Modulation of Single-Iron-Atom Coordination Environment Toward Three-Electron Oxygen Reduction for Photocatalytic CH4 Conversion to CH3OH

Laiquan Li; Xiuwen Shi; Lingyue Liu; Ying Tu; Yuhang Liu; Yuhang Zhang; Hong Bin Yang; Shixue Dou; Bin Liu

doi:10.1002/smll.202500835

Modulation of Single-Iron-Atom Coordination Environment Toward Three-Electron Oxygen Reduction for Photocatalytic CH₄ Conversion to CH₃OH

Laiquan Li^* (Co-first Author)
, Xiuwen Shi (Co-first Author)
, Lingyue Liu (Co-first Author)
, Ying Tu
, Yuhang Liu
, Yuhang Zhang
, Hong Bin Yang^*
, Shixue Dou
, Bin Liu^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

8 Citations (Scopus)

Abstract

By modifying the coordination environment of single-Fe-atom active site, effective regulation of the photocatalytic oxygen reduction pathway can be achieved to attain high activity for photocatalytic oxidation of CH₄ to CH₃OH in an aqueous solution. A comprehensive investigation is conducted to study the impact of different coordination numbers of single Fe atoms on photocatalytic CH₄ oxidation reaction over carbon nitride. Among which, Fe₁/C_3-xN₄ with a Fe-N3 coordination exhibit an exceptional photocatalytic performance in CH₄ oxidation, reaching a remarkable methanol yield of 928.27 µmol g_cat⁻¹, much higher than Fe₁/C₃N₄ and Fe₁/C₃N_4-x (308.47 and 473.26 µmol g_cat⁻¹, respectively). Based on a collection of in situ characterizations and time-dependent density functional theory calculations, it is determined that Fe₁/C_3-xN₄ with an optimal coordination number possesses the optimized electronic configuration that enables three-electron oxygen reduction to generate hydroxyl radicals for photocatalytic conversion of CH₄ to CH₃OH. © 2025 Wiley-VCH GmbH.

Original language	English
Article number	2500835
Number of pages	10
Journal	Small
Volume	21
Issue number	11
Online published	11 Feb 2025
DOIs	https://doi.org/10.1002/smll.202500835
Publication status	Published - 19 Mar 2025

Funding

L.L., X.S., and L.L. contributed equally to this work. This work was supported by the National Natural Science Foundation of China (22405173, 22475145), the Natural Science Foundation of Jiangsu Province (BK20210870), the City University of Kong Hong startup fund (9020003), ITF–RTH–Global STEM Professorship (9446006), JC STEM lab of Advanced CO2 Upcycling (9228005), the NSFC Center for Single-Atom Catalysis (22388102) and Photon Science Research center for Carbon Dioxide.

Research Keywords

3e− ORR
CH4 oxidation
coordination environment
photocatalysis
single atom catalyst

RGC Funding Information

RGC-funded

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10.1002/smll.202500835

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Cite this

@article{581e0da0075a464aab6dde0bb702f150,

title = "Modulation of Single-Iron-Atom Coordination Environment Toward Three-Electron Oxygen Reduction for Photocatalytic CH4 Conversion to CH3OH",

abstract = "By modifying the coordination environment of single-Fe-atom active site, effective regulation of the photocatalytic oxygen reduction pathway can be achieved to attain high activity for photocatalytic oxidation of CH4 to CH3OH in an aqueous solution. A comprehensive investigation is conducted to study the impact of different coordination numbers of single Fe atoms on photocatalytic CH4 oxidation reaction over carbon nitride. Among which, Fe1/C3-xN4 with a Fe-N3 coordination exhibit an exceptional photocatalytic performance in CH4 oxidation, reaching a remarkable methanol yield of 928.27 µmol gcat−1, much higher than Fe1/C3N4 and Fe1/C3N4-x (308.47 and 473.26 µmol gcat−1, respectively). Based on a collection of in situ characterizations and time-dependent density functional theory calculations, it is determined that Fe1/C3-xN4 with an optimal coordination number possesses the optimized electronic configuration that enables three-electron oxygen reduction to generate hydroxyl radicals for photocatalytic conversion of CH4 to CH3OH. {\textcopyright} 2025 Wiley-VCH GmbH.",

keywords = "3e− ORR, CH4 oxidation, coordination environment, photocatalysis, single atom catalyst",

author = "Laiquan Li and Xiuwen Shi and Lingyue Liu and Ying Tu and Yuhang Liu and Yuhang Zhang and Yang, \{Hong Bin\} and Shixue Dou and Bin Liu",

