Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Hydrogen generation from ammonia borane by chemically dealloyed platinum nanoparticles

  • 50 Accesses


In this study, platinum catalysts were prepared from cosputtered platinum-aluminum alloys by dealloying method and utilized in hydrogen generation from ammonia borane. Aluminum was selectively removed from the alloy by sodium hydroxide. The resultant platinum particles obtained after dealloying was found to have nanoporous structure. The effect of Al sputtering power on hydrogen generation performance of particles was evaluated. The catalysts were characterized by SEM, TEM, and Zeta-Sizer. The maximum hydrogen generation rate of the catalysts was measured as 82.8 (± 2.2) L H2 min−1 g−1catalyst. The effect of catalyst amount was also evaluated. The activation energy of the reaction was calculated as 20.4 (± 0.8) kJ mol−1. Furthermore, the catalysts could preserve their catalytic activity upon consecutive runs with effective washing steps.

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

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


  1. 1.

    Sankir M, Semiz L, Sankir ND (2015) Catalyst free hydrogen generation from directly disulfonated poly(arylene ether sulfone) copolymer membranes. J Memb Sci 496:318–324

  2. 2.

    Chen X, Xu XJ, Zheng XC, Guan XX, Liu P (2018) Chitosan supported palladium nanoparticles: the novel catalysts for hydrogen generation from hydrolysis of ammonia borane. Mater Res Bull 103:89–95

  3. 3.

    Men Y, Su J, Du X, Liang L, Cheng G, Luo W (2018) CoBP nanoparticles supported on three-dimensional nitrogen-doped graphene hydrogel and their superior catalysis for hydrogen generation from hydrolysis of ammonia borane. J Alloys Compd 735:1271–1276

  4. 4.

    Xu M, Huai X, Zhang H (2018) Highly dispersed CuCo nanoparticles supported on reduced graphene oxide as high-activity catalysts for hydrogen evolution from ammonia borane hydrolysis. J Nanoparticle Res. https://doi.org/10.1007/s11051-018-4429-6

  5. 5.

    Cui L, Xu Y, Niu L, Yang W, Liu J (2017) Monolithically integrated CoP nanowire array: An on/off switch for effective on-demand hydrogen generation via hydrolysis of NaBH 4 and NH 3 BH 3. Nano Res 10:595–604

  6. 6.

    Chen G, Wang R, Zhao W, Kang B, Gao D, Li C, Lee JY (2018) Effect of Ru crystal phase on the catalytic activity of hydrolytic dehydrogenation of ammonia borane. J Power Sources 396:148–154

  7. 7.

    Sankir M, Semiz L, Serin RB, Sankir ND (2015) Hydrogen generation from nanoflower platinum films. Int J Hydrog Energy 40:8522–8529

  8. 8.

    Yang J, Cui Z, Ma J, Dong Z (2018) Ru coated Co nanoparticles decorated on cotton derived carbon fibers as a highly efficient and magnetically recyclable catalyst for hydrogen generation from ammonia borane. Int J Hydrog Energy 43:1355–1364

  9. 9.

    Echeverri A, Gomez T, Hadad CZ (2019) Ammonia borane dehydrogenation tendencies using Pt 4, Au 4, and Pt 2 Au 2 clusters as catalysts. Mol Catal 471:9–20

  10. 10.

    Al-Enizi AM, Brooks RM, Abutaleb A, El-Halwany MM, El-Newehy MH, Yousef A (2017) Electrospun carbon nanofibers containing Co-TiC nanoparticles-like superficial protrusions as a catalyst for H2 gas production from ammonia borane complex. Ceram Int 43:15735–15742

  11. 11.

    Yao Q, Lu ZH, Yang Y, Chen Y, Chen X, Jiang HL (2018) Facile synthesis of graphene-supported Ni-CeO x nanocomposites as highly efficient catalysts for hydrolytic dehydrogenation of ammonia borane. Nano Res 11:4412–4422

  12. 12.

    Wu Z, Duan Y, Ge S, Yip ACK, Yang F, Li Y, Dou T (2017) Promoting hydrolysis of ammonia borane over multiwalled carbon nanotube-supported Ru catalysts via hydrogen spillover. Catal Commun 91:10–15

  13. 13.

