Formic acid dehydrogenation reaction on high-performance PdxAu1−x alloy nanoparticles prepared by the eco-friendly slow synthesis methodology
Yibo GAO1, Erjiang HU1(), Bo HUANG2, Zuohua HUANG1()
1. State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, China 2. Institute of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 712000, China
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 PdxAu1−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 Pd0.5Au0.5 obtained exhibits a turnover frequency (TOF) value of up to 1648 h−1 (313 K, nPd+Au/nFA = 0.01, nHCOOH/nHCOONa = 1:3) with a high activity, selectivity, and reusability in the FA dehydrogenation.
M Peplow. Hydrogen economy looks out of reach. Nature, 2004, https://doi.org/10.1038/news041004-13
2
S K Singh, X B Zhang, Q Xu. Room-temperature hydrogen generation from hydrous hydrazine for chemical hydrogen storage. Journal of the American Chemical Society, 2009, 131(29): 9894–9895 https://doi.org/10.1021/ja903869y
3
M E Scofield, H Liu, S S Wong. 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 https://doi.org/10.1039/C5CS00302D
4
S J Li, Y T Zhou, X Kang. et al.. A simple and effective principle for a rational design of heterogeneous catalysts for dehydrogenation of formic acid. Advanced Materials, 2019, 31(15): 1806781 https://doi.org/10.1002/adma.201806781
5
W Wang, T He, X Yang. et al.. General synthesis of amorphous PdM (M = Cu, Fe, Co, Ni) alloy nanowires for boosting HCOOH dehydrogenation. Nano Letters, 2021, 21(8): 3458–3464 https://doi.org/10.1021/acs.nanolett.1c00074
6
M Yadav, Q Xu. Liquid-phase chemical hydrogen storage materials. Energy & Environmental Science, 2012, 5(12): 9698 https://doi.org/10.1039/c2ee22937d
7
O Grad, M Mihet, M Dan. et al.. 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 https://doi.org/10.1007/s10853-019-03394-y
8
M Nielsen, E Alberico, W Baumann. et al.. Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide. Nature, 2013, 495(7439): 85–89 https://doi.org/10.1038/nature11891
9
N Yi, H Saltsburg, M Flytzani-Stephanopoulos. Hydrogen production by dehydrogenation of formic acid on atomically dispersed gold on Ceria. ChemSusChem, 2013, 6(5): 816–819 https://doi.org/10.1002/cssc.201200957
10
J Shen, W Chen, G Lv. et al.. 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 https://doi.org/10.1016/j.ijhydene.2020.09.153
11
Y Wang, X Liu. 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 https://doi.org/10.1021/acsanm.1c03067
12
Z Zhang, Z Lu, H Tan. et al.. CeOx-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 https://doi.org/10.1039/C5TA06197K
13
X Hong, Q Yao, M Huang. et al.. 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 https://doi.org/10.1039/C9QI00848A
14
Y Jiang, Q Kang, J Zhang. et al.. High-performance nickel–platinum nanocatalyst supported on mesoporous alumina for hydrogen generation from hydrous hydrazine. Journal of Power Sources, 2015, 273: 554–560 https://doi.org/10.1016/j.jpowsour.2014.09.119
15
H Dai, Y Qiu, H Dai. et al.. 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 https://doi.org/10.1016/j.ijhydene.2017.05.086
16
W Huang, X Liu. The “on–off” switch for on-demand H2 evolution from hydrous hydrazine over Ni8Pt1/C nano-catalyst. Fuel, 2022, 315: 123210 https://doi.org/10.1016/j.fuel.2022.123210
17
J Zheng, H Zhou, C Wang. et al.. Current research progress and perspectives on liquid hydrogen rich molecules in sustainable hydrogen storage. Energy Storage Materials, 2021, 35: 695–722 https://doi.org/10.1016/j.ensm.2020.12.007
18
