Formic acid dehydrogenation reaction on high-performance Pd_xAu_1−x alloy nanoparticles prepared by the eco-friendly slow synthesis methodology

Abstract

Dehydrogenation of formic acid (FA) is considered to be an effective solution for efficient storage and transport of hydrogen. For decades, highly effective catalysts for this purpose have been widely investigated, but numerous challenges remain. Herein, the Pd_xAu_1−x (x = 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1) alloys over the whole composition range were successfully prepared and used to catalyze FA hydrogen production efficiently near room temperature. Small PdAu nanoparticles (5–10 nm) were well-dispersed and supported on the activated carbon to form PdAu solid solution alloys via the eco-friendly slow synthesis methodology. The physicochemical properties of the PdAu alloys were comprehensively studied by utilizing various measurement methods, such as X-ray diffraction (XRD), N₂ adsorption–desorption, high angle annular dark field-scanning transmission electron microscope (HAADF-STEM), X-ray photoelectrons spectroscopy (XPS). Notably, owing to the strong metal-support interaction (SMSI) and electron transfer between active metal Au and Pd, the Pd_0.5Au_0.5 obtained exhibits a turnover frequency (TOF) value of up to 1648 h⁻¹ (313 K, n_Pd+Au/n_FA = 0.01, n_HCOOH/n_HCOONa = 1:3) with a high activity, selectivity, and reusability in the FA dehydrogenation.

Key words： FA dehydrogenation; face-centred cubic structures; PdAu solid solution alloy nanoparticles; slow synthesis methodology; SMSI effect

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 52176131 and 51888103), the Natural Science Foundation of Shaanxi Province, China (Grant Nos. 2021JLM-18, 2020JC-04, and 2023KXJ-228), the National Science and Technology Major Project of China (No. J2019-III-0018-0062), and Xi’an Jiaotong University Special Research Project for Basic Research Business Expenses (No. xzy022022043).

Competing interests

The authors declare that they have no competing interests.

References

1 PeplowM. Hydrogen economy looks out of reach. Nature, 2004, https://doi.org/10.1038/news041004-13

2 Singh S K, Zhang X B, Xu Q. Room-temperature hydrogen generation from hydrous hydrazine for chemical hydrogen storage. Journal of the American Chemical Society, 2009, 131(29): 9894–9895

3 Scofield M E, Liu H, Wong S S. A concise guide to sustainable PEMFCs: Recent advances in improving both oxygen reduction catalysts and proton exchange membranes. Chemical Society Reviews, 2015, 44(16): 5836–5860

4 Li S J, Zhou Y T, Kang X. . A simple and effective principle for a rational design of heterogeneous catalysts for dehydrogenation of formic acid. Advanced Materials, 2019, 31(15): 1806781

5 Wang W, He T, Yang X. . General synthesis of amorphous PdM (M = Cu, Fe, Co, Ni) alloy nanowires for boosting HCOOH dehydrogenation. Nano Letters, 2021, 21(8): 3458–3464

6 Yadav M, Xu Q. Liquid-phase chemical hydrogen storage materials. Energy & Environmental Science, 2012, 5(12): 9698

7 Grad O, Mihet M, Dan M. . Au/reduced graphene oxide composites: Eco-friendly preparation method and catalytic applications for formic acid dehydrogenation. Journal of Materials Science, 2019, 54(9): 6991–7004

8 Nielsen M, Alberico E, Baumann W. . Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide. Nature, 2013, 495(7439): 85–89

9 Yi N, Saltsburg H, Flytzani-Stephanopoulos M. Hydrogen production by dehydrogenation of formic acid on atomically dispersed gold on Ceria. ChemSusChem, 2013, 6(5): 816–819

10 Shen J, Chen W, Lv G. . Hydrolysis of NH₃BH₃ and NaBH₄ by graphene quantum dots-transition metal nanoparticles for highly effective hydrogen evolution. International Journal of Hydrogen Energy, 2021, 46(1): 796–805

