzgi MS, Şahin Ö, Saka C (2016) Hydrogen production from NaBH4 using Co–Cu–B catalysts prepared in methanol: effect of plasma treatment. Int J Hydrogen Energy 41(3):1600–1608

    Google Scholar 

  19. Kazici HC, Salman F, Caglar A, Kivrak H, Aktas N (2018) Synthesis, characterization, and voltammetric hydrogen peroxide sensing on novel monometallic (Ag, Co/MWCNT) and bimetallic (AgCo/MWCNT) alloy nanoparticles. Fuller Nanotubes Carbon Nanostruct 26(3):145–151

    CAS  Google Scholar 

  20. Kazici HC, Salman F, Izgi MS, Sahin O (2020) Synthesis of metal-oxide-supported triple nano catalysts and application to H-2 production and H2O2 oxidation. J Electron Mater 49(6):3634–3644

    Google Scholar 

  21. Wang XP, Liao JY, Li H, Wang H, Wang RF, Pollet BG, Ji S (2018) Highly active porous Co–B nanoalloy synthesized on liquid-gas interface for hydrolysis of sodium borohydride. Int J Hydrogen Energy 43(37):17543–17555

    CAS  Google Scholar 

  22. Netskina OV, Kochubey DI, Prosvirin IP, Malykhin SE, Komova OV, Kanazhevskiy VV, Chukalkin YG, Bobrovskii VI, Kellerman DG, Ishchenko AV, Simagina VI (2017) Cobalt–boron catalyst for NaBH4 hydrolysis: the state of the active component forming from cobalt chloride in a reaction medium. Mol Catal 441:100–108

    CAS  Google Scholar 

  23. İzgi MS (2016) Effect of microwave irritated Co–B–Cr catalyst on the hydrolysis of sodium borohydride. Energy Sour Part A Recovery Util Environ Effects 38(17):2590–2597

    Google Scholar 

  24. Guo J, Hou YJ, Li B, Liu YL (2018) Novel Ni–Co–B hollow nanospheres promote hydrogen generation from the hydrolysis of sodium borohydride. Int J Hydrogen Energy 43(32):15245–15254

    CAS  Google Scholar 

  25. Wang WL, Zhao YC, Chen DH, Wang X, Peng XL, Tian JN (2014) Promoted Mo incorporated Co–Ru–B catalyst for fast hydrolysis of NaBH4 in alkaline solutions. Int J Hydrogen Energy 39(28):16202–16211

    CAS  Google Scholar 

  26. Aydin M, Hasimoglu A, Ozdemir OK (2016) Kinetic properties of cobalt–titanium–boride (Co–Ti–B) catalysts for sodium borohydride hydrolysis reaction. Int J Hydrogen Energy 41(1):239–248

    CAS  Google Scholar 

  27. Kazici HC, Salman F, Kivrak HD (2017) Synthesis of Pd–Ni/C bimetallic materials and their application in non-enzymatic hydrogen peroxide detection. Mater Sci Pol 35(3):660–666

    CAS  Google Scholar 

  28. Kazici HC, Yilmaz S, Sahan T, Yildiz F, Er OF, Kivrak H (2020) A comprehensive study of hydrogen production from ammonia borane via PdCoAg/AC nanoparticles and anodic current in alkaline medium: experimental design with response surface methodology. Front Energy

  29. Kazici HC, Yayla M, Ulas B, Aktas N, Kivrak H (2019) Development of nonenzymatic benzoic acid detection on PdSn/GCE/Vulcan XC-72R prepared via polyol method. Electroanalysis 31(6):1118–1124

    CAS  Google Scholar 

  30. Kazici HC, Yayla M (2019) An electrocatalyst for detection of glucose in human blood: synergy in Pd–AuNPs/GOx/C surfaces. Chem Eng Commun 206(12):1731–1742

    Google Scholar 

  31. Izgi MS, Onat E, Kazici HC, Sahin O (2020) Hydrogen production through the cooperation of a catalyst synthesized in ethanol medium and the effect of the plasma. Energy Sources Part A Recovery Util Environ Effects

  32. Kazici HC, Caglar A, Aydogmus T, Aktas N, Kivrak H (2018) Microstructured prealloyed titanium–nickel powder as a novel nonenzymatic hydrogen peroxide sensor. J Colloid Interface Sci 530:353–360

    Google Scholar 

  33. Duzenli D, Sahin O, Kazici HC, Aktas N, Kivrak H (2018) Synthesis and characterization of novel Ti doped hexagonal mesoporous silica catalyst for nonenzymatic hydrogen peroxide oxidation. Microporous Mesoporous Mater 257:92–98

    CAS  Google Scholar 

  34. Mao S, Wen ZH, Huang TZ, Hou Y, Chen JH (2014) High-performance bi-functional electrocatalysts of 3D crumpled graphene-cobalt oxide nanohybrids for oxygen reduction and evolution reactions. Energy Environ Sci 7(2):609–616

