Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site

Bing An; Zhe Li; Zi Wang; Xiangdi Zeng; Xue Han; Yongqiang Cheng; Alena M. Sheveleva; Zhongyue Zhang; Floriana Tuna; Eric J.L. McInnes; Mark D. Frogley; Anibal J. Ramirez-Cuesta; Louise S. Natrajan; Cheng Wang; Wenbin Lin; Sihai Yang; Martin Schröder

doi:10.1038/s41563-022-01279-1

Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site

Bing An, Zhe Li, Zi Wang, Xiangdi Zeng, Xue Han, Yongqiang Cheng, Alena M. Sheveleva, Zhongyue Zhang, Floriana Tuna, Eric J.L. McInnes, Mark D. Frogley, Anibal J. Ramirez-Cuesta, Louise S. Natrajan, Cheng Wang, Wenbin Lin, Sihai Yang, Martin Schröder

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

107 Scopus citations

Abstract

Natural gas, consisting mainly of methane (CH₄), has a relatively low energy density at ambient conditions (~36 kJ l⁻¹). Partial oxidation of CH₄ to methanol (CH₃OH) lifts the energy density to ~17 MJ l⁻¹ and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely challenging to mimic in artificial systems due to the high dissociation energy of the C–H bond in CH₄ (439 kJ mol⁻¹) and facile over-oxidation of CH₃OH to CO and CO₂. Here we report the direct photo-oxidation of CH₄ over mono-iron hydroxyl sites immobilized within a metal–organic framework, PMOF-RuFe(OH). Under ambient and flow conditions in the presence of H₂O and O₂, CH₄ is converted to CH₃OH with 100% selectivity and a time yield of 8.81 ± 0.34 mmol g_cat⁻¹ h⁻¹ (versus 5.05 mmol g_cat⁻¹ h⁻¹ for methane monooxygenase). By using operando spectroscopic and modelling techniques, we find that confined mono-iron hydroxyl sites bind CH₄ by forming an [Fe–OH···CH₄] intermediate, thus lowering the barrier for C–H bond activation. The confinement of mono-iron hydroxyl sites in a porous matrix demonstrates a strategy for C–H bond activation in CH₄ to drive the direct photosynthesis of CH₃OH.

Original language	English
Pages (from-to)	932-938
Number of pages	7
Journal	Nature Materials
Volume	21
Issue number	8
DOIs	https://doi.org/10.1038/s41563-022-01279-1
State	Published - Aug 2022

Funding

We thank EPSRC (EP/I011870, EPSRC EP/V056409), the Royal Society and University of Manchester for funding. We thank EPSRC for funding and the EPSRC National Service for EPR Spectroscopy at Manchester. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 742401, NANOCHEM). We thank I. da Silva, B. Wang, W. Lu, Y. Ma, J. Zhang, L. Zeng, R. Wei and H. Wilson for help. We thank Diamond Light Source for access to the beamline B22. We acknowledge Advanced Photon Source (APS) at Argonne National Laboratory and Aichi Synchrotron Radiation Centre (AichiSR) for the provision of beamtime at 10-BM and BL11S. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by Oak Ridge National Laboratory (ORNL). The computing resources at ORNL were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Computer and Data Environment for Science (CADES). We thank EPSRC (EP/I011870, EPSRC EP/V056409), the Royal Society and University of Manchester for funding. We thank EPSRC for funding and the EPSRC National Service for EPR Spectroscopy at Manchester. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement no. 742401, NANOCHEM). We thank I. da Silva, B. Wang, W. Lu, Y. Ma, J. Zhang, L. Zeng, R. Wei and H. Wilson for help. We thank Diamond Light Source for access to the beamline B22. We acknowledge Advanced Photon Source (APS) at Argonne National Laboratory and Aichi Synchrotron Radiation Centre (AichiSR) for the provision of beamtime at 10-BM and BL11S. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by Oak Ridge National Laboratory (ORNL). The computing resources at ORNL were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development program and Computer and Data Environment for Science (CADES).

Funders	Funder number
Aichi Synchrotron Radiation Centre	BL11S
CADES
Laboratory Directed Research and Development program and Computer and Data Environment for Science
Office of Science
Argonne National Laboratory
Oak Ridge National Laboratory
Horizon 2020 Framework Programme	742401
Engineering and Physical Sciences Research Council	EP/V056409, EP/I011870
Royal Society
University of Manchester
European Research Council

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An, B., Li, Z., Wang, Z., Zeng, X., Han, X., Cheng, Y., Sheveleva, A. M., Zhang, Z., Tuna, F., McInnes, E. J. L., Frogley, M. D., Ramirez-Cuesta, A. J., S. Natrajan, L., Wang, C., Lin, W., Yang, S., & Schröder, M. (2022). Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site. Nature Materials, 21(8), 932-938. https://doi.org/10.1038/s41563-022-01279-1