Y Wang, X Liu. Enhanced catalytic performance of cobalt ferrite by a facile reductive treatment for H2 release from ammonia borane. Journal of Molecular Liquids, 2021, 343: 117697 https://doi.org/10.1016/j.molliq.2021.117697
19
Q Sun, N Wang, Q Xu. et al.. Nanopore-supported metal nanocatalysts for efficient hydrogen generation from liquid-phase chemical hydrogen storage materials. Advanced Materials, 2020, 32(44): 2001818 https://doi.org/10.1002/adma.202001818
20
L Yang, X Hua, J Su. et al.. 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 https://doi.org/10.1016/j.apcatb.2015.01.003
21
Y Gao, E Hu, G Yin. et al.. Pd nanoparticles supported on CeO2 nanospheres as efficient catalysts for dehydrogenation from additive-free formic acid at low temperature. Fuel, 2021, 302: 121142 https://doi.org/10.1016/j.fuel.2021.121142
22
M P Suh, H Park, T Prasad. et al.. Hydrogen storage in metal–organic frameworks. Chemical Reviews, 2012, 112(2): 782–835 https://doi.org/10.1021/cr200274s
23
H Lee, D Kang, S Pyen. et al.. Production of H2-free CO by decomposition of formic acid over ZrO2 catalysts. Applied Catalysis A, General, 2017, 531: 13–20 https://doi.org/10.1016/j.apcata.2016.11.032
24
B M Faroldi, J M Conesa, A Guerrero-Ruiz. et al.. 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 https://doi.org/10.1016/j.apcata.2021.118419
25
Y Lyu, J Xie, D Wang. et al.. Review of cell performance in solid oxide fuel cells. Journal of Materials Science, 2020, 55(17): 7184–7207 https://doi.org/10.1007/s10853-020-04497-7
26
K Wei, X Wang, R Budiman. et al.. Progress in Ni-based anode materials for direct hydrocarbon solid oxide fuel cells. Journal of Materials Science, 2018, 53(12): 8747–8765 https://doi.org/10.1007/s10853-018-2205-8
27
E A Bielinski, P O Lagaditis, Y Zhang. et al.. Lewis acid-assisted formic acid dehydrogenation using a pincer-supported iron catalyst. Journal of the American Chemical Society, 2014, 136(29): 10234–10237 https://doi.org/10.1021/ja505241x
28
M Deng, J Ma, Y Liu. et al.. 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 https://doi.org/10.1016/j.fuel.2022.126466
29
K Mori, M Dojo, H Yamashita. 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 https://doi.org/10.1021/cs400148n
30
W Peng, S Liu, X Li. et al.. Robust hydrogen production from HCOOH over amino-modified KIT-6-confined PdIr alloy nanoparticles. Chinese Chemical Letters, 2022, 33(3): 1403–1406 https://doi.org/10.1016/j.cclet.2021.08.033
31
D Bulushev, S Beloshapkin, P Plyusnin. et al.. Vapour phase formic acid decomposition over PdAu/γ-Al2O3 catalysts: Effect of composition of metallic particles. Journal of Catalysis, 2013, 299: 171–180 https://doi.org/10.1016/j.jcat.2012.12.009
32
R Nasiri, B Gholipour, M Nourmohammadi. et al.. 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 https://doi.org/10.1016/j.ijhydene.2022.04.242
33
H Alamgholiloo, S Rostamnia, A Hassankhani. et al.. 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 https://doi.org/10.1016/j.jcis.2020.01.087
34
E Doustkhah, S Rostamnia, M Imura. et al.. Thiourea bridged periodic mesoporous organosilica with ultra-small Pd nanoparticles for coupling reactions. RSC Advances, 2017, 7(89): 56306–56310 https://doi.org/10.1039/C7RA11711F
35
A Ahadi, S Rostamnia, P Panahi. et al.. 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 https://doi.org/10.3390/catal9020140
36
M Farajzadeh, H Alamgholiloo, F Nasibipour. et al.. Anchoring Pd-nanoparticles on dithiocarbamate-functionalized SBA-15 for hydrogen generation from formic acid. Scientific Reports, 2020, 10(1): 18188 https://doi.org/10.1038/s41598-020-75369-y
37