    CAS  Google Scholar 

  35. Yang CL, Men YN, Xu YZ, Liang LJ, Cai P, Luo W (2019) In situ synthesis of NiCoP nanoparticles supported on reduced graphene oxide for the catalytic hydrolysis of ammonia borane. ChemPlusChem 84(4):382–386

    CAS  Google Scholar 

  36. Zhou YH, Zhang ZY, Wang SQ, Williams N, Cheng Y, Luo SZ, Gu J (2018) rGO supported PdNi–CeO2 nanocomposite as an efficient catalyst for hydrogen evolution from the hydrolysis of NH3BH3. Int J Hydrogen Energy 43(41):18745–18753

    CAS  Google Scholar 

  37. Baytar O, Izgi MS, Horoz S, Sahin O, Nar S (2019) Al2O3 Supported Co–Cu–B (Co–Cu–B/Al2O3) catalyst for hydrogen generation by hydrolysis of aqueous sodium borohydride (NaBH4) solutions. Dig J Nanomater Biostruct 14(3):673–681

    Google Scholar 

  38. Kazici HC, Yildiz F, Izgi MS, Ulas B, Kivrak H (2019) Novel activated carbon supported trimetallic PdCoAg nanoparticles as efficient catalysts for the hydrolytic dehydrogenation of ammonia borane. Int J Hydrogen Energy 44(21):10561–10572

    Google Scholar 

  39. Moon IK, Lee J, Ruoff RS, Lee H (2010) Reduced graphene oxide by chemical graphitization. Nat Commun 1:73

    Google Scholar 

  40. Ding X-L, Yuan X, Jia C, Ma Z-F (2010) Hydrogen generation from catalytic hydrolysis of sodium borohydride solution using cobalt–copper–boride (Co–Cu–B) catalysts. Int J Hydrogen Energy 35(20):11077–11084

    CAS  Google Scholar 

  41. Chou CC, Hsieh CH, Chen BH (2015) Hydrogen generation from catalytic hydrolysis of sodium borohydride using bimetallic Ni–Co nanoparticles on reduced graphene oxide as catalysts. Energy 90:1973–1982

    CAS  Google Scholar 

  42. Zhang H, Xu CJ, Ding JF, Su HQ, Zeng SH (2017) RGO/MWCNTs/CuxO–CeO2 ternary nanocomposites for preferential CO oxidation in hydrogen-rich streams. Appl Surf Sci 426:50–55

    CAS  Google Scholar 

  43. Du C, Su J, Luo W, Cheng GZ (2014) Graphene supported Ag@Co core-shell nanoparticles as efficient catalysts for hydrolytic dehydrogenation of amine boranes. J Mol Catal Chem 383:38–45

    Google Scholar 

  44. Mohan S, Kumar V, Singh DK, Hasan SH (2016) Synthesis and characterization of rGO/ZrO2 nanocomposite for enhanced removal of fluoride from water: kinetics, isotherm, and thermodynamic modeling and its adsorption mechanism. RSC Adv 6(90):87523–87538

    CAS  Google Scholar 

  45. Metin O, Ozkar S (2009) Hydrogen generation from the hydrolysis of ammonia-borane and sodium borohydride using water-soluble polymer-stabilized cobalt(0) nanoclusters catalyst. Energy Fuels 23(7):3517–3526

    CAS  Google Scholar 

  46. Yao QL, Yang K, Hong XL, Chen XS, Lu ZH (2018) Base-promoted hydrolytic dehydrogenation of ammonia borane catalyzed by noble-metal-free nanoparticles. Catal Sci Technol 8(3):870–877

    CAS  Google Scholar 

  47. Fu ZC, Xu Y, Chan SLF, Wang WW, Li F, Liang F, Chen Y, Lin ZS, Fu WF, Che CM (2017) Highly efficient hydrolysis of ammonia borane by anion (−OH, F–, Cl–)-tuned interactions between reactant molecules and CoP nanoparticles. Chem Commun 53(4):705–708

    CAS  Google Scholar 

  48. Shi LM, Xie W, Jian ZY, Liao XM, Wang YJ (2019) Graphene modified Co–B catalysts for rapid hydrogen production from NaBH4 hydrolysis. Int J Hydrogen Energy 44(33):17954–17962

    CAS  Google Scholar 

  49. Jeong SU, Kim RK, Cho EA, Kim HJ, Nam SW, Oh IH, Hong SA, Kim SH (2005) A study on hydrogen generation from NaBH4 solution using the high-performance Co–B catalyst. J Power Sources 144(1):129–134

    CAS  Google Scholar 

  50. Zhao JZ, Ma H, Chen J (2007) Improved hydrogen generation from alkaline NaBH4 solution using carbon-supported Co–B as catalysts. Int J Hydrogen Energy 32(18):4711–4716

