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J. Mater. Sci. Technol.  2018, Vol. 34 Issue (12): 2350-2358    DOI: 10.1016/j.jmst.2018.06.003
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Hydrolytic dehydrogenation of ammonia borane catalyzed by poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets supported Ag0.3Co0.7 nanoparticles
Dandan Keab, Jin Wangab, Hongming Zhangab, Yuan Liab*(), Lu Zhangab, Xin Zhaoc, Shumin Hanab*()
a Hebei Key Laboratory of Applied Chemistry, School of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, China
b State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China
c School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014030, China
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Poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets (PAMAM/rGO) composite was selected as a carrier of heterogeneous Ag0.3Co0.7 nanoparticles in order to obtain an excellent catalyst for ammonia borane (AB) hydrolysis. During the synthetic processes, GO could easily assembled with PAMAM by the electrostatic and hydrogen-bonding interactions. Structural characterization revealed that Ag0.3Co0.7 bimetallic nanoparticles with uniform size distribution of 5 nm are well dispersed on PAMAM/rGO composite architecture. Ag0.3Co0.7@PAMAM/rGO was found to be a highly active and reusable catalyst in hydrogen generation from the hydrolysis of AB with a turnover frequency value (TOF) of 19.79 molH2 min-1 molM-1 at 25.0 ± 0.1 °C and retained 75.4% of their initial activity with a complete release of hydrogen in five runs. The relatively high TOF value and low apparent activation energy (34.21 kJ mol-1) make these Ag0.3Co0.7@PAMAM/rGO NPs as a high-efficient catalyst for catalytic dehydrogenation of AB facilitating the development of practically applicable energy storage materials.

Key words:  Ammonia borane      Reduced graphene oxide      Ammonia borane      Ag0.3Co0.7 bimetallic nanoparticles      Hydrolytic dehydrogenation     
Received:  02 August 2017      Published:  15 November 2018
Corresponding Authors:  Li Yuan,Han Shumin     E-mail:;

Cite this article: 

Dandan Ke, Jin Wang, Hongming Zhang, Yuan Li, Lu Zhang, Xin Zhao, Shumin Han. Hydrolytic dehydrogenation of ammonia borane catalyzed by poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets supported Ag0.3Co0.7 nanoparticles. J. Mater. Sci. Technol., 2018, 34(12): 2350-2358.

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Fig. 1.  (a) Schematic illustration of self-assembly of PAMAM/GO suspensions, followed by chemical reduction of Ag+ and Co2+ and (b) photographs of PAMAM dendrimers, GO dispersion, PAMAM/GO, and Ag0.3Co0.7@PAMAM/rGO suspensions; (c) Schematic illustration of the synthesized Ag-Co@PAMAM/rGO NPs applied for hydrolytic dehydrogenation of AB.
Fig. 2.  TEM images of (a) Ag0.3Co0.7, (b) Ag0.3Co0.7@rGO, (c) Ag0.3Co0.7@PAMAM, (d) Ag0.3Co0.7@PAMAM/rGO, (e) the corresponding the selected-area electron diffraction (SAED) pattern and (f) EDAX of Ag0.3Co0.7@PAMAM/rGO.
Fig. 3.  XRD patterns of GO, PAMAM/GO, Ag0.3Co0.7@PAMAM/rGO composite.
Fig. 4.  FT-IR results of GO, PAMAM, PAMAM/GO composite and Ag0.3Co0.7@PAMAM/rGO NPs.
Fig. 5.  (a) XPS survey of Ag0.3Co0.7@PAMAM/rGO; (b-e) high-resolution XPS spectrum of C1s, N1s, Ag3d5/2 and Co2p3/2 respectively; (f) high-resolution Co2p3/2XPS spectrum ofCo@PAMAM/rGO.
Fig. 6.  (a) Hydrogen evolution plots and (b) the corresponding TOF values of the AB hydrolysis (1.5 mmol, 6 mL) in the presence of Ag0.3Co0.7, Co@rGO, Co@PAMAM/rGO, Ag0.3Co0.7/PAMAM, Ag0.3Co0.7@rGO, Ag0.3Co0.7@PAMAM/rGO catalysts.
Fig. 7.  Kinetic studies of Ag0.3Co0.7@PAMAM/rGO catalyst towards hydrolysis of NH3·BH3 under different reaction parameters: (a) different NH3·BH3 concentrations; (b) plot of ln [AB] vs lnr; (c) different catalyst concentrations; (d) plot of ln [cat.] vs ln r; (e) effect of NaOH concentration from 0 to 0.25 M on NH3·BH3 hydrolysis reaction; (f) plot of ln [NaOH] vs ln r.
Fig. 8.  Effect of temperature on the hydrolysis of AB solution without (a); (b) lnk versus 1/T (Arrhenius eq.); and (c) ln (k/T) versus 1/T (Eyring eq.), [0.25 M AB, 0.05 mmol Ag0.3Co0.7@PAMAM/rGO NPs].
Catalyst TOF
(total metal)
(kJ mol-1)
Ag0.3Co0.7/PAMAM/rGO 19.79 34.21 This study
Ag0.3Co0.7/PAMAM 15.84 35.66 [8]
PSSA-co-MA stabilized Co(0) nanoclusters 25.7 34 [34]
PEI-capped Co 39.9 28.2 [30]
PEI-GO/Fe-Ni 4.4 - [22]
Ag@Co/graphene 10.24 20.03 [12]
Ag@CoFe/graphene 8.29 32.79 [35]
graphene-CoNi 16.4 13.49 [36]
RuCo (1:1)/γ-Al2O3 16.4 47 [37]
Cryogel p(4-VP)-Co - 34.98 [38]
Amorphous Co-B, Ultrasonic hydrolysis 21.8 47.50 [39]
Co/Pdop-o-MWCNT - 50.41 [40]
Table 1  Catalytic activity of reported Ag- and/or Co- based catalysts applied for the hydrolysis of NH3·BH3.
Fig. 9.  Hydrolysis of aqueous NH3·BH3 solution catalyzed by Ag0.3Co0.7@PAMAM/rGO catalyst from the 1st to 5th cycle, insert: dehydrogenation rate values after five cycles.
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