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


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Article Info

DATE

2022-06-30

AUTHORS

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

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. More... »

PAGES

932-938

Identifiers

URI

http://scigraph.springernature.com/pub.10.1038/s41563-022-01279-1

DOI

http://dx.doi.org/10.1038/s41563-022-01279-1

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1149104594

PUBMED

https://www.ncbi.nlm.nih.gov/pubmed/35773491


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20 schema:description 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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26 schema:keywords CH3OH
27 CH4
28 CO
29 CO2
30 H bond activation
31 H bonds
32 H2O
33 MJ
34 O2
35 PMOF
36 activation
37 ambient
38 ambient conditions
39 artificial systems
40 barriers
41 bond activation
42 bonds
43 chemicals
44 conditions
45 confinement
46 density
47 di-iron site
48 direct photosynthesis
49 dissociation energies
50 energy
51 energy density
52 facile
53 flow conditions
54 framework
55 gas
56 high dissociation energy
57 hydroxyl sites
58 low energy density
59 matrix
60 metal-organic frameworks
61 methane
62 methane monooxygenase
63 monooxygenase
64 natural gas
65 nature
66 numerous chemicals
67 operando
68 oxidation
69 oxidation of CH3OH
70 partial oxidation
71 photosynthesis
72 porous matrix
73 presence
74 presence of H2O
75 production
76 selectivity
77 sites
78 strategies
79 system
80 technique
81 time yield
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