    CAS  Google Scholar 

  51. Liang JY, Li YL, Huang YQ, Yang JY, Tang HL, Wei ZD, Shen PK (2008) Sodium borohydride hydrolysis on highly efficient Co–B/Pd catalysts. Int J Hydrogen Energy 33(15):4048–4054

    CAS  Google Scholar 

  52. Shen XC, Wang Q, Wu QQ, Guo SQ, Zhang ZY, Sun ZY, Liu BS, Wang ZB, Zhao B, Ding WP (2015) CoB supported on Ag-activated TiO2 as a highly active catalyst for hydrolysis of alkaline NaBH4 solution. Energy 90:464–474

    CAS  Google Scholar 

  53. Wei YS, Wang R, Meng LY, Wang Y, Li GD, Xin SG, Zhao XS, Zhang K (2017) Hydrogen generation from alkaline NaBH4 solution using a dandelion-like Co–Mo–B catalyst supported on carbon cloth. Int J Hydrogen Energy 42(15):9945–9951

    CAS  Google Scholar 

  54. Ding XL, Yuan XX, Jia C, Ma ZF (2010) Hydrogen generation from catalytic hydrolysis of sodium borohydride solution using cobalt–copper–boride (Co–Cu–B) catalysts. Int J Hydrogen Energy 35(20):11077–11084

    CAS  Google Scholar 

  55. Zhao YC, Ning Z, Tian JN, Wang HW, Liang XY, Nie SL, Yu Y, Li XX (2012) Hydrogen generation by hydrolysis of alkaline NaBH4 solution on Co–Mo–Pd–B amorphous catalyst with efficient catalytic properties. J Power Sources 207:120–126

    CAS  Google Scholar 

  56. Fernandes R, Patel N, Miotello A (2009) Efficient catalytic properties of Co–Ni–P–B catalyst powders for hydrogen generation by hydrolysis of alkaline solution of NaBH4. Int J Hydrogen Energy 34(7):2893–2900

    CAS  Google Scholar 

  57. Guo YP, Dong ZP, Cui ZK, Zhang XJ, Ma JT (2012) Promoting effect of W doped in electrodeposited Co–P catalysts for hydrogen generation from alkaline NaBH4 solution. Int J Hydrogen Energy 37(2):1577–1583

    CAS  Google Scholar 

  58. Wang L, Li Z, Zhang Y, Zhang T, Xie GW (2017) Hydrogen generation from alkaline NaBH4 solution using electroless-deposited Co–Ni–W–P/gamma-Al2O3 as catalysts. J Alloys Compd 702:649–658

    CAS  Google Scholar 

  59. Wang J, Ke DD, Li Y, Zhang HM, Wang CX, Zhao X, Yuan YJ, Han SM (2017) Efficient hydrolysis of alkaline sodium borohydride catalyzed by cobalt nanoparticles supported on three-dimensional graphene oxide. Mater Res Bull 95:204–210

    CAS  Google Scholar 

  60. Cui ZK, Guo YP, Ma JT (2016) In situ synthesis of graphene supported Co–Sn–B alloy as an efficient catalyst for hydrogen generation from sodium borohydride hydrolysis. Int J Hydrogen Energy 41(3):1592–1599

    CAS  Google Scholar 

  61. Xiang CL, Jiang DD, She Z, Zou YJ, Chu HL, Qiu SJ, Zhang HZ, Xu F, Tang CY, Sun LX (2015) Hydrogen generation by hydrolysis of alkaline sodium borohydride using a cobalt–zinc–boron/graphene nanocomposite treated with sodium hydroxide. Int J Hydrogen Energy 40(11):4111–4118

    CAS  Google Scholar 

  62. Duman S, Ozkar S (2018) Ceria supported manganese(0) nanoparticle catalysts for hydrogen generation from the hydrolysis of sodium borohydride. Int J Hydrogen Energy 43(32):15262–15274

    CAS  Google Scholar 

Download references

Acknowledgement

This work was supported by SİÜFEB-27-2016.

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, Faculty of Engineering, Siirt University, Siirt, 56100, Turkey

    Ömer Şahin, Ali Bozkurt & Mehmet Sait İzgi

  2. Department of Chemical Engineering, Faculty of Engineering, Van Yuzuncu Yil University, Van, 65080, Turkey

    Müge Yayla & Hilal Çelik Kazıcı

Authors
  1. Ömer Şahin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ali Bozkurt
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Müge Yayla
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Hilal Çelik Kazıcı
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Mehmet Sait İzgi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ömer Şahin.

Ethics declarations

Conflict of interest

The authors declare no competing financial interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Şahin, Ö., Bozkurt, A., Yayla, M. et al. As a highly efficient reduced graphene oxide-supported ternary catalysts for the fast hydrogen release from NaBH4. Graphene Technol 5, 103–111 (2020). https://doi.org/10.1007/s41127-020-00036-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s41127-020-00036-y

Keywords

Search

Navigation