Y Yang, H Xu, D Cao. et al.. 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 https://doi.org/10.1021/acscatal.8b03485
38
Z Wang, S Liang, X Meng. et al.. 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 https://doi.org/10.1016/j.apcatb.2021.120140
39
X Gu, Z Lu, H Jiang. et al.. 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 https://doi.org/10.1021/ja200122f
40
J Pritchard, L Kesavan, M Piccinini. et al.. Direct synthesis of hydrogen peroxide and benzyl alcohol oxidation using Au−Pd catalysts prepared by sol immobilization. Langmuir, 2010, 26(21): 16568–16577 https://doi.org/10.1021/la101597q
41
A Al-Nayili, M Albdiry. 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 https://doi.org/10.1039/D1NJ01658J
42
F Sanchez, L Bocelli, D Motta. et al.. 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 https://doi.org/10.3390/app10051752
43
A Dong, Q Jiang, Y Zhou. 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 https://doi.org/10.1016/j.ijhydene.2023.04.113
44
I Barlocco, S Capelli, X Lu. et al.. Disclosing the role of gold on palladium—Gold alloyed supported catalysts in formic acid decomposition. ChemCatChem, 2021, 13(19): 4210–4222 https://doi.org/10.1002/cctc.202100886
45
C Feng, Y Wang, S Gao. et al.. 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 https://doi.org/10.1016/j.catcom.2016.01.034
46
H Dai, B Xia, L Wen. et al.. Synergistic catalysis of AgPd@ZIF-8 on dehydrogenation of formic acid. Applied Catalysis B: Environmental, 2015, 165: 57–62 https://doi.org/10.1016/j.apcatb.2014.09.065
47
B Gholipour, A Zonouzi, M Shokouhimehr. et al.. 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 https://doi.org/10.1038/s41598-022-17238-4
48
T Feng, J Wang, S Gao. et al.. Covalent triazine frameworks supported CoPd nanoparticles for boosting hydrogen generation from formic acid. Applied Surface Science, 2019, 469: 431–436 https://doi.org/10.1016/j.apsusc.2018.11.036
49
J Cheng, X Gu, P Liu. et al.. 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 https://doi.org/10.1039/C6TA05790J
50
N Cao, S Tan, W Luo. et al.. 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 https://doi.org/10.1007/s10562-015-1671-8
51
J Yan, Z Wang, L Gu. et al.. AuPd–MnOx/MOF–graphene: An efficient catalyst for hydrogen production from formic acid at room temperature. Advanced Energy Materials, 2015, 5(10): 1500107 https://doi.org/10.1002/aenm.201500107
52
M Jin, D Oh, J Park. et al.. Mesoporous silica supported Pd-MnOx catalysts with excellent catalytic activity in room-temperature formic acid decomposition. Scientific Reports, 2016, 6(1): 33502 https://doi.org/10.1038/srep33502
53
X Sun, Y Ding, G Feng. et al.. 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 https://doi.org/10.1016/j.jcis.2023.05.002
54
Y Luo, Q Yang, W Y Nie. et al.. 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 https://doi.org/10.1021/acsami.9b16981
55
H Zhong, M Iguchi, M Chatterjee. et al.. Formic acid-based liquid organic hydrogen carrier system with heterogeneous catalysts. Advanced Sustainable Systems, 2018, 2(2): 1700161 https://doi.org/10.1002/adsu.201700161
56
H Zhong, M Iguchi, M Chatterjee. et al.. 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 https://doi.org/10.1021/acscatal.8b00294
57
T Szumełda, A Drelinkiewicz, E Lalik. et al.. Carbon-supported Pd100−XAuX 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 https://doi.org/10.1016/j.apcatb.2017.09.039
58
K Tedsree, T Li, S Jones. et al.. Hydrogen production from formic acid decomposition at room temperature using a Ag-Pd core-shell nanocatalyst. Nature Nanotechnology, 2011, 6(5): 302–307 https://doi.org/10.1038/nnano.2011.42
