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Acta Metall Sin  2018, Vol. 54 Issue (9): 1289-1296    DOI: 10.11900/0412.1961.2017.00481
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Tuning Surface Composition of Ni-Pt/CeO2 Catalyst for Hydrogen Generation from Hydrous Hydrazine Decomposition
Yuping QIU, Hao DAI, Hongbin DAI, Ping WANG()
Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, China
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Yuping QIU, Hao DAI, Hongbin DAI, Ping WANG. Tuning Surface Composition of Ni-Pt/CeO2 Catalyst for Hydrogen Generation from Hydrous Hydrazine Decomposition. Acta Metall Sin, 2018, 54(9): 1289-1296.

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Abstract  

Hydrous hydrazine (N2H4·H2O) is a water-like liquid with a high hydrogen density (8%, mass fraction), relatively low cost, and satisfactory stability under ambient conditions. Owing to these favorable attributes, N2H4·H2O has attracted considerable attention as a promising hydrogen carrier for onboard or portable applications. The synthesis of highly active and selective catalysts is a central issue in developing practical hydrous hydrazine-based hydrogen generation systems. The development of high-performance catalysts requires fundamental knowledge of the correlation between the surface composition of the catalyst and its catalytic performance. In the present work, a supported Ni-Pt/CeO2 bimetallic nanocatalyst was prepared by a one-pot co-reduction method, and its use for catalyzing hydrous hydrazine decomposition to generate hydrogen was reported. The surface composition of the Ni-Pt/CeO2 catalyst was regulated by heat treatments under different atmospheres, such as air, NH3, H2, and CO and at different temperatures. It was found that changing the annealing conditions may result in altered Ni/Pt ratio at the catalyst surface, and as a consequence the catalytic performance can be tailored. When the molar Ni/Pt ratio at the catalyst surface was 0.8~1.14, the catalyst has been found to possess remarkable catalytic activity towards hydrous hydrazine decomposition. Additionally, it was found that incorporation of non-metallic N element on the catalyst surface may result in remarkably improved catalytic activity of Ni-Pt/CeO2 towards hydrous hydrazine decomposition. This finding may open new avenues for the development of high-performance catalyst for promoting hydrogen generation from hydrous hydrazine.

Key words:  hydrous hydrazine      hydrogen generation      alloy catalyst      surface composition      heat treatment     
Received:  15 November 2017     
ZTFLH:  O643  
Fund: Supported by National Natural Science Foundation of China (Nos.51471168 and 51671087), Foundation for Innovative Research Groups of the National Natural Science Foundation of China (No.51621001), Foundation for Research Groups of the Natural Science Foundation of Guangdong Province (No.2016A030312011) and 985 Project of South China University of Technology

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https://www.ams.org.cn/EN/10.11900/0412.1961.2017.00481     OR     https://www.ams.org.cn/EN/Y2018/V54/I9/1289