    Xu C, Wang H, Wang Q, Wang Y, Zhang Y, Fan G (2019) Ruthenium coordinated with triphenylphosphine-hyper-crosslinked polymer: an efficient catalyst for hydrogen evolution reaction and hydrolysis of ammonia borane. Appl Surf Sci 466:193–201

  14. 14.

    Ma Y, Li X, Zhang Y, Chen L, Wu J, Gao D, Bi J, Fan G (2017) Ruthenium nanoparticles supported on TiO2 (B) nanotubes: effective catalysts in hydrogen evolution from the hydrolysis of ammonia borane. J Alloys Compd 708:270–277

  15. 15.

    Semiz L, Abdullayeva N, Sankir M (2018) Nanoporous Pt and Ru catalysts by chemical dealloying of Pt-Al and Ru-Al alloys for ultrafast hydrogen generation. J Alloys Compd 744:110–115

  16. 16.

    Wang L, Li H, Zhang W, Zhao X, Qiu J, Li A, Zheng X, Hu Z, Si R, Zeng , (2017) Supported rhodium catalysts for ammonia-borane hydrolysis: dependence of the catalytic activity on the highest occupied state of the single rhodium atoms. Angew Chem Int Ed 56:4712–4718

  17. 17.

    Liu Q, Zhang S, Liao J, Feng K, Zheng Y, Pollet BG, Li H (2017) CuCo2O4 nanoplate film as a low-cost, highly active and durable catalyst towards the hydrolytic dehydrogenation of ammonia borane for hydrogen production. J Power Sources 355:191–198

  18. 18.

    Yang X, Li Q, Li L, Lin J, Yang X, Yu C, Liu Z, Fang Y, Huang Y, Tang C (2019) CuCo binary metal nanoparticles supported on boron nitride nanofibers as highly efficient catalysts for hydrogen generation from hydrolysis of ammonia borane. J Power Sources. 431:135–143

  19. 19.

    Filiz BC, Figen AK, Pişkin S (2018) Dual combining transition metal hybrid nanoparticles for ammonia borane hydrolytic dehydrogenation. Appl Catal Gen 550:320–330

  20. 20.

    Yousef A, Brooks RM, El-Halwany MM, Abutaleb A, El-Newehy MH, Al-Deyab SS, Kim HY (2017) Electrospun CoCr7C3-supported C nanofibers: effective, durable, and chemically stable catalyst for H2 gas generation from ammonia borane. Mol Catal 434:32–38

  21. 21.

    Figen AK, Filiz BC (2019) Polymeric and metal oxide structured nanofibrous composites fabricated by electrospinning as highly efficient hydrogen evolution catalyst. J Colloid Interface Sci 533:82–94

  22. 22.

    Zhang H, Ke D, Cheng L, Feng X, Hou X, Wang J, Li Y, Han S (2019) CoPt-Co hybrid supported on amino modified SiO 2 nanospheres as a high performance catalyst for hydrogen generation from ammonia borane. Prog Nat Sci Mater Int 29:1–9

  23. 23.

    Yan H, Lin Y, Wu H, Zhang W, Sun Z, Cheng H, Liu W, Wang C, Li J, Huang X, Yao T, Yang J, Wei S, Lu J (2017) Bottom-up precise synthesis of stable platinum dimers on graphene. Nat Commun 8:1–10

  24. 24.

    Chen W, Wang Z, Duan X, Qian G, Chen D, Zhou X (2018) Structural and kinetic insights into Pt/CNT catalysts during hydrogen generation from ammonia borane. Chem Eng Sci 192:1242–1251

  25. 25.

    Lizundia E, Jimenez M, Altorfer C, Niederberger M, Caseri W (2019) Electroless plating of platinum nanoparticles onto mesoporous cellulose films for catalytically active free-standing materials. Cellulose 26:5513–5527

  26. 26.

    Ye W, Ge Y, Gao Z, Lu R, Zhang S (2017) Enhanced catalytic activity and stability of Pt nanoparticles by surface coating of nanosized graphene oxide for hydrogen production from hydrolysis of ammonia-borane. Sustain Energy Fuels 1:2128–2133

  27. 27.

    Verma P, Yuan K, Kuwahara Y, Mori K, Yamashita H (2018) Enhancement of plasmonic activity by Pt/Ag bimetallic nanocatalyst supported on mesoporous silica in the hydrogen production from hydrogen storage material. Appl Catal B 223:10–15

  28. 28.

