Ionic Liquid-Modulated Synthesis of Pt-Pd Bimetallic Nanomaterials and Their Catalytic Performance for Ammonia Borane Hydrolysis to Generate Hydrogen

doi:10.19894/j.issn.1000-0518.220321

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (4): 597-609.DOI: 10.19894/j.issn.1000-0518.220321

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Ionic Liquid-Modulated Synthesis of Pt-Pd Bimetallic Nanomaterials and Their Catalytic Performance for Ammonia Borane Hydrolysis to Generate Hydrogen

Hui-Hui LI, Kai-Sheng YAO(), Ya-Nan ZHAO, Li-Na FAN, Yu-Lin TIAN, Wei-Wei LU()

Chemical Engineering & Pharmaceutics School，Henan University of Science & Technology，Luoyang 471023，China

Received:2022-10-07 Accepted:2023-02-22 Published:2023-04-01 Online:2023-04-17
Contact: Kai-Sheng YAO,Wei-Wei LU
About author:luwei1980@126.com
ksyao@haust.edu.cn
Supported by:
the National Natural Science Foundation of China(21673067);the Key Science and Technology Project of Henan Province(192102210043)

Abstract

Abstract:

Herein， under the modulation of an ionic liquid 1-tetradecyl-3-methylimidazole bromide （［C₁₄mim］Br）， Pt-Pd bimetallic nanomaterials are prepared in one-pot at 90 ℃ in aqueous solution with polyvinylpyrrolidone （PVP） as the stabilizer. The morphology， structure， components and valence states of the products are characterized and analyzed in detail by transmission electron microscopy （TEM）， scanning electron microscopy （SEM）， high-angle annular dark-field scanning transmission electron microscopy （HAADF-STEM）， energy dispersive X-ray spectroscopy （EDS）， X-ray diffractometry （XRD） and X-ray photoelectron spectrometer （XPS）. The results show that except for pure Pd sample， Pt-Pd bimetallic nanomaterials with other Pt/Pd ratios have porous structures. ［C₁₄mim］Br plays an important role in regulating the synthesis of Pt-Pd porous nanomaterials. For the ionic liquids ［C _n mim］Br with the alkyl chain length≥C12， it is beneficial for the formation of porous Pd@Pt spherical structures. In the experiment of the ammonia borane hydrolysis， Pt-Pd bimetallic nanomaterials with various ratios show higher catalytic activities than commercial Pd/C， among which Pt₃Pd₇ nanomaterials have the best catalytic performance. The hydrogen generation reaction can be quickly achieved within only 6 min and the hydrogen yield is up to 100%. At 25 ℃， the activation energy （E_a） and the turnover frequency （TOF） values are calculated to be 36.15 kJ/mol and 35.72 mol/（mol·min）， respectively. Furthermore， the reaction for the five catalytic cycles can be achieved within 51 min， and the yield can still reach 100%， indicating that the catalyst has high activity and good stability.

Key words: Ionic liquids, Pt-Pd bimetals, Nanomaterials, Hydrogen production of ammonia borane hydrolysis

CLC Number:

O643.3

Hui-Hui LI, Kai-Sheng YAO, Ya-Nan ZHAO, Li-Na FAN, Yu-Lin TIAN, Wei-Wei LU. Ionic Liquid-Modulated Synthesis of Pt-Pd Bimetallic Nanomaterials and Their Catalytic Performance for Ammonia Borane Hydrolysis to Generate Hydrogen[J]. Chinese Journal of Applied Chemistry, 2023, 40(4): 597-609.

Figures/Tables 14

Fig.1 TEM images of Pt-Pd samples with different Pt/Pd molar ratios

Fig.2 The as-prepared Pt7Pd3 and Pt3Pd7 samples：（A） HAADF-STEM image，（B-D） elemental mapping images，（E） HAADF-STEM compositional curves of Pd （red lines） and Pt （green lines） along with the orange line in （A），（F） EDS spectra of Pt7Pd3 sample；（G） HAADF-STEM image，（H-J） elemental mapping images，（K） HAADF-STEM compositional curves of Pd （green lines） and Pt （red lines） along with the orange line in （G） and （L） EDS spectra of Pt3Pd7 sample

Fig.3 XRD patterns of the Pt-Pd samples with different molar ratios

Fig.4 High-resolution XPS spectra of Pt4f and Pd3d for porous Pt7Pd3 sample （A， B） and Pt3Pd7 sample （C， D）， respectively

Fig.5 SEM images of Pt7Pd3 samples prepared in the presence of ionic liquids with different alkyl chain lengths

Fig.6 TEM images of Pt7Pd3 samples prepared in the presence of ［C14min］Br with different concentrations

Fig.7 The curves of equivalent H2 produced by per mole of AB hydrolysis in the presence of various catalysts as a function of reaction time at 25 ℃

Fig.8 Plots of time versus hydrogen volume generated from AB catalyzed by Pt3Pd7 with different catalyst amounts； Inset： plot of hydrogen generation rate versus Pt3Pd7 concentration （both in logaritmic scale）

Fig.9 Plots of moles of H2 versus time for the hydrolysis of AB at different concentrations （40，50，60，70 mmol/L） keeping Pt3Pd7 catalyst concentration at 7.0 mmol/L； Inset： plot of hydrogen generation rate versus AB concentration （both in logaritmic scale）

Fig.10 Plots of equivalent H2 produced by per mole of AB hydrolysis versus time in the presence of porous Pt3Pd7 catalyst at different temperature； Inset： the linear fitting of Arrhenius equation between ln k and 1000/T

Table 1 TOF and Ea values for AB hydrolysis to produce hydrogen with different catalysts

Catalysts	Temperature/℃	TOF/（mol·mol^-1·min^-1）	E_a/（kJ·mol^-1）	Ref.
Pt₃Pd₇	25	35.72	36.15	This work
PdPt spherical NPs	25	22.5	57.3	［17］
AuCo/CNT-2	25	8.47	34.83	［43］
Au@AuCo/CNT	25	13.24	41.91	［43］
1/1000Pt+Ni/CNT	25	17.8	－	［44］
1/100Pt+Ni/CNT	25	33.3	－	［44］
Pd₈₀Ni₂₀-CeO₂/rGO	25	30.5	－	［45］
Ru₁Co₁/γ-Al₂O₃	65	32.9	47	［46］

Fig.11 Recyclability test using Pt3Pd7 sample as catalyst for AB hydrolysis to produce hydrogen for five cycles

Fig.12 TEM images of Pt3Pd7 catalyst after five catalytic cycles

Fig.13 FT-IR spectrum of Pt3Pd7 nanomaterials after five catalytic cycles

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Ionic Liquid-Modulated Synthesis of Pt-Pd Bimetallic Nanomaterials and Their Catalytic Performance for Ammonia Borane Hydrolysis to Generate Hydrogen

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