研究背景

综述目录

1. Introduction

2. Thermal-catalytic methane hydroxylation

    2.1. Cu- and Fe-based catalysts

    2.2. AuPd based catalysts

    2.3. Metal-oxo based catalysts

3. Photo-catalytic methane hydroxylation

    3.1. Metal oxide semiconductor catalysts

    3.2. Hybrid semiconductor catalysts

4. Electro-catalytic methane hydroxylation

5. Conclusion and perspective

    5.1. Design of efficient catalysts

    5.2. Construction of optimal reaction systems

    5.3. Advanced characterization and artificial intelligence (AI) assistance

图文导读

• Fig. 1. Schematic illustration of low-temperature methane hydroxylation with nearly 100% selectivity in thermal-, photo- and electro-activation

• Table 1. Representative works on low temperature methane hydroxylation with nearly total selectivity

• Fig. 2. (a) Yields of products during the transformation of CH₄ catalyzed by 0.01%, 0.10%, and 2% (mass) Pd/ZSM-5 at 50 °C. Catalytic performance of (b) 0.01% Pd/ZSM-5 at 50, 70, and 95 °C, and (c) 0.01 % Pd/ZSM-5 loaded with 2% (mass) CuO at 50, 70, and 95 °C. (d) Proposed scheme of reaction pathway for direct methane oxidation over Cu-BTC-P-235 using H₂O₂. (e) Structure of the Fe₁/Cu₁–C₃N_x. (f) Catalytic performance of DSOM on Fe₁–C₃N_x, Fe₁/Cu₁–C₃N_x, Cu₁–C₃N_x, and C₃N_x.

• Fig. 3. (a-c) Models and TEM images of the AuPd@ZSM-5-R catalysts. (d) Reaction performance for the oxidation of methane with H₂ and O₂ over various catalysts. (e) Structural model of four Pd_xAu_y nanosheet. (f) The relationship of the coverage of Au atoms dotted Pd surface to the energy barrier of H₂O₂ decomposition.

• Fig. 4. (a) Room-temperature CH₄ conversion by O₂ over the MoS₂ and MMO catalysts. (b) The catalytic performance of ER-MoS₂ catalyst at different CH₄ partial pressures. (c) The reversible reduction/oxidation of Pd/CsPMA at room temperature. (d) Methanol productivity for different POM-based catalysts.

• Fig. 5. (a) The schematic description of three-dimensional structure of UiO-66-X (-X= -NH₂, -H, and -NO₂) based MOFs. (b) The relationship of the Bader charge of adsorbed •OH, the energy barrier for CH₄ activation and the specific activity for the DSOM reaction with the electronic property of Zr-oxo nodes (the Zr-O bond position according to Raman spectra) over the UiO-66-X catalysts. (c) The total energy and the initial and the final snapshots of Ab initio molecular dynamics (AIMD) simulation on the structure evolution of Zr-oxo nodes with high •OH concentration at 25 °C. (d) The linear relationship between the p-band centers of reactive oxygenic sites on (•OH)* /UiO-66-H and the barrier energies of RDSs (E_RDS) for the DSOM reaction, as well as the adsorption energies (E_ads) of CH₄. (e) Structure of the Ru₁/UiO-66 catalyst in aqueous solution. (f) Activation of CH₄ on Ru₁=O* and Zr_oxo−•OH* sites under the presence of •OOH species. (g) Relative intensity of •OH and •OOH (•O₂⁻) over Ru₁/UiO-66 and Ru₁/AC, respectively.

• Fig. 6. (a) Mechanism illustration for photo-catalytic CH₄ conversion based on Au_x/ZnO. (b) Proposed reaction process of photo-catalytic CH₄ oxidation on Au/TiO₂ and Au-CoO_x/TiO₂ using O₂ as the oxidant. (c) Proposed reaction mechanism for HCHO generation over c-WO₃. (d) HRTEM image of the ZnO/Fe₂O₃ porous nanosheets. (e) Proposed mechanism of photo-catalytic conversion of CH₄ to HCHO or CH₃OH on Au₁/In₂O₃ or AuNPs/In₂O₃, respectively.

• Fig. 7. (a) Schematic representation for the possible reaction mechanism of selective CH₄ partial photooxidation to CH₃OOH over 0.75FeCA800-4 under atmospheric pressure and mild temperature. (b) Design and synthesis of the PMOF-RuFe(OH) catalyst and the flow reactor for photo-oxidation of CH₄ to CH₃OH. (c) Isotope labeling, in situ DRIFTS spectra of BN under light irradiation with the introduction of CH₄, O₂, and H₂O mixtures. (d) Schematic illustration of oxygen activation on BP nanosheets and reaction path for partial oxidation of methane over Au₁/BP nanosheets under light irradiation.

• Fig. 8. (a) The reaction process of electrochemical oxidation of methane gas. (b) Catalytic properties of the Sn_0.9In_0.1P₂O₇ + Pd-Au-Cu/C mixed catalyst. (c) Possible reaction pathways for methane oxidation and OER in an aqueous electrolyte where M represents TMO.

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