Photocatalytic selective oxidation of the terminal methyl group of dodecane with molecular oxygen over atomically dispersed Ti in a mesoporous SiO2 matrix

Kim, Jae Yul; Jang, Ji‐Wook; Youn, Duck Hyun; Kim, Eun Sun; Choi, Sun Hee; Shin, Tae Joo; Lee, Jae Sung

doi:10.1039/c3gc41343h

Cited by 10 publications

(10 citation statements)

References 36 publications

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“…Notably, for the linear aliphatic alkanes (from C 5 to C 8 ), the reaction rate increased as the carbon chain length increased, which could be ascribed to the more stable alkyl radical intermediates.F or the longer alkanes (C 10 and C 16 ), the dramatically decreased activity might be originated from the diffusion limitations and steric hindrances owing to larger size and higher viscosity of substrates.B esides,l inear ketones appeared as the dominant products with the secondary C À H bonds cleaved, which generally have lower BDEs than the terminal ones. [28] Interaction of Catalysts with Hydrocarbons ADFT study was conducted to investigate the electronic structure of halide perovskite and its interactions with hydrocarbons (Supporting Information, Figures S13-S17 and Tables S6, S7). Figure 4s hows modeling of as table Cs 12 Bi 14 Br 54 cluster with BiBr 3 and BiBr 5 motifs on the surface (size ca.…”

Section: Catalyst Characterizationmentioning

confidence: 99%

A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation

et al. 2020

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Direct selective oxidation of hydrocarbons to oxygenates by O2 is challenging. Catalysts are limited by the low activity and narrow application scope, and the main focus is on active C−H bonds at benzylic positions. In this work, stable, lead‐free, Cs3Bi2Br9 halide perovskites are integrated within the pore channels of mesoporous SBA‐15 silica and demonstrate their photocatalytic potentials for C−H bond activation. The composite photocatalysts can effectively oxidize hydrocarbons (C5 to C16 including aromatic and aliphatic alkanes) with a conversion rate up to 32900 μmol gcat−1 h−1 and excellent selectivity (>99 %) towards aldehydes and ketones under visible‐light irradiation. Isotopic labeling, in situ spectroscopic studies, and DFT calculations reveal that well‐dispersed small perovskite nanoparticles (2–5 nm) possess enhanced electron–hole separation and a close contact with hydrocarbons that facilitates C(sp3)−H bond activation by photoinduced charges.

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Section: Catalyst Characterizationmentioning

confidence: 99%

A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation

et al. 2020

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“…This technique can be used to modify different supports, such as membranes, to produce photocatalytic membranes, control their porosity [12][13][14][15], and eliminate surface defects. The combination of silicon dioxide (SiO 2 ) and TiO 2 has been reported to improve the photocatalytic activity of TiO 2 [16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Solvent-Free Process for the Development of Photocatalytic Membranes

et al. 2019

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This work described a new sustainable method for the fabrication of ceramic membranes with high photocatalytic activity, through a simple sol-gel route. The photocatalytic surfaces, prepared at low temperature and under solvent-free conditions, exhibited a narrow pore size distribution and homogeneity without cracks. These surfaces have shown a highly efficient and reproducible behavior for the degradation of methylene blue. Given their characterization results, the microfiltration photocatalytic membranes produced in this study using solvent-free conditions are expected to effectively retain microorganisms, such as bacteria and fungi that could then be inactivated by photocatalysis.

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“…It was observed that the actual OA conversion and AA yield almost matched the predicted conversion and yield. The advantage of the present conditions compared to the previously described chemical routes (i.e., oxidation by photocatalyst [23], catalytic Shilov [24] and molecular-sieve catalyst [25]) was found to be the total selectivity towards carboxylic acid and the high conversion rate of the starting material. In addition, the purification of high melting point azelaic acid (~ 382-384 K) may be carried out through the process of crystallization by separating the low melting point mother-liquor consisting of AcOH, OA and PA (< 290 K) along with soluble catalysts (i.e., Co(OAc) 2 ·4H 2 O, Mn(OAc) 2 ·4H 2 O and HBr).…”

Section: Effect Of Catalyst Loadingmentioning

confidence: 78%

“…The chemical route for this reaction is a very challenging one. In this regard, photocatalytic oxidation [23], catalytic Shilov [24] and the molecular-sieve catalyst [25] were important for the selective oxidation of the terminal methyl group in the alkane. Catalytic Shilov leads to the hydroxylation of the terminal methyl group, whereas photocatalytic and catalytic conditions lead to a mixture of different oxidation products: aldehydes, acids and ketones on the terminal group.…”

Section: Introductionmentioning

confidence: 99%

Liquid Phase Selective Catalytic Oxidation of Oleic Acid to Azelaic Acid Using Air and Transition Metal Acetate Bromide Complex

Hajra

Sultana

Guria

et al. 2017

J Americ Oil Chem Soc

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Industrially important di‐carboxylic acids are synthesized from mono‐carboxylic unsaturated and unsaturated fatty acids. In this study, the aim is to perform the simultaneous catalytic oxidative C=C cleavage of oleic acid (OA) to azelaic acid and pelargonic acid, and oxidation of the terminal methyl group in pelargonic acid to azelaic acid using cobalt‐ and manganese‐acetate as catalyst, hydrogen bromide as co‐catalyst and air in acetic acid at elevated pressure (2.8–5.8 barg) and temperature (353–383 K). Oxygen solubility is determined under varying pressure, temperature and OA loading. The effect of OA loading, pressure and temperature on OA conversion and azelaic acid selectivity is studied by varying one variable at a time; however, the presence of the synergistic effect of the catalyst and co‐catalyst is investigated by central composite design assisted response surface methodology. Oxidation of terminal methyl group in saturated fatty acid is also confirmed by the oxidation of stearic acid to octadecanedioic acid using identical oxidation conditions of OA. Oxidation products of fatty acids are quantified by gas chromatographic analysis. The innovation of the work is thus the ability of the catalytic system to perform a total oxidation of a terminal methyl group of the hydrocarbon chain. OA oxidation kinetics relating to catalyst and co‐catalyst concentration along with oxygen solubility at elevated temperature and pressure is established. The frequency factor and activation energy for OA oxidation is determined using the Arrhenius equation.

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Photocatalytic selective oxidation of the terminal methyl group of dodecane with molecular oxygen over atomically dispersed Ti in a mesoporous SiO2 matrix

Cited by 10 publications

References 36 publications

A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation

A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation

Solvent-Free Process for the Development of Photocatalytic Membranes

Liquid Phase Selective Catalytic Oxidation of Oleic Acid to Azelaic Acid Using Air and Transition Metal Acetate Bromide Complex

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