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
Cite this article:
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.
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.
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
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)
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