11 Wang Y, Liu X. Catalytic hydrolysis of sodium borohydride for hydrogen production using magnetic recyclable CoFe₂O₄-modified transition-metal nanoparticles. ACS Applied Nano Materials, 2021, 4(10): 11312–11320

12 Zhang Z, Lu Z, Tan H. . CeO_x-modified RhNi nanoparticles grown on rGO as highly efficient catalysts for complete hydrogen generation from hydrazine borane and hydrazine. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2015, 3(46): 23520–23529

13 Hong X, Yao Q, Huang M. . Bimetallic NiIr nanoparticles supported on lanthanum oxy-carbonate as highly efficient catalysts for hydrogen evolution from hydrazine borane and hydrazine. Inorganic Chemistry Frontiers, 2019, 6(9): 2271–2278

14 Jiang Y, Kang Q, Zhang J. . High-performance nickel–platinum nanocatalyst supported on mesoporous alumina for hydrogen generation from hydrous hydrazine. Journal of Power Sources, 2015, 273: 554–560

15 Dai H, Qiu Y, Dai H. . A study of degradation phenomenon of Ni–Pt/CeO₂ catalyst towards hydrogen generation from hydrous hydrazine. International Journal of Hydrogen Energy, 2017, 42(26): 16355–16361

16 Huang W, Liu X. The “on–off” switch for on-demand H₂ evolution from hydrous hydrazine over Ni₈Pt₁/C nano-catalyst. Fuel, 2022, 315: 123210

17 Zheng J, Zhou H, Wang C. . Current research progress and perspectives on liquid hydrogen rich molecules in sustainable hydrogen storage. Energy Storage Materials, 2021, 35: 695–722

18 Wang Y, Liu X. Enhanced catalytic performance of cobalt ferrite by a facile reductive treatment for H₂ release from ammonia borane. Journal of Molecular Liquids, 2021, 343: 117697

19 Sun Q, Wang N, Xu Q. . Nanopore-supported metal nanocatalysts for efficient hydrogen generation from liquid-phase chemical hydrogen storage materials. Advanced Materials, 2020, 32(44): 2001818

20 Yang L, Hua X, Su J. . Highly efficient hydrogen generation from formic acid-sodium formate over monodisperse AgPd nanoparticles at room temperature. Applied Catalysis B: Environmental, 2015, 168–169: 423–428

21 Gao Y, Hu E, Yin G. . Pd nanoparticles supported on CeO₂ nanospheres as efficient catalysts for dehydrogenation from additive-free formic acid at low temperature. Fuel, 2021, 302: 121142

22 Suh M P, Park H, Prasad T. . Hydrogen storage in metal–organic frameworks. Chemical Reviews, 2012, 112(2): 782–835

23 Lee H, Kang D, Pyen S. . Production of H₂-free CO by decomposition of formic acid over ZrO₂ catalysts. Applied Catalysis A, General, 2017, 531: 13–20

24 Faroldi B M, Conesa J M, Guerrero-Ruiz A. . Efficient nickel and copper-based catalysts supported on modified graphite materials for the hydrogen production from formic acid decomposition. Applied Catalysis A, General, 2022, 629: 118419

25 Lyu Y, Xie J, Wang D. . Review of cell performance in solid oxide fuel cells. Journal of Materials Science, 2020, 55(17): 7184–7207

26 Wei K, Wang X, Budiman R. . Progress in Ni-based anode materials for direct hydrocarbon solid oxide fuel cells. Journal of Materials Science, 2018, 53(12): 8747–8765

27 Bielinski E A, Lagaditis P O, Zhang Y. . Lewis acid-assisted formic acid dehydrogenation using a pincer-supported iron catalyst. Journal of the American Chemical Society, 2014, 136(29): 10234–10237

28 Deng M, Ma J, Liu Y. . Pd nanoparticles confined in pure Silicalite-2 zeolite with enhanced catalytic performance for the dehydrogenation of formic acid at room temperature. Fuel, 2023, 333: 126466