year = "2025",

month = mar,

day = "19",

doi = "10.1002/smll.202500835",

language = "English",

volume = "21",

journal = "Small",

issn = "1613-6810",

publisher = "Wiley-VCH Verlag GmbH",

number = "11",

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Modulation of Single-Iron-Atom Coordination Environment Toward Three-Electron Oxygen Reduction for Photocatalytic CH₄ Conversion to CH₃OH. / Li, Laiquan (Co-first Author); Shi, Xiuwen (Co-first Author); Liu, Lingyue (Co-first Author) et al.
In: Small, Vol. 21, No. 11, 2500835, 19.03.2025.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Modulation of Single-Iron-Atom Coordination Environment Toward Three-Electron Oxygen Reduction for Photocatalytic CH4 Conversion to CH3OH

AU - Li, Laiquan

AU - Shi, Xiuwen

AU - Liu, Lingyue

AU - Tu, Ying

AU - Liu, Yuhang

AU - Zhang, Yuhang

AU - Yang, Hong Bin

AU - Dou, Shixue

AU - Liu, Bin

PY - 2025/3/19

Y1 - 2025/3/19

N2 - By modifying the coordination environment of single-Fe-atom active site, effective regulation of the photocatalytic oxygen reduction pathway can be achieved to attain high activity for photocatalytic oxidation of CH4 to CH3OH in an aqueous solution. A comprehensive investigation is conducted to study the impact of different coordination numbers of single Fe atoms on photocatalytic CH4 oxidation reaction over carbon nitride. Among which, Fe1/C3-xN4 with a Fe-N3 coordination exhibit an exceptional photocatalytic performance in CH4 oxidation, reaching a remarkable methanol yield of 928.27 µmol gcat−1, much higher than Fe1/C3N4 and Fe1/C3N4-x (308.47 and 473.26 µmol gcat−1, respectively). Based on a collection of in situ characterizations and time-dependent density functional theory calculations, it is determined that Fe1/C3-xN4 with an optimal coordination number possesses the optimized electronic configuration that enables three-electron oxygen reduction to generate hydroxyl radicals for photocatalytic conversion of CH4 to CH3OH. © 2025 Wiley-VCH GmbH.

AB - By modifying the coordination environment of single-Fe-atom active site, effective regulation of the photocatalytic oxygen reduction pathway can be achieved to attain high activity for photocatalytic oxidation of CH4 to CH3OH in an aqueous solution. A comprehensive investigation is conducted to study the impact of different coordination numbers of single Fe atoms on photocatalytic CH4 oxidation reaction over carbon nitride. Among which, Fe1/C3-xN4 with a Fe-N3 coordination exhibit an exceptional photocatalytic performance in CH4 oxidation, reaching a remarkable methanol yield of 928.27 µmol gcat−1, much higher than Fe1/C3N4 and Fe1/C3N4-x (308.47 and 473.26 µmol gcat−1, respectively). Based on a collection of in situ characterizations and time-dependent density functional theory calculations, it is determined that Fe1/C3-xN4 with an optimal coordination number possesses the optimized electronic configuration that enables three-electron oxygen reduction to generate hydroxyl radicals for photocatalytic conversion of CH4 to CH3OH. © 2025 Wiley-VCH GmbH.

KW - 3e− ORR

KW - CH4 oxidation

KW - coordination environment

KW - photocatalysis

KW - single atom catalyst

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U2 - 10.1002/smll.202500835

DO - 10.1002/smll.202500835

M3 - RGC 21 - Publication in refereed journal

SN - 1613-6810

VL - 21

JO - Small

JF - Small

IS - 11

M1 - 2500835

ER -

Modulation of Single-Iron-Atom Coordination Environment Toward Three-Electron Oxygen Reduction for Photocatalytic CH₄ Conversion to CH₃OH

Abstract

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Research Keywords

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Don-HKJC: JC STEM Lab of Advanced C02 Upcycling

ITF-RTH: GSP212 - Research Talent Hub

RMGS: On-site Green Hydrogen Production and Storage for Distributed Carbon Neutral Applications

Cite this

Modulation of Single-Iron-Atom Coordination Environment Toward Three-Electron Oxygen Reduction for Photocatalytic CH4 Conversion to CH3OH

Abstract

Funding

Research Keywords

RGC Funding Information

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

Projects

Don-HKJC: JC STEM Lab of Advanced C02 Upcycling

ITF-RTH: GSP212 - Research Talent Hub

RMGS: On-site Green Hydrogen Production and Storage for Distributed Carbon Neutral Applications

Cite this

Modulation of Single-Iron-Atom Coordination Environment Toward Three-Electron Oxygen Reduction for Photocatalytic CH₄ Conversion to CH₃OH