Fig.1  A comparison of catalytic performances of Ni-Pt/CeO2 catalysts before and after heat treatment under air (a), H2 (b), NH3 (c) and CO (d) atmospheres and at different temperatures (The measurements were conducted in 4 mL of aqueous solution containing 0.5 mol/L N2H4·H2O+2.0 mol/L NaOH at 303 K, the catalyst/N2H4 molar ratio was fixed at 1/40)
Catalyst Atmosphere Temperature
K
Reaction rate
h-1
Selectivity
%
Ni-Pt/CeO2 (as-prepared) - - 336 96
Ni-Pt/CeO2 (annealed) Air (O2) 473 134 96
573 103 87
673 96 89
773 88 91
H2 473 278 97
573 327 100
673 234 97
773 177 99
NH3 573 315 98
673 490 100
773 404 100
CO 373 204 97
473 323 99
573 93 86
673 33 68
Table 1  Catalytic performances of Ni-Pt/CeO2 catalysts before and after heat treatment under different atmospheres at different temperatures
Fig.2  XRD spectra of the Ni-Pt/CeO2 catalyst samples as-prepared and annealed under different atmospheres at 573 K
Fig.3  TEM (a) and HRTEM (b) images of the annealed Ni-Pt/CeO2 catalyst under H2 atmosphere at 573 K (Inset in Fig.3a shows the SAED pattern, insets in Fig.3b show the enlarged views of square areas)
Fig.4  XPS of the annealed Ni-Pt/CeO2 catalyst under H2 atmosphere at 573 K
(a) Ni2p (b) Pt4f (c) Ce3d (d) O1s
Fig.5  XPS-determined surface Ni/Pt ratios of the Ni-Pt/CeO2 catalyst samples annealed under different atmospheres at different temperatures
Fig.6  Effect of Ni/Pt ratio of Ni-Pt/CeO2 catalyst surface on the catalytic decomposition rate of N2H4·H2O
Fig.7  HAADF-STEM image of Ni-Pt/CeO2 catalysts annealed under NH3 atmosphere at 673 K (a), element maps of Ni (b), Pt (c), Ce (d) and N (e), and XPS of N1s (f)
[1] Wang D S, Li Y D.Bimetallic nanocrystals: Liquid-phase synthesis and catalytic applications[J]. Adv. Mater., 2011, 23: 1044
[2] Yu W T, Porosoff M D, Chen J G.Review of Pt-based bimetallic catalysis: From model surfaces to supported catalysts[J]. Chem. Rev., 2012, 112: 5780
[3] De S, Zhang J G, Luque R, et al.Ni-based bimetallic heterogeneous catalysts for energy and environmental applications[J]. Energy Environ. Sci., 2016, 9: 3314
[4] Wang P, Kang X D.Hydrogen-rich boron-containing materials for hydrogen storage[J]. Dalton Trans., 2008, 40: 5400
[5] Singh S K, Xu Q.Nanocatalysts for hydrogen generation from hydrazine[J]. Catal. Sci. Technol., 2013, 3: 1889
[6] He L, Liang B L, Huang Y Q, et al.Design strategies of highly selective nickel catalysts for H2 production via hydrous hydrazine decomposition: A review[J]. Nat. Sci. Rev., 2018, 5: 356
[7] Cho S J, Lee J, Lee Y S, et al.Characterization of iridium catalyst for decomposition of hydrazine hydrate for hydrogen generation[J]. Catal. Lett., 2006, 109: 181
[8] Singh S K, Zhang X B, Xu Q.Room-temperature hydrogen generation from hydrous hydrazine for chemical hydrogen storage[J]. J. Am. Chem. Soc., 2009, 131: 9894
[9] Du X Q, Cai P, Luo W, et al.Facile synthesis of P-doped Rh nanoparticles with superior catalytic activity toward dehydrogenation of hydrous hydrazine[J]. Int. J. Hydrogen Energy, 2017, 42: 6137
[10] He L, Liang B L, Li L, et al.Cerium-oxide-modified nickel as a non-noble metal catalyst for selective decomposition of hydrous hydrazine to hydrogen[J]. ACS Catal., 2015, 5: 1623
[11] Kang W, Varma A.Hydrogen generation from hydrous hydrazine over Ni/CeO2 catalysts prepared by solution combustion synthesis[J]. Appl. Catal. Environ., 2018, 220B: 406
[12] He L, Huang Y Q, Wang A Q, et al.A noble-metal-free catalyst derived from Ni-Al hydrotalcite for hydrogen generation from N2H4·H2O decomposition[J]. Angew. Chem. Int. Ed. Engl., 2012, 51: 6191
[13] He L, Huang Y Q, Wang A Q, et al.Surface modification of Ni/Al2O3 with Pt: Highly efficient catalysts for H2 generation via selective decomposition of hydrous hydrazine[J]. J. Catal., 2013, 298: 1
[14] He L, Huang Y Q, Liu X Y, et al.Structural and catalytic properties of supported Ni-Ir alloy catalysts for H2 generation via hydrous hydrazine decomposition[J]. Appl. Catal. Environ., 2014, 147B: 779