29 Mori K, Dojo M, Yamashita H. Pd and Pd–Ag nanoparticles within a macroreticular basic resin: An efficient catalyst for hydrogen production from formic acid decomposition. ACS Catalysis, 2013, 3(6): 1114–1119

30 Peng W, Liu S, Li X. . Robust hydrogen production from HCOOH over amino-modified KIT-6-confined PdIr alloy nanoparticles. Chinese Chemical Letters, 2022, 33(3): 1403–1406

31 Bulushev D, Beloshapkin S, Plyusnin P. . Vapour phase formic acid decomposition over PdAu/γ-Al₂O₃ catalysts: Effect of composition of metallic particles. Journal of Catalysis, 2013, 299: 171–180

32 Nasiri R, Gholipour B, Nourmohammadi M. . Mesoporous hybrid organosilica for stabilizing Pd nanoparticles and aerobic alcohol oxidation through Pd hydride (Pd–H₂) species. International Journal of Hydrogen Energy, 2023, 48(17): 6488–6498

33 Alamgholiloo H, Rostamnia S, Hassankhani A. . Formation and stabilization of colloidal ultra-small palladium nanoparticles on diamine-modified Cr-MIL-101: Synergic boost to hydrogen production from formic acid. Journal of Colloid and Interface Science, 2020, 567: 126–135

34 Doustkhah E, Rostamnia S, Imura M. . Thiourea bridged periodic mesoporous organosilica with ultra-small Pd nanoparticles for coupling reactions. RSC Advances, 2017, 7(89): 56306–56310

35 Ahadi A, Rostamnia S, Panahi P. . Palladium comprising dicationic bipyridinium supported periodic mesoporous organosilica (PMO): Pd@Bipy–PMO as an efficient hybrid catalyst for Suzuki–Miyaura cross-coupling reaction in water. Catalysts, 2019, 9(2): 140

36 Farajzadeh M, Alamgholiloo H, Nasibipour F. . Anchoring Pd-nanoparticles on dithiocarbamate-functionalized SBA-15 for hydrogen generation from formic acid. Scientific Reports, 2020, 10(1): 18188

37 Yang Y, Xu H, Cao D. . Hydrogen production via efficient formic acid decomposition: Engineering the surface structure of Pd-based alloy catalysts by design. ACS Catalysis, 2019, 9(1): 781–790

38 Wang Z, Liang S, Meng X. . Ultrasmall PdAu alloy nanoparticles anchored on amine-functionalized hierarchically porous carbon as additive-free catalysts for highly efficient dehydrogenation of formic acid. Applied Catalysis B: Environmental, 2021, 291: 120140

39 Gu X, Lu Z, Jiang H. . Synergistic catalysis of metal–organic framework-immobilized Au–Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage. Journal of the American Chemical Society, 2011, 133(31): 11822–11825

40 Pritchard J, Kesavan L, Piccinini M. . Direct synthesis of hydrogen peroxide and benzyl alcohol oxidation using Au−Pd catalysts prepared by sol immobilization. Langmuir, 2010, 26(21): 16568–16577

41 Al-Nayili A, Albdiry M. AuPd bimetallic nanoparticles supported on reduced graphene oxide nanosheets as catalysts for hydrogen generation from formic acid under ambient temperature. New Journal of Chemistry, 2021, 45(22): 10040–10048

42 Sanchez F, Bocelli L, Motta D. . Preformed Pd-based nanoparticles for the liquid phase decomposition of formic acid: Effect of stabiliser, support and Au–Pd ratio. Applied Sciences, 2020, 10(5): 1752

43 Dong A, Jiang Q, Zhou Y. Au₃Pd₁ intermetallic compound as single atom catalyst for formic acid decomposition with highly hydrogen selectivity. International Journal of Hydrogen Energy, 2023, 48(76): 29542–29551