    Ke D, Wang J, Zhang H, Li Y, Zhang L, Zhao X, Han S (2017) Fabrication of Pt–Co NPs supported on nanoporous graphene as high-efficient catalyst for hydrolytic dehydrogenation of ammonia borane. Int J Hydrog Energy 42:26617–26625

  29. 29.

    Karaca T, Sevim M, Metin Ö (2017) Facile synthesis of monodisperse copper-platinum alloy nanoparticles and their superb catalysis in the hydrolytic dehydrogenation of ammonia borane and hydrazine borane. ChemCatChem 9:4185–4190

  30. 30.

    Chen W, Li D, Peng C, Qian G, Duan X, Chen D, Zhou X (2017) Mechanistic and kinetic insights into the Pt-Ru synergy during hydrogen generation from ammonia borane over PtRu/CNT nanocatalysts. J Catal 356:186–196

  31. 31.

    Gao M, Yang W, Yu Y (2018) Monodisperse PtCu alloy nanoparticles as highly efficient catalysts for the hydrolytic dehydrogenation of ammonia borane. Int J Hydrog Energy 43:14293–14300

  32. 32.

    Zhou Q, Xu C (2017) Stratified nanoporous PtTi alloys for hydrolysis of ammonia borane. J Colloid Interface Sci 496:235–242

  33. 33.

    Zhang J, Chen W, Ge H, Chen C, Yan W, Gao Z, Gan J, Zhang B, Duan X, Qin Y (2018) Synergistic effects in atomic-layer-deposited PtCox/CNTs catalysts enhancing hydrolytic dehydrogenation of ammonia borane. Appl Catal B 235:256–263

  34. 34.

    Zhao X, Fu Y, Yao C, Xu S, Shen Y, Ding Q, Liu W, Zhang H, Zhou X (2019) From boron organic polymers to in situ ultrafine nano Pd and Pt: green synthesis and application for high efficiency hydrogen evolution. ChemCatChem 11:2362–2369

  35. 35.

    Monai M, Montini T, Fonda E, Crosera M, Delgado JJ, Adami G, Fornasiero P (2018) Nanostructured Pd-Pt nanoparticles: evidences of structure/performance relations in catalytic H 2 production reactions. Appl Catal B 236:88–98

  36. 36.

    Zhan W-W, Zhu Q-L, Dang S, Liu Z, Kitta M, Suenaga K, Zheng L-S, Xu Q (2017) Synthesis of highly active sub-nanometer Pt@Rh core-shell nanocatalyst via a photochemical route: porous titania nanoplates as a superior photoactive support. Small 13:1603879

  37. 37.

    Chen J, Lu ZH, Huang W, Kang Z, Chen X (2017) Galvanic replacement synthesis of NiPt/graphene as highly efficient catalysts for hydrogen release from hydrazine and hydrazine borane. J Alloys Compd 695:3036–3043

  38. 38.

    Zhou Q, Qi L, Yang H, Xu C (2018) Hierarchical nanoporous platinum–copper alloy nanoflowers as highly active catalysts for the hydrolytic dehydrogenation of ammonia borane. J Colloid Interface Sci 513:258–265

  39. 39.

    Kazici HÇ, Yildiz F, İzgi MS, Ulaş B, Kivrak H (2019) Novel activated carbon supported trimetallic PdCoAg nanoparticles as efficient catalysts for the hydrolytic dehydrogenation of ammonia borane. Int J Hydrog Energy 44:10561–10572

  40. 40.

    Wang W, Miao L, Wu K, Chen G, Huang Y, Yang Y (2019) Hydrogen evolution in the dehydrogenation of methylcyclohexane over Pt/Ce–Mg–Al–O catalysts derived from their layered double hydroxides. Int J Hydrog Energy 44:2918–2925

  41. 41.

    Chen Y, Yang X, Kitta M, Xu Q (2017) Monodispersed Pt nanoparticles on reduced graphene oxide by a non-noble metal sacrificial approach for hydrolytic dehydrogenation of ammonia borane. Nano Res 10:3811–3816

  42. 42.

    Lara P, Philippot K, Suárez A (2019) Phosphane-decorated platinum nanoparticles as efficient catalysts for h2 generation from ammonia borane and methanol. ChemCatChem 11:766–771

  43. 43.

