Recent Advances in Facile Liquid Phase Epoxidation of Light Olefins over Heterogeneous Molybdenum Catalysts

Abstract

Molybdenum complexes are versatile and efficient for liquid phase olefin epoxidation reactions. Rational design of catalysts is critical to achieve high atom efficiency during epoxidation processes. Although liquid phase epoxidation has been a popular topic for decades, three key issues, (a) rational control of morphology of molybdenum nanoparticles, (b) manipulating metal‐support interaction and (c) altering electronic configuration at molybdenum center remains unsolved in this area. Therefore, in this paper, we have critically revised recent research progress on heterogeneous molybdenum catalysts for facile liquid phase olefin epoxidation in terms of catalyst synthesis, surface characterization, catalytic performance and structure‐function relationship. Furthermore, plausible reaction mechanisms will be systematically discussed with the aim to provide insights into fundamental understanding on novel epoxidation chemistry.

Hydrophobic/Hydrophilic Interplay in 1,2,4‐Triazole‐ or Carboxylate‐Based Molybdenum(VI) Oxide Hybrids: A Step Toward Development of Reaction‐Induced Self‐Separating Catalysts

“…Graphical visualization of the structures was made using the program Diamond 2.1e. [32] The crystallographic material can be obtained from Cambridge Crystallographic Data Centre through deposition numbers CCDC 2050966 (1) and 2050967 (2).…”

“…The capability of Mo VI compounds to react with peroxides, resulting in reactive peroxo intermediates, provides an essential paradigm for the development and study of highly efficient homogeneous catalysts for many oxidation processes. During the last decade numerous Mo VI -containing inorganic salts and complexes were tested for the epoxidation of olefins, [1][2][3][4][5] sulfoxidation, [6,7] deoxydehydration of 1,2-diols to olefins, [8,9] etc. [10] Among these compounds, the molybdenum(VI)-oxide coordination polymers templated by carboxylates or N-donor heterocyclic ligands have proven their value as promising catalysts which combine high structural and thermal stability (up to 450°C).…”

Non-aqueous synthesis of homogeneous molybdenum silicate microspheres and their application as heterogeneous catalysts in olefin epoxidation and selective aniline oxidation

“…The epoxidation of olefins has gained immense attention in both academic and industrial research fields. Epoxides are highly versatile intermediates and valuable compounds produced on an industrial scale [2]. Further, a ringopening reaction of the epoxides provides a wide range of chemicals, such as pharmaceuticals, detergents, paints, agrochemicals, polymers, surfactants, corrosion protection agents, lubricating oils, food additives, cosmetics, etc.…”

“…High activity and selectivity of molybdenum, tungsten, vanadium, and titanium silicatebased catalysts in olefin epoxidation have been demonstrated when using hydroperoxides (e.g., tertbutyl hydroperoxide (TBHP) and H2O2) as oxidizing agents [7,9,10]. Moreover, the advantages of Mo compounds such as low cost, availability, environmental friendliness, and non-toxicity are getting closer to meet the green principles [2,11,12].…”

Remarkable binuclear Schiff‐based complex catalyze the epoxidation of alkenes: effects of substituent group

“…The catalytic epoxidation of olefins is one of the effective methods to produce epoxy products corresponding epoxy products . There are two key parameters for the design of efficient catalyst for olefine epoxidation: first, the type and charge of a central metal ion, and