Preparation and Dehydrogenation Property of NH2-UIO-66 Supported RuCuMo Nanocatalyst

doi:10.15541/jim20190903

Abstract

Abstract:

Amine-functionalize metal organic framework (NH₂-UIO-66) was successfully synthesized by solvothermal method with zirconium salt and 2-aminoterephtalic acid. Tri-metallic RuCuMo nanoparticles (NPs) were immobilized by a facile impregnation-reduction method to prepare RuCuMo@NH₂-UIO-66 catalysts. The structure, morphology, composition and specific surface area of the above catalysts were characterized. Ru₁Cu₂Mo_0.5@NH₂-UIO-66 catalyst exhibits the highest catalytic activity comparing with Ru, RuCu and CuMo counterparts as well as pure tri-metallic RuCuMo NPs in hydrolytic dehydrogenation of ammonia borane at room temperature, and the correspoding activation energy (E_a) and turnover frequency values (TOF) are 30.1 kJ?mol ^-1 and 180.83 mol H₂ min ^-1(mol Ru) ^-1, respectively. Addition of Cu and Mo can significantly enhance the catalytic activity of Ru counterparts, owing to the synergistic effect among Ru, Cu and Mo atoms, bi-functional effect generated between RuCuMo NPs and NH₂-UIO-66 support, and the amine as anchoring groups in the NH₂-UIO-66 framework, which facilitate the formation and stabilization of ultra-small RuCuMo NPs by preventing their aggregation. The addition of non-noble metals Cu and Mo provides an important approach for the improvement of catalytic activity and industrial application.

Key words: metal organic frameworks (NH₂-UIO-66), RuCuMo@NH₂-UIO-66, solvothermal method, synergistic catalysis, releasing hydrogen

CLC Number:

O643

ZHANG Yi-Qing, LIU Li, ZHANG Shu-Juan, WAN Zheng-Rui, LIU Hong-Ying, ZHOU Li-Qun. Preparation and Dehydrogenation Property of NH₂-UIO-66 Supported RuCuMo Nanocatalyst[J]. Journal of Inorganic Materials, 2019, 34(12): 1316-1324.

Figures/Tables 9

Fig. 1 XRD patterns of NH2-UIO-66, Ru@NH2-UIO-66, CuMo@NH2-UIO-66, RuCu@NH2-UIO-66 and Ru1Cu2Mo0.5@NH2-UIO-66

Fig. 2 TEM images of (a, b) NH2-UIO-66, (c) Ru1Cu2Mo0.5@NH2-UIO-66, (e) RuCuMo NPs, (d, f) particle size distributions of (d) Ru1Cu2Mo0.5@NH2-UIO-66 and (f) RuCuMo NPs

Fig. 3 (a, c) FESEM image, (b) EDS analysis of Ru1Cu2Mo0.5@NH2-UIO-66 and (d-f) elemental mappings of Ru, Cu and Mo

Fig. 4 XPS spectra of the Ru1Cu2Mo0.5@NH2-UIO-66 catalysts survey, (b) Ru3p, (c)Cu2p, (d) Mo3d, (e)N1s

Fig. 5 FT-IR spectra of NH2-UIO-66, Ru1Cu2Mo0.5@NH2-UIO- 66 and Ru1Cu2Mo0.5@NH2-UIO-66 after 5 runs

Table 1 ICP-AES analyses of RuCuMo@NH2-UIO-66 catalysts with different molar ratios

Catalyst	Initial ratio of Ru : Cu : Mo	Actual ratio of Ru : Cu : Mo	Actual Ru loading/wt%
Ru₁Cu₂Mo_0.25@NH₂-UIO-66	1.00 : 2.00 : 0.25	1.00 : 2.20 : 0.04	4.89
Ru₁Cu₂Mo_0.5@NH₂-UIO-66	1.00 : 2.00 : 0.50	1.00 : 1.82 : 0.09	5.48
Ru₁Cu₂Mo_1.0@NH₂-UIO-66	1.00 : 2.00 : 1.00	1.00 : 2.04 : 0.19	5.16

Fig. 6 Plots of time vs. n(H2)/n(NH3BH3) from the hydrolysis of AB (18.5 mg): (a) RuCuMo NPs, Ru@NH2-UIO-66+Cu@NH2-UIO-66+Mo@NH2-UIO-66, Ru@NH2-UIO-66, Ru1Cu2 @NH2-UIO-66, CuMo@NH2-UIO-66, Ru1Cu2Mo0.5@NH2-UIO-66, NH2-UIO-66; (b) Ru1CuxMo0.5@NH2-UIO-66, and (c) Ru1Cu2Moy@NH2-UIO-66

Table 2 Catalytic activities of different Ru-based catalysts used for the hydrolytic dehydrogenation of AB

Catalyst	TOF/($\text{mo}{{\text{l}}_{{{\text{H}}_{2}}}}\cdot \text{mol}_{\text{Ru}}^{-1}\cdot {{\min }^{-1}}$)	E_a/(kJ?mol^-1)	Ref.
Ru NPs	26.70	66.50	[34]
RuCu(1:1)/γ-Al₂O₃	16.40	52.00	[35]
RuCo(1:1)/γ-Al₂O₃	32.90	47.00	[35]
Ru(0)/TiO₂	241.00	70.00	[36]
RuCo@MIL-53	87.24	34.32	[16]
Ru@g-C₃N₄	313.00	37.40	[37]
RuCu/graphene	135.00	30.60	[38]
RuCuMo@NH₂-UIO-66	180.83	30.10	This study

Fig. 7 Plots of time vs. n(H2)/n(NH3BH3) for the hydrolysis of AB (18.5 mg) aqueous solution catalyzed by Ru1Cu2Mo0.5@NH2-UIO-66 at different temperatures(a), and the corresponding Arrhenius plot (b), and reusability test for the Ru1Cu2Mo0.5@NH2-UIO-66 within five cycles(c)

References 38

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Preparation and Dehydrogenation Property of NH₂-UIO-66 Supported RuCuMo Nanocatalyst

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