title: Intracrystalline diffusion in metal organic framework during heterogeneous catalysis: influence of particle size on the activity of MIL-100 (Fe) for oxidation reactions.
abstract: Three MIL-100 (Fe) samples differing in average crystal size (from 60-70 to >400 nm) have been synthesized by microwave heating using three HF/Fe(3+) ratios. Oxidation of diphenylmethane with tert-butylhydroperoxide (TBHP) and thiophenol with oxygen are catalyzed by three MIL-100 (Fe) samples with similar reaction rates regardless of its average particle size. In contrast, the activity of the three MIL-100 (Fe) samples for the oxidation of bulky triphenylmethane by TBHP largely depends on the average crystal size of the sample: the smaller the average particle size, the larger the initial reaction rate of triphenylmethane oxidation. These results show that diffusion limitation takes place on MOF catalysis depending on the substrate size and provides indirect evidence that these reactions take place inside the intracrystalline space of the porous catalysts.
authors: Instituto Universitario de Tecnología Química CSIC-UPV and Departamento de Química, Universidad Politécnica de Valencia, Av., De los Naranjos s/n, 46022, Valencia, Spain.
authors: Amarajothi
authors: A
authors: Dhakshinamoorthy
authors: Mercedes
authors: M
authors: Alvaro
authors: Young Kyu
authors: YK
authors: Hwang
authors: You-Kyong
authors: YK
authors: Seo
authors: Avelino
authors: A
authors: Corma
authors: Hermenegildo
authors: H
authors: Garcia
mesh_terms: D001559:Benzhydryl Compounds / Q000737:chemistry; D002384:Catalysis; D004058:Diffusion; D005290:Ferric Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D010316:Particle Size; D010636:Phenols / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry; D020122:tert-Butylhydroperoxide / Q000737:chemistry
chemical_list: D001559:Benzhydryl Compounds; D005290:Ferric Compounds; D008670:Metals; D009930:Organic Chemicals; D010636:Phenols; D013438:Sulfhydryl Compounds; C042983:thiophenol; D020122:tert-Butylhydroperoxide; C010129:diphenylmethane; D010100:Oxygen