Affiliation:
1. Institute for New Energy Materials and Low Carbon Technologies School of Materials Science & Engineering Tianjin University of Technology 391 West Binshui Road Tianjin 300384 China
2. State Key Laboratory of Elemento‐Organic Chemistry College of Chemistry Nankai University 94 Weijin Road Tianjin 300071 China
3. Department of Chemistry The Hong Kong University of Science and Technology Clear Water Bay Hong Kong 999077 China
Abstract
AbstractDirect methane conversion to value‐added oxygenates under mild conditions with in‐depth mechanism investigation has attracted wide interest. Inspired by methane monooxygenase, the K9Na2Fe(H2O)2{[γ‐SiW9O34Fe(H2O)]}2·25H2O polyoxometalate (Fe‐POM) with well‐defined Fe(H2O)2 sites is synthesized to clarify the key role of Fe species and their microenvironment toward CH4 photooxidation. The Fe‐POM can efficiently drive the conversion of CH4 to HCOOH with a yield of 1570.0 µmol gPOM−1 and 95.8% selectivity at ambient conditions, much superior to that of [Fe(H2O)SiW11O39]5− with Fe(H2O) active site, [Fe2SiW10O38(OH)]214− and [P8W48O184Fe16(OH)28(H2O)4]20− with multinuclear Fe−OH−Fe active sites. Single‐dispersion of Fe‐POM on polymeric carbon nitride (PCN) is facilely achieved to provide single‐cluster functionalized PCN with well‐defined Fe(H2O)2 site, the HCOOH yield can be improved to 5981.3 µmol gPOM−1. Systemic investigations demonstrate that the (WO)4−Fe(H2O)2 can supply Fe═O active center for C−H activation via forming (WO)4−Fea−Ot···CH4 intermediate, similar to that for CH4 oxidation in the monooxygenase. This work highlights a promising and facile strategy for single dispersion of ≈1–2 Å metal center with precise coordination microenvironment by uniformly anchoring nanoscale molecular clusters, which provides a well‐defined model for in‐depth mechanism research.
Funder
National Natural Science Foundation of China
Natural Science Foundation of Tianjin Municipal Science and Technology Commission
Cited by
1 articles.
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