44 Barlocco I, Capelli S, Lu X. . Disclosing the role of gold on palladium—Gold alloyed supported catalysts in formic acid decomposition. ChemCatChem, 2021, 13(19): 4210–4222

45 Feng C, Wang Y, Gao S. . Hydrogen generation at ambient conditions: AgPd bimetal supported on metal–organic framework derived porous carbon as an efficient synergistic catalyst. Catalysis Communications, 2016, 78: 17–21

46 Dai H, Xia B, Wen L. . Synergistic catalysis of AgPd@ZIF-8 on dehydrogenation of formic acid. Applied Catalysis B: Environmental, 2015, 165: 57–62

47 Gholipour B, Zonouzi A, Shokouhimehr M. . Integration of plasmonic AgPd alloy nanoparticles with single-layer graphitic carbon nitride as Mott-Schottky junction toward photo-promoted H₂ evolution. Scientific Reports, 2022, 12(1): 13583

48 Feng T, Wang J, Gao S. . Covalent triazine frameworks supported CoPd nanoparticles for boosting hydrogen generation from formic acid. Applied Surface Science, 2019, 469: 431–436

49 Cheng J, Gu X, Liu P. . Controlling catalytic dehydrogenation of formic acid over low-cost transition metal-substituted AuPd nanoparticles immobilized by functionalized metal–organic frameworks at room temperature. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2016, 4(42): 16645–16652

50 Cao N, Tan S, Luo W. . Ternary CoAgPd nanoparticles confined inside the pores of MIL-101 as efficient catalyst for dehydrogenation of formic acid. Catalysis Letters, 2016, 146(2): 518–524

51 Yan J, Wang Z, Gu L. . AuPd–MnO_x/MOF–graphene: An efficient catalyst for hydrogen production from formic acid at room temperature. Advanced Energy Materials, 2015, 5(10): 1500107

52 Jin M, Oh D, Park J. . Mesoporous silica supported Pd-MnO_x catalysts with excellent catalytic activity in room-temperature formic acid decomposition. Scientific Reports, 2016, 6(1): 33502

53 Sun X, Ding Y, Feng G. . Carbon bowl-confined subnanometric palladium-gold clusters for formic acid dehydrogenation and hexavalent chromium reduction. Journal of Colloid and Interface Science, 2023, 645: 676–684

54 Luo Y, Yang Q, Nie W Y. . Anchoring IrPdAu nanoparticles on NH₂-SBA-15 for fast hydrogen production from formic acid at room temperature. ACS Applied Materials & Interfaces, 2020, 12(7): 8082–8090

55 Zhong H, Iguchi M, Chatterjee M. . Formic acid-based liquid organic hydrogen carrier system with heterogeneous catalysts. Advanced Sustainable Systems, 2018, 2(2): 1700161

56 Zhong H, Iguchi M, Chatterjee M. . Interconversion between CO₂ and HCOOH under basic conditions catalyzed by PdAu nanoparticles supported by amine-functionalized reduced graphene oxide as a dual catalyst. ACS Catalysis, 2018, 8(6): 5355–5362

57 Szumełda T, Drelinkiewicz A, Lalik E. . Carbon-supported Pd_100−XAu_X alloy nanoparticles for the electrocatalytic oxidation of formic acid: Influence of metal particles composition on activity enhancement. Applied Catalysis B: Environmental, 2018, 221: 393–405

58 Tedsree K, Li T, Jones S. . Hydrogen production from formic acid decomposition at room temperature using a Ag-Pd core-shell nanocatalyst. Nature Nanotechnology, 2011, 6(5): 302–307

59 Zhao X, Xu D, Liu K. . Remarkable enhancement of PdAg/rGO catalyst activity for formic acid dehydrogenation by facile boron-doping through NaBH₄ reduction. Applied Surface Science, 2020, 512: 145746

60 Zhao X, Dai P, Xu D. . Ultrafine palladium nanoparticles anchored on NH₂-functionalized reduced graphene oxide as efficient catalyst towards formic acid dehydrogenation. International Journal of Hydrogen Energy, 2020, 45(55): 30396–30403

