Synergetic photocatalytic and thermocatalytic reforming of methanol for hydrogen production based on Pt@TiO2 catalyst

doi:10.1016/S1872-2067(21)63963-3

Abstract

Abstract:

In order to efficiently produce H₂, conventional methanol-water thermocatalytic (TC) reforming requires a very high temperature due to high Gibbs free energy, while the energy conversion efficiency of methanol-water photocatalytic (PC) reforming is far from satisfaction because of the kinetic limitation. To address these issues, herein, we incorporate PC and TC processes together in a specially designed reactor and realize simultaneous photocatalytic/thermocatalytic (PC-TC) reforming of methanol in an aqueous phase. Such a design facilitates the synergetic effect of the PC and TC process for H₂ production due to a lower energy barrier and faster reaction kinetics. The methanol-water reforming based on the optimized 0.05%Pt@TiO₂catalyst delivers an outstanding H₂ production rate in the PC-TC process (5.66 μmol H₂·g^‒1 catalyst·s^‒1), which is about 3 and 7 times than those of the TC process (1.89 μmol H₂·g^‒1 catalyst·s^‒1) and the PC process (0.80 μmol H₂·g^‒1 catalyst·s^‒1), respectively. Isotope tracer experiments, active intermediate trapping experiments, and theoretical calculations demonstrate that the photo-generated holes and hydroxyl radicals could enhance the methanol dehydrogenation, water molecule splitting, and water-gas shift reaction, while high temperature accelerates reaction kinetics. The proposed PC-TC reforming of methanol for hydrogen production can be a promising technology to solve the energy and environmental issue in the closed-loop hydrogen economy in the near future.

Key words: Aqueous-phase reforming, Photocatalysis, Thermocatalysis, Pt@TiO₂ catalyst, Methanol, Hydrogen

Lei Li, Wenjun Ouyang, Zefeng Zheng, Kaihang Ye, Yuxi Guo, Yanlin Qin, Zhenzhen Wu, Zhan Lin, Tiejun Wang, Shanqing Zhang. Synergetic photocatalytic and thermocatalytic reforming of methanol for hydrogen production based on Pt@TiO₂ catalyst[J]. Chinese Journal of Catalysis, 2022, 43(5): 1258-1266.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63963-3

https://www.cjcatal.com/EN/Y2022/V43/I5/1258

Figures/Tables 8

Scheme 1. Schematic illustration of the hydrogen production process.

Fig. 1. Hydrogen production from MeOH/water over Pt@TiO2 catalysts. (a) Reaction rates of H2 over x%Pt@TiO2 (x = 0.05, 0.1, 0.2, 0.5) under PC, TC and PC-TC conditions; (b) ATOF of H2 over x%Pt@TiO2 (x = 0.05, 0.1, 0.2, 0.5) under PC, TC and PC-TC conditions. Reaction conditions: n(CH3OH):n(H2O)=1:3, 40 mL total volume of liquid, 50 mg catalysts, 190 °C; reaction for 1.25 h; 2.0 MPa N2.

Fig. 2. Morphology characterizations of x%Pt@TiO2. (a?d) TEM image of x%Pt@TiO2 (x = 0.05, 0.1, 0.2, 0.5); (e) HRTEM image of 0.05%Pt@TiO2; (f) PXRD patterns of the x%Pt@TiO2 (x = 0.05, 0.1, 0.2, 0.5) samples.

Fig. 3. The characterizations of x%Pt@TiO2 catalysts. (a) Raman spectra of x%Pt@TiO2 (x = 0.05, 0.1, 0.2); (b) EPR profiles of TiO2 and 0.05%Pt@TiO2; (c,d) High-resolution XPS spectra for O 2s and Ti 2p of 0.1%Pt@TiO2.

Fig. 4. The photo-related properties of x% Pt@TiO2. (a) Tauc plot for the band gap calculation of TiO2 and 0.1%Pt@TiO2; (b) Schematic illustration for the electronic structures of TiO2 and 0.1%Pt@TiO2; (c) VB XPS spectra of TiO2 and 0.1%Pt@TiO2; (d) Photocurrent of TiO2 and 0.05%Pt@TiO2.

Fig. 5. (a) TC and PC-TC H2 production rates over 0.5%Pt@TiO2 catalyst at various temperatures; (b) Arrhenius plot of TC and PC-TC performance over 0.5%Pt@TiO2 catalyst at various temperatures.

Fig. 6. Reaction rates values of H2 were obtained under PC (a), TC (b), PC-TC (c) catalytic conditions with hydroxyl radical and hole scavenger.

Scheme 2. Proposed reaction mechanisms of H2 production in the TC (up) and PC-TC (down) process.

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Synergetic photocatalytic and thermocatalytic reforming of methanol for hydrogen production based on Pt@TiO₂ catalyst

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