Cleaner industrial processes using hydrogen peroxide

Abstract

Recent research progress in catalytic systems for potential use with hydrogen peroxide in industrial chemical synthesis is reviewed, with special focus on work published in the last five years. The main types of chemistry employed are critically appraised regarding their suitability for industrial exploitation. The most significant catalyst types are discussed in terms of the positive features identified to date, and the obstacles yet to be surmounted in order to become more widely adopted. It is believed that fully inorganic systems have more scope for commercialization than those containing organic ligands or supports, however robust. Critical targets are larger-pore analogs of titanium silicalite TS-1, more exploration of smectitebased materials, effective immobilization of activated metal peroxo systems, and improvements in design and manipulation of polyoxometallate compounds. Cooperation between branches of chemistry that have not traditionally worked closely together is advocated.

Synthetic utility of metal catalyzed hydrogen peroxide oxidation of C-H, C-C and C=C bonds in alkanes, arenes and alkenes: Recent advances

“…SiO 2 grafted with propionate groups gave ∼50% cis-diol selectivity, but further modification with alkyl or perfluoroalkyl silanes increased cis-diol selectivity up to ∼60%. Dihydroxylation selectivity is also ∼60% for SiO 2 The catalytic property of phosphomolybdic acid (PMA) functionalized knitting aryl network polymer (KAP) was investigated for the selective oxidation of cyclooctene and other olefins with H 2 O 2 as oxidant. When ethyl acetate was used as reaction medium, the catalyst gave a 78.6% conversion of cyclooctene with nearly 100% selectivity for epoxide.…”

“…A highly selective Pd-catalyzed oxidative intramolecular chloroamination of unactivated alkenes has been developed by using a environmentally benign catalytic system, in which H 2 The effect of 6-methyl-substituted di(2-pyridyl)methanesulfonate (Me-dpms) and di(2-pyridyl)ketone (dpk) ligands on the selectivity oxidation of ethylene with H 2 O 2 in acetic acid solution has been explored. The results indicated that the palladium complexes supported by dpk and Me-dpms ligands are efficient catalysts for selective oxidation of ethylene with 30% aqueous H 2 O 2 to glycol acetates.…”

“…Hydrogen peroxide by itself is only moderately reactive towards most organic substrates, and in some reactions with electrophiles it reacts as a nucleophile rather than an oxidant. [1][2][3][4][5][6] The most common oxidation catalysts contain a transition metal that activates hydrogen peroxide for the oxyfunctionalization of the organic substrate. The broad spectrum of applications of metal catalysts for hydrogen peroxide oxidation have been reviewed elsewhere e.g.…”

“…In contrast, in dilute acidic solution the nitrido diiron phthalocyanineH 2 O 2 system, exhibits 5 times higher activity in the oxidation of a methane C-H bond compared to an ethane C-H bond. 78 A new μ-oxo diiron(III) complex of the lithium salt of the pyridine-based unsymmetrical ligand 3- 2 , was synthesized and the ability of the complex to catalyze oxidation of several alkanes and alkenes has been investigated by using CH 3 COOH/H 2 O 2 (1:1) as an oxidative system. Moderate activity in cyclohexane oxidation to cyclohexanol (18% yield) and cyclohexanone (15% yield), and in cyclohexene oxidation to epoxyclohexane (13% yield), 2-cyclohexenol (15% yield) and 2-hydroxycyclohexanone (8% yield) was detected.…”

11-Tungstophosphate with Iron(II) and Hydrogen Peroxide Efficiently Detached Bacterial Biofilm

“…40) According to this equation, complete decomposition of 1 mM PW 11 will produce ca. 20 mM H ϩ (pH 1.7), and the extent of PW 11 decomposition can be estimated from the decrease in pH.…”