61 Kusada K, Wu D, Nanba Y. . Highly stable and active solid-solution-alloy three-way catalyst by utilizing configurational-entropy effect. Advanced Materials, 2021, 33(16): 2005206

62 Zhang Q, Kusada K, Wu D. . Solid-solution alloy nanoparticles of a combination of immiscible Au and Ru with a large gap of reduction potential and their enhanced oxygen evolution reaction performance. Chemical Science, 2019, 10(19): 5133–5137

63 Zhang Q, Kusada K, Wu D. . Selective control of fcc and hcp crystal structures in Au-Ru solid-solution alloy nanoparticles. Nature Communications, 2018, 9(1): 510

64 Deng C, Li Y, Sun W. . Supported AuPd nanoparticles with high catalytic activity and excellent separability based on the magnetic polymer carriers. Journal of Materials Science, 2019, 54(17): 11435–11447

65 Huang B, Kobayashi H, Yamamoto T. . Solid-solution alloying of immiscible Ru and Cu with enhanced CO oxidation activity. Journal of the American Chemical Society, 2017, 139(13): 4643–4646

66 Zhang Z J, Zhang S L, Yao Q L. . Metal–organic framework immobilized RhNi alloy nanoparticles for complete H₂ evolution from hydrazine borane and hydrous hydrazine. Inorganic Chemistry Frontiers, 2018, 5(2): 370–377

67 Gao S, Wang L, Li H. . Core–shell PdAu nanocluster catalysts to suppress sulfur poisoning. Physical Chemistry Chemical Physics, 2021, 23(28): 15010–15019

68 Scott R, Wilson O, Oh S. . Bimetallic palladium-gold dendrimer-encapsulated catalysts. Journal of the American Chemical Society, 2004, 126(47): 15583–15591

69 Zhu C, Guo S, Dong S. PdM (M = Pt, Au) bimetallic alloy nanowires with enhanced electrocatalytic activity for electro-oxidation of small molecules. Advanced Materials, 2012, 24(17): 2326–2331

70 Tan Z, Haneda M, Kitagawa H. . Slow synthesis methodology-directed immiscible octahedral Pd_xRh_1−x dual-atom-site catalysts for superior three-way catalytic activities over Rh. Angewandte Chemie International Edition, 2022, 61(23): 202202588

71 Chu P K, Li L H. Characterization of amorphous and nanocrystalline carbon films. Materials Chemistry and Physics, 2006, 96(2–3): 253–277

72 Zhang A, Xia J, Yao Q. . Pd–WO heterostructures immobilized by MOFs-derived carbon cage for formic acid dehydrogenation. Applied Catalysis B: Environmental, 2022, 309: 121278

73 Zhang B, Su D. Probing the metal-support interaction in carbon-supported catalysts by using electron microscopy. ChemCatChem, 2015, 7(22): 3639–3645

74 Guerrero-Ortega L, Ramírez-Meneses E, Cabrera-Sierra R. . Pd and Pd@PdO core–shell nanoparticles supported on Vulcan carbon XC-72R: Comparison of electroactivity for methanol electro-oxidation reaction. Journal of Materials Science, 2019, 54(21): 13694–13714

75 Nowicka E, Althahban S, Luo Y. . Highly selective PdZn/ZnO catalysts for the methanol steam reforming reaction. Catalysis Science & Technology, 2018, 8(22): 5848–5857

76 Costa L, Vasconcelos S, Pinto A. . Rh/CeO₂ catalyst preparation and characterization for hydrogen production from ethanol partial oxidation. Journal of Materials Science, 2008, 43(2): 440–449

77 Jiang K, Xu K, Zou S. . B-doped Pd catalyst: Boosting room-temperature hydrogen production from formic acid-formate solutions. Journal of the American Chemical Society, 2014, 136(13): 4861–4864