[15] Zhang J J, Kang Q, Yang Z Q, et al.A cost-effective NiMoB-La(OH)3 catalyst for hydrogen generation from decomposition of alkaline hydrous hydrazine solution[J]. J. Mater. Chem., 2013, 1A: 11623
[16] Jiang Y Y, Dai H B, Zhong Y J, et al.Complete and rapid conversion of hydrazine monohydrate to hydrogen over supported Ni-Pt nanoparticles on mesoporous ceria for chemical hydrogen storage[J]. Chem. Eur. J., 2015, 21: 15439
[17] Jiang Y Y, Kang Q, Zhang J J, et al.High-performance nickel-platinum nanocatalyst supported on mesoporous alumina for hydrogen generation from hydrous hydrazine[J]. J. Power Sources, 2015, 273: 554
[18] Zhong Y J, Dai H B, Jiang Y Y, et al.Highly efficient Ni@Ni-Pt/La2O3 catalyst for hydrogen generation from hydrous hydrazine decomposition: Effect of Ni-Pt surface alloying[J]. J. Power Sources, 2015, 300: 294
[19] Dai H, Dai H B, Zhong Y J, et al.Kinetics of catalytic decomposition of hydrous hydrazine over CeO2-supported bimetallic Ni-Pt nanocatalysts[J]. Int. J. Hydrogen Energy, 2017, 42: 5684
[20] Wang H L, Yan J M, Wang Z L, et al.Highly efficient hydrogen generation from hydrous hydrazine over amorphous Ni0.9Pt0.1/Ce2O3 nanocatalyst at room temperature[J]. J. Mater. Chem., 2013, 1A: 14957
[21] Dai H B, Zhong Y J, Wang P.Hydrogen generation from decomposition of hydrous hydrazine over Ni-Ir/CeO2 catalyst[J]. Prog. Nat. Sci. Mater. Int., 2017, 27: 121
[22] Du X Q, Liu C, Du C, et al.Nitrogen-doped graphene hydrogel-supported NiPt-CeOx nanocomposites and their superior catalysis for hydrogen generation from hydrazine at room temperature[J]. Nano Res., 2017, 10: 2856
[23] Oliaee S N, Zhang C L, Hwang S Y, et al.Hydrogen production via hydrazine decomposition on model platinum-nickel nanocatalyst with a single (111) facet[J]. J. Phys. Chem., 2016, 120C: 9764
[24] Wang J, Zhang X B, Wang Z L, et al.Rhodium-nickel nanoparticles grown on graphene as highly efficient catalyst for complete decomposition of hydrous hydrazine at room temperature for chemical hydrogen storage[J]. Energy Environ. Sci., 2012, 5: 6885
[25] Mu R T, Guo X G, Fu Q, et al.Oscillation of surface structure and reactivity of PtNi bimetallic catalysts with redox treatments at variable temperatures[J]. J. Phys. Chem., 2011, 115C: 20590
[26] Ahmadi M, Behafarid F, Cui C H, et al.Long-range segregation phenomena in shape-selected bimetallic nanoparticles: Chemical state effects[J]. ACS Nano, 2013, 7: 9195
[27] Zhong Y J, Dai H B, Wang P.Preparation of Ni-Pt/La2O3 catalyst and its kinetics study of hydrous hydrazine for hydrogen generation[J]. Acta Metall. Sin., 2016, 52: 505(钟玉洁, 戴洪斌, 王平. 水合肼制氢Ni-Pt/La2O3催化剂研制及其反应动力学研究[J]. 金属学报, 2016, 52: 505)
[28] Song F Z, Zhu Q L, Xu Q.Monodispersed PtNi nanoparticles deposited on diamine-alkalized graphene for highly efficient dehydrogenation of hydrous hydrazine at room temperature[J]. J. Mater. Chem., 2015, 3A: 23090
[29] Zhong Y J, Dai H B, Zhu M, et al.Catalytic decomposition of hydrous hydrazine over Ni-Pt/La2O3 catalyst: A high-performance hydrogen storage system[J]. Int. J. Hydrogen Energy, 2016, 41: 11042
[30] Singh S K, Xu Q.Complete conversion of hydrous hydrazine to hydrogen at room temperature for chemical hydrogen storage[J]. J. Am. Chem. Soc., 2009, 131: 18032
[31] Zhao P P, Cao N, Su J, et al.NiIr nanoparticles immobilized on the pores of MIL-101 as highly efficient catalyst toward hydrogen generation from hydrous hydrazine[J]. ACS Sustain. Chem. Eng., 2015, 3: 1086
[32] Zhu Q L, Xu Q.Liquid organic and inorganic chemical hydrides for high-capacity hydrogen storage[J]. Energy Environ. Sci., 2015, 8: 478
[33] Singh S K, Singh A K, Aranishi K, et al.Noble-metal-free bimetallic nanoparticle-catalyzed selective hydrogen generation from hydrous hydrazine for chemical hydrogen storage[J]. J. Am. Chem. Soc., 2011, 133: 19638
[34] O Song-II, Yan J M, Wang H L, et al. Ni/La2O3 catalyst containing low content platinum-rhodium for the dehydrogenation of N2H4·H2O at room temperature[J]. J. Power Sources, 2014, 262: 386
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