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title = "Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site",

abstract = "Natural gas, consisting mainly of methane (CH4), has a relatively low energy density at ambient conditions (~36 kJ l−1). Partial oxidation of CH4 to methanol (CH3OH) lifts the energy density to ~17 MJ l−1 and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely challenging to mimic in artificial systems due to the high dissociation energy of the C–H bond in CH4 (439 kJ mol−1) and facile over-oxidation of CH3OH to CO and CO2. Here we report the direct photo-oxidation of CH4 over mono-iron hydroxyl sites immobilized within a metal–organic framework, PMOF-RuFe(OH). Under ambient and flow conditions in the presence of H2O and O2, CH4 is converted to CH3OH with 100% selectivity and a time yield of 8.81 ± 0.34 mmol gcat−1 h−1 (versus 5.05 mmol gcat−1 h−1 for methane monooxygenase). By using operando spectroscopic and modelling techniques, we find that confined mono-iron hydroxyl sites bind CH4 by forming an [Fe–OH···CH4] intermediate, thus lowering the barrier for C–H bond activation. The confinement of mono-iron hydroxyl sites in a porous matrix demonstrates a strategy for C–H bond activation in CH4 to drive the direct photosynthesis of CH3OH.",

author = "Bing An and Zhe Li and Zi Wang and Xiangdi Zeng and Xue Han and Yongqiang Cheng and Sheveleva, {Alena M.} and Zhongyue Zhang and Floriana Tuna and McInnes, {Eric J.L.} and Frogley, {Mark D.} and Ramirez-Cuesta, {Anibal J.} and {S. Natrajan}, Louise and Cheng Wang and Wenbin Lin and Sihai Yang and Martin Schr{\"o}der",

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doi = "10.1038/s41563-022-01279-1",

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T1 - Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site

AU - An, Bing

AU - Li, Zhe

AU - Wang, Zi

AU - Zeng, Xiangdi

AU - Han, Xue

AU - Cheng, Yongqiang

AU - Sheveleva, Alena M.

AU - Zhang, Zhongyue

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Frogley, Mark D.

AU - Ramirez-Cuesta, Anibal J.

AU - S. Natrajan, Louise

AU - Wang, Cheng

AU - Lin, Wenbin

AU - Yang, Sihai

AU - Schröder, Martin

PY - 2022/8

Y1 - 2022/8

N2 - Natural gas, consisting mainly of methane (CH4), has a relatively low energy density at ambient conditions (~36 kJ l−1). Partial oxidation of CH4 to methanol (CH3OH) lifts the energy density to ~17 MJ l−1 and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely challenging to mimic in artificial systems due to the high dissociation energy of the C–H bond in CH4 (439 kJ mol−1) and facile over-oxidation of CH3OH to CO and CO2. Here we report the direct photo-oxidation of CH4 over mono-iron hydroxyl sites immobilized within a metal–organic framework, PMOF-RuFe(OH). Under ambient and flow conditions in the presence of H2O and O2, CH4 is converted to CH3OH with 100% selectivity and a time yield of 8.81 ± 0.34 mmol gcat−1 h−1 (versus 5.05 mmol gcat−1 h−1 for methane monooxygenase). By using operando spectroscopic and modelling techniques, we find that confined mono-iron hydroxyl sites bind CH4 by forming an [Fe–OH···CH4] intermediate, thus lowering the barrier for C–H bond activation. The confinement of mono-iron hydroxyl sites in a porous matrix demonstrates a strategy for C–H bond activation in CH4 to drive the direct photosynthesis of CH3OH.

AB - Natural gas, consisting mainly of methane (CH4), has a relatively low energy density at ambient conditions (~36 kJ l−1). Partial oxidation of CH4 to methanol (CH3OH) lifts the energy density to ~17 MJ l−1 and drives the production of numerous chemicals. In nature, this is achieved by methane monooxygenase with di-iron sites, which is extremely challenging to mimic in artificial systems due to the high dissociation energy of the C–H bond in CH4 (439 kJ mol−1) and facile over-oxidation of CH3OH to CO and CO2. Here we report the direct photo-oxidation of CH4 over mono-iron hydroxyl sites immobilized within a metal–organic framework, PMOF-RuFe(OH). Under ambient and flow conditions in the presence of H2O and O2, CH4 is converted to CH3OH with 100% selectivity and a time yield of 8.81 ± 0.34 mmol gcat−1 h−1 (versus 5.05 mmol gcat−1 h−1 for methane monooxygenase). By using operando spectroscopic and modelling techniques, we find that confined mono-iron hydroxyl sites bind CH4 by forming an [Fe–OH···CH4] intermediate, thus lowering the barrier for C–H bond activation. The confinement of mono-iron hydroxyl sites in a porous matrix demonstrates a strategy for C–H bond activation in CH4 to drive the direct photosynthesis of CH3OH.

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VL - 21

SP - 932

EP - 938

JO - Nature Materials

JF - Nature Materials

IS - 8

ER -

Direct photo-oxidation of methane to methanol over a mono-iron hydroxyl site

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