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

Department of Chemical and Biological Engineering

Xi'an Jiaotong University
University of Science and Technology Beijing

Research output: Contribution to journal › Article › peer-review

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 (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.

Original language	English
Article number	e70312
Journal	AIChE Journal
Volume	72
Issue number	6
DOIs	https://doi.org/10.1002/aic.70312
State	Published - Jun 2026

Keywords

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

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@article{2ecd0913b68a4010a8ce2ab57a566865,

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",

note = "Publisher Copyright: {\textcopyright} 2026 American Institute of Chemical Engineers.",

year = "2026",

month = jun,

doi = "10.1002/aic.70312",

language = "English",

volume = "72",

journal = "AIChE Journal",

issn = "0001-1541",

publisher = "American Institute of Chemical Engineers",

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TY - JOUR

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

UR - https://www.scopus.com/pages/publications/105037663080

U2 - 10.1002/aic.70312

DO - 10.1002/aic.70312

M3 - Article

AN - SCOPUS:105037663080

SN - 0001-1541

VL - 72

JO - AIChE Journal

JF - AIChE Journal

IS - 6

M1 - e70312

ER -

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

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