59
X Zhao, D Xu, K Liu. et al.. Remarkable enhancement of PdAg/rGO catalyst activity for formic acid dehydrogenation by facile boron-doping through NaBH4 reduction. Applied Surface Science, 2020, 512: 145746 https://doi.org/10.1016/j.apsusc.2020.145746
60
X Zhao, P Dai, D Xu. et al.. 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 https://doi.org/10.1016/j.ijhydene.2020.08.025
61
K Kusada, D Wu, Y Nanba. et al.. Highly stable and active solid-solution-alloy three-way catalyst by utilizing configurational-entropy effect. Advanced Materials, 2021, 33(16): 2005206 https://doi.org/10.1002/adma.202005206
62
Q Zhang, K Kusada, D Wu. et al.. 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 https://doi.org/10.1039/C9SC00496C
63
Q Zhang, K Kusada, D Wu. et al.. Selective control of fcc and hcp crystal structures in Au-Ru solid-solution alloy nanoparticles. Nature Communications, 2018, 9(1): 510 https://doi.org/10.1038/s41467-018-02933-6
64
C Deng, Y Li, W Sun. et al.. 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 https://doi.org/10.1007/s10853-019-03701-7
65
B Huang, H Kobayashi, T Yamamoto. et al.. Solid-solution alloying of immiscible Ru and Cu with enhanced CO oxidation activity. Journal of the American Chemical Society, 2017, 139(13): 4643–4646 https://doi.org/10.1021/jacs.7b01186
66
Z J Zhang, S L Zhang, Q L Yao. et al.. 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 https://doi.org/10.1039/C7QI00555E
67
S Gao, L Wang, H Li. et al.. Core–shell PdAu nanocluster catalysts to suppress sulfur poisoning. Physical Chemistry Chemical Physics, 2021, 23(28): 15010–15019 https://doi.org/10.1039/D1CP01274F
68
R Scott, O Wilson, S Oh. et al.. Bimetallic palladium-gold dendrimer-encapsulated catalysts. Journal of the American Chemical Society, 2004, 126(47): 15583–15591 https://doi.org/10.1021/ja0475860
69
C Zhu, S Guo, S Dong. PdM (M = Pt, Au) bimetallic alloy nanowires with enhanced electrocatalytic activity for electro-oxidation of small molecules. Advanced Materials, 2012, 24(17): 2326–2331 https://doi.org/10.1002/adma.201104951
70
Z Tan, M Haneda, H Kitagawa. et al.. Slow synthesis methodology-directed immiscible octahedral PdxRh1−x dual-atom-site catalysts for superior three-way catalytic activities over Rh. Angewandte Chemie International Edition, 2022, 61(23): 202202588 https://doi.org/10.1002/anie.202202588
A Zhang, J Xia, Q Yao. et al.. Pd–WO heterostructures immobilized by MOFs-derived carbon cage for formic acid dehydrogenation. Applied Catalysis B: Environmental, 2022, 309: 121278 https://doi.org/10.1016/j.apcatb.2022.121278
73
B Zhang, D Su. Probing the metal-support interaction in carbon-supported catalysts by using electron microscopy. ChemCatChem, 2015, 7(22): 3639–3645 https://doi.org/10.1002/cctc.201500666
74
L Guerrero-Ortega, E Ramírez-Meneses, R Cabrera-Sierra. et al.. 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 https://doi.org/10.1007/s10853-019-03843-8
75
E Nowicka, S Althahban, Y Luo. et al.. Highly selective PdZn/ZnO catalysts for the methanol steam reforming reaction. Catalysis Science & Technology, 2018, 8(22): 5848–5857 https://doi.org/10.1039/C8CY01100A
76
L Costa, S Vasconcelos, A Pinto. et al.. Rh/CeO2 catalyst preparation and characterization for hydrogen production from ethanol partial oxidation. Journal of Materials Science, 2008, 43(2): 440–449 https://doi.org/10.1007/s10853-007-1982-2
77
K Jiang, K Xu, S Zou. et al.. 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 https://doi.org/10.1021/ja5008917
