Hydrogen Generation from Formic Acid Boosted by Functionalized Graphene Supported AuPd Nanocatalysts

doi:10.15541/jim20210311

Abstract

Abstract:

Formic acid (FA) is considered as a new type of hydrogen storage material with great application prospect due to its high hydrogen content and easy recharging as a liquid. Seeking high efficiency catalysts to solve the problem of slow reaction kinetics of hydrogen evolution from FA is vital. In this work, polyethyleneimine modified graphene (PEI-rGO) was used as the catalyst substrate, and PEI-rGO supported AuPd nanocomposite material (Au_0.3Pd_0.7/PEI-rGO) was prepared by wet chemical method. The Au_0.3Pd_0.7/PEI-rGO catalyst exhibits remarkable activity for the hydrogen generation from FA, affording an unprecedented turnover frequency (TOF) of 2357.5 mol_H2∙ mol_catalyst ^-1∙h ^-1 without any additives, which is superior to most heterogeneous catalysts under similar reaction conditions. Its excellent catalytic performance is attributed to the strong interaction between PEI-rGO substrate and AuPd nanoparticles, which regulates the size, dispersion and electronic structure of metal active components. Furthermore, the recycle test result shows that the catalyst has good stability.

Key words: functionalized graphene, nano metal catalyst, formic acid, hydrogen generation reaction

CLC Number:

TQ174

WANG Hongli, WANG Nan, WANG Liying, SONG Erhong, ZHAO Zhankui. Hydrogen Generation from Formic Acid Boosted by Functionalized Graphene Supported AuPd Nanocatalysts[J]. Journal of Inorganic Materials, 2022, 37(5): 547-553.

Figures/Tables 5

Fig. 2 TEM images, XRD pattern and EDX spectrum of Au0.3Pd0.7/PEI-rGO (a-b) TEM images and (c)HRTEM image for Au0.3Pd0.7/PEI-rGO with inset in (b) showing corresponding histogram of particle size distribution, (d) XRD pattern and (e) EDX pattern for Au0.3Pd0.7/PEI-rGO

Fig. 3 XPS spectra of Au0.3Pd0.7/PEI-rGO and Au0.3Pd0.7/rGO (a) XPS total spectra for (1) Au0.3Pd0.7/rGO and (2) Au0.3Pd0.7/PEI-rGO; (b) High resolution XPS spectra of N1s for Au0.3Pd0.7/PEI-rGO; (c) Au4f, (d) Pd3d XPS spectra for (1) Au0.3Pd0.7/PEI-rGO and (2) Au0.3Pd0.7/rGO

Fig. 4 Comparison of the catalytic performances for hydrogen evolution from FA dehydrogenation reaction of Au0.3Pd0.7/PEI-rGO, Au0.3Pd0.7/rGO and Au0.3Pd0.7 catalysts (a) Volume of gas versus time for the dehydrogenation of FA (1 mol/L, 5 mL) catalyzed by (1) Au0.3Pd0.7/PEI-rGO, (2) Au0.3Pd0.7/rGO and (3) Au0.3Pd0.7; (b) Corresponding TOF values

Table 1 TOF of different catalysts for FA dehydrogenation

Catalyst	Temperature/K	n_catalyst/n_FA	TOF/(mol_H2∙ mol_catalyst^-1∙h^-1)
Pd-NPs@TA-CoP^[22]	328	0.013	233.0^a
Pd@ED/Cr-MIL-101^[23]	328	0.003	583.0^b
Ni_0.4Pd_0.6/NH₂-N-rGO^[10]	298	0.020	954.3^a
Pd_0.7Ag_0.3/CeO_x-NPC^[24]	323	0.008	1101.9^a
Pd@TB-POP^[7]	323	0.100	1344.0^b
Pd/ImIP-2^[25]	323	0.008	1593.0^b
AuPd/n-CNS^[26]	333	0.020	1896.0^a
PdAg-CeO₂^[27]	303	0.033	2272.8^a
Au_0.3Pd_0.7/PEI-rGO	323	0.020	2357.5^a
Pd/MSC-30^[28]	323	0.013	2623.0^a
Pd-Co₂P/NPC^[13]	323	0.026	2980.0^b

Fig.5 (a) Volume of gas versus time for the dehydrogenation of FA at different temperatures over Au0.3Pd0.7/PEI-rGO catalyst; (b) Arrhenius plot (lnTOF versus 1/T) for Au0.3Pd0.7/PEI-rGO; (c) Volume of gas versus time for the dehydrogenation of FA at different ratios of AuxPd1-x/PEI-rGO (x=0, 0.1, 0.3, 0.7, 0.9, 1.0) at 323 K; (d) Durability tests of Au0.3Pd0.7/PEI-rGO towards the decomposition of FA (1.0 mol/L, 5.0 mL)

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