Bimetallic MIL-68 for methane selective oxidation: Trade-off photon utilization and radical generation

Ke Xin Li; Weimin Huang; Qingyao Li; Hao Yuan; Shanshan Chen; Yuanhao Wang; Ralph T. Yang; Zhun Hu

doi:10.1002/aic.70312

Bimetallic MIL-68 for methane selective oxidation: Trade-off photon utilization and radical generation

Ke Xin Li
, Weimin Huang
, Qingyao Li
, Hao Yuan
, Shanshan Chen
, Yuanhao Wang
, Ralph T. Yang
, Zhun Hu

化学工程与技术学院

Xi'an Jiaotong University
University of Science and Technology Beijing
University of Michigan, Ann Arbor

科研成果: 期刊稿件 › 文章 › 同行评审

摘要

Methane selective oxidation was regarded as the “Holy Grail” reaction in C₁ chemistry but remained limited by low yield and selectivity. Here, we reported an indium-iron bimetallic catalyst (In_xFe_y) with tunable In/Fe ratios for efficient oxidation of methane to methanol. Quenching experiments revealed that photogenerated holes derived CH₄ activation, ·OOH coupled with ·CH₃ to form CH₃OH whereas ·OH caused overoxidation. Photoelectric testing indicated that Fe³⁺ incorporation increased surface electron density and Fe³⁺ centers, enhancing light absorption, charge separation, and ·CH₃/·OOH generation. Excessive Fe³⁺ shifted the HOMO positively and favored ·OH formation. In_0.6Fe_0.4 achieved an optimal balance between ·CH₃/·OOH generation and ·OH suppression, reaching the highest yield and selectivity (52.2 μmol·g⁻¹·h⁻¹, 94.3%). This work highlighted reactive species regulation and band-structure design, and provided a guideline for designing photothermal catalysts for methane selective oxidation to future demands.

源语言	英语
文章编号	e70312
期刊	AIChE Journal
卷	72
期	6
DOI	https://doi.org/10.1002/aic.70312
出版状态	已出版 - 6月 2026

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title = "Bimetallic MIL-68 for methane selective oxidation: Trade-off photon utilization and radical generation",

abstract = "Methane selective oxidation was regarded as the “Holy Grail” reaction in C1 chemistry but remained limited by low yield and selectivity. Here, we reported an indium-iron bimetallic catalyst (InxFey) with tunable In/Fe ratios for efficient oxidation of methane to methanol. Quenching experiments revealed that photogenerated holes derived CH4 activation, ·OOH coupled with ·CH3 to form CH3OH whereas ·OH caused overoxidation. Photoelectric testing indicated that Fe3+ incorporation increased surface electron density and Fe3+ centers, enhancing light absorption, charge separation, and ·CH3/·OOH generation. Excessive Fe3+ shifted the HOMO positively and favored ·OH formation. In0.6Fe0.4 achieved an optimal balance between ·CH3/·OOH generation and ·OH suppression, reaching the highest yield and selectivity (52.2 μmol·g−1·h−1, 94.3\%). This work highlighted reactive species regulation and band-structure design, and provided a guideline for designing photothermal catalysts for methane selective oxidation to future demands.",

keywords = "bandgap narrowing, metal–organic framework, photothermal catalysis, reactive oxygen species modulation, selective oxidation of methane",

author = "Li, \{Ke Xin\} and Weimin Huang and Qingyao Li and Hao Yuan and Shanshan Chen and Yuanhao Wang and Yang, \{Ralph T.\} and Zhun Hu",

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year = "2026",

month = jun,

doi = "10.1002/aic.70312",

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T1 - Bimetallic MIL-68 for methane selective oxidation

T2 - Trade-off photon utilization and radical generation

AU - Li, Ke Xin

AU - Huang, Weimin

AU - Li, Qingyao

AU - Yuan, Hao

AU - Chen, Shanshan

AU - Wang, Yuanhao

AU - Yang, Ralph T.

AU - Hu, Zhun

PY - 2026/6

Y1 - 2026/6

N2 - Methane selective oxidation was regarded as the “Holy Grail” reaction in C1 chemistry but remained limited by low yield and selectivity. Here, we reported an indium-iron bimetallic catalyst (InxFey) with tunable In/Fe ratios for efficient oxidation of methane to methanol. Quenching experiments revealed that photogenerated holes derived CH4 activation, ·OOH coupled with ·CH3 to form CH3OH whereas ·OH caused overoxidation. Photoelectric testing indicated that Fe3+ incorporation increased surface electron density and Fe3+ centers, enhancing light absorption, charge separation, and ·CH3/·OOH generation. Excessive Fe3+ shifted the HOMO positively and favored ·OH formation. In0.6Fe0.4 achieved an optimal balance between ·CH3/·OOH generation and ·OH suppression, reaching the highest yield and selectivity (52.2 μmol·g−1·h−1, 94.3%). This work highlighted reactive species regulation and band-structure design, and provided a guideline for designing photothermal catalysts for methane selective oxidation to future demands.

AB - Methane selective oxidation was regarded as the “Holy Grail” reaction in C1 chemistry but remained limited by low yield and selectivity. Here, we reported an indium-iron bimetallic catalyst (InxFey) with tunable In/Fe ratios for efficient oxidation of methane to methanol. Quenching experiments revealed that photogenerated holes derived CH4 activation, ·OOH coupled with ·CH3 to form CH3OH whereas ·OH caused overoxidation. Photoelectric testing indicated that Fe3+ incorporation increased surface electron density and Fe3+ centers, enhancing light absorption, charge separation, and ·CH3/·OOH generation. Excessive Fe3+ shifted the HOMO positively and favored ·OH formation. In0.6Fe0.4 achieved an optimal balance between ·CH3/·OOH generation and ·OH suppression, reaching the highest yield and selectivity (52.2 μmol·g−1·h−1, 94.3%). This work highlighted reactive species regulation and band-structure design, and provided a guideline for designing photothermal catalysts for methane selective oxidation to future demands.

KW - bandgap narrowing

KW - metal–organic framework

KW - photothermal catalysis

KW - reactive oxygen species modulation

KW - selective oxidation of methane

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DO - 10.1002/aic.70312

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SN - 0001-1541

VL - 72

JO - AIChE Journal

JF - AIChE Journal

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Bimetallic MIL-68 for methane selective oxidation: Trade-off photon utilization and radical generation

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