Photocatalytic methane activation by dual reaction sites co-modified WO3

doi:10.1016/S1872-2067(22)64169-X

Abstract

Abstract:

Methane (CH₄) upgrading into liquid oxygenates under mild conditions is of great significance to sustainable energy and clean environment, whilst holds great challenges of achieving superior activity and selectivity. Herein, tungsten oxide (WO₃) modified with palladium (Pd) nanoparticles and oxygen vacancies (OVs) was employed as dual reaction sites to drive CH₄ conversion with O₂ at room temperature. Optimized Pd_0.5-def-WO₃ photocatalyst enables almost 33 times improvement in oxygenates production compared with WO₃, with a yield of 7018 μmol·g^-1·h^-1, and a high selectivity of 81% towards primary products (CH₃OH and CH₃OOH), which is superior to most of the previous reported. In-situ XPS spectra proved Pd nanoparticles were the hole acceptors based on the shift of Pd₃_d to high binding energy under light irradiation. The in-situ solid-state EPR spectra demonstrate an enhancement of OVs signal which proves the role of OVs as the electron acceptors. Consequently, efficient charge separation has been achieved, contributing to the superior activity and selectivity for CH₄ conversion.

Key words: Photocatalytic methane conversion, ocatalyst, Tungsten oxide, Oxygen vacancies

Keran Wang, Lei Luo, Chao Wang, Junwang Tang. Photocatalytic methane activation by dual reaction sites co-modified WO₃[J]. Chinese Journal of Catalysis, 2023, 46: 103-112.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64169-X

https://www.cjcatal.com/EN/Y2023/V46/I3/103

Figures/Tables 7

Fig. 1. XRD patterns (a) and EPR spectra (b) of WO3, def-WO3, Pd0.5-def-WO3 and Pd0.5-WO3. High-resolution W 4f (c) and O 1s (d) XPS spectra of WO3 and Pd0.5-def-WO3.

Fig. 2. HRTEM images (a,b), and EDS-mapping images (c-e) of Pd0.5-def-WO3. Tungsten (c), palladium (d), and oxygen (e) elements were represented by red, green and blue colors, respectively. HAADF-STEM image (f) and O-K EELS at different positions (g) on amorphous layer of Pd0.5-def-WO3. Positions 1, 2 and 3 were three different positions on amorphous layer in (f).

Fig. 3. (a) Photocatalytic CH4 conversion over WO3, def-WO3, Pdx-def-WO3 and Pd0.5-WO3 photocatalysts. Reaction conditions: 20 mg catalyst, 100 mL H2O, 1.9 MPa CH4, 0.1 MPa O2, 2 h, 25 °C, 100 mW·cm-2. Investigation on effects of molar ratio of CH4 to O2 (b) and H2O amount (c).

Fig. 4. (a) UV-DRS spectra of different photocatalysts. (b) In-situ Pd 3d XPS spectra of Pd0.5-def-WO3 in dark and under light irradiation. (c) In-situ solid-state EPR spectra of def-WO3 in dark and under light irradiation; Steady-state PL spectra (d), transient photocurrent responses (e) and EIS plots (f) of different photocatalysts.

Fig. 5. (a) In-situ EPR spectra to monitor of DMPO-OOH over Pd0.5-def-WO3 in CH3OH solution. (b) First-order kinetic constant of NBT photodegradation reaction for detection of ·OOH radicals formation. (c) In-situ EPR spectra to monitor of DMPO-OH over Pd0.5-def-WO3 in water. (d) PL spectra of the as-generated 7-HC over different photocatalysts.

Fig. 6. GC-MS spectra of the generated CH3OH over Pd0.5-def-WO3 with 18O2 + H216O or 16O2 + H218O in photocatalytic CH4 oxidation.

Scheme 1. Proposed reaction process of photocatalytic CH4 oxidation over Pd0.5-def-WO3 with O2 as the oxidant.

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Photocatalytic methane activation by dual reaction sites co-modified WO₃

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