    Fu W, Han C, Li D, Chen W, Ji J, Qian G, Yuan W, Duan X, Zhou X (2020) Polyoxometalates-engineered hydrogen generation rate and durability of Pt/CNT catalysts from ammonia borane. J Energy Chem 41:142–148

  44. 44.

    Deka JR, Budi CS, Lin C-H, Saikia D, Yang Y-C, Kao H-M (2018) Carboxylic acid functionalized cage-type mesoporous silica FDU-12 as support for controlled synthesis of platinum nanoparticles and their catalytic applications. Chem Eur J 24(51):13540–13548

  45. 45.

    Wu C, Zhang J, Guo J, Sun L, Ming J, Dong H, Zhao Y, Tian J, Yang X (2018) Ceria-induced strategy to tailor Pt atomic clusters on cobalt-nickel oxide and the synergetic effect for superior hydrogen generation. ACS Sustain Chem Eng 6(6):7451–7457

  46. 46.

    Oh S, Song D, Kim H, Sohn D, Hong K, Lee M, Son S, Cho E, Kwon H (2019) Cobalt-iron-phosphorus catalysts for efficient hydrogen generation from hydrolysis of ammonia borane solution. J Alloys Compd 806:643–649

  47. 47.

    Wang Y, Wang D, Zhao C, Meng W, Zhao T, Cao Z, Zhang K, Bai S, Li G (2019) Co-Mo-B nanoparticles supported on foam Ni as efficient catalysts for hydrogen generation from hydrolysis of ammonia borane solution. Int J Hydrog Energy 44(21):10508–10518

  48. 48.

    Wang C, Sun D, Yu X, Zhang X, Lu Z, Wang X, Zhao J, Li L, Yang X (2018) Cu/Ni nanoparticles supported on TiO2(B) nanotubes as hydrogen generation photocatalysts via hydrolysis of ammonia borane. Inorg Chem Front 5:2038–2044

  49. 49.

    Qi X, Li X, Chen B, Lu H, Wang L, He G (2016) Highly active nanoreactors: patchlike or thick Ni coating on Pt nanoparticles based on confined catalysis. ACS Appl Mater Interfaces 8(3):1922–1928

  50. 50.

    Rakap M (2015) Poly(N-vinyl-2-pyrrolidone)-stabilized palladium–platinum nanoparticles-catalyzed hydrolysis of ammonia borane for hydrogen generation. J Power Sources 276:320–327

  51. 51.

    Fernandes R, Patel N, Edla R, Bazzamella N, Kothari DC, Miotello A (2015) Ruthenium nanoparticles supported over carbon thin film catalyst synthesized by pulsed laser deposition for hydrogen production from ammonia borane. Appl Catal A 495:23–29

  52. 52.

    Yu P-J, Lee M-H, Hsu H-M, Tsai H-M, Chean-Yang YW (2015) Silica aerogel-supported cobalt nanocomposites as efficient catalysts toward hydrogen generation from aqueous ammonia borane. RSC Adv 5(13985):13992

  53. 53.

    Filiz BC, Figen AK, Pişkin S (2018) The remarkable role of metal promoters on the catalytic activity of Co-Cu based nanoparticles for boosting hydrogen evolution: ammonia borane hydrolysis. Appl Catal B 238:365–380

  54. 54.

    Wang Y, Meng W, Wang D, Wang Z, Zou K, Cao Z, Zhang K, Wu S, Li G (2019) Ultrafine cobalt–molybdenum–boron nanocatalyst for enhanced hydrogen generation property from the hydrolysis of ammonia borane. Int J Hydrog Energy 44(41):23267–23276

Download references


This study was partly supported financially by The Research Centre of Amasya University under the project number FMB-BAP 18-0378.

Author information

Correspondence to Levent Semiz.

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

Verify currency and authenticity via CrossMark

Cite this article

Semiz, L. Hydrogen generation from ammonia borane by chemically dealloyed platinum nanoparticles. Reac Kinet Mech Cat 129, 205–218 (2020). https://doi.org/10.1007/s11144-019-01700-y

Download citation


  • Platinum
  • Catalyst
  • Hydrogen
  • Ammonia borane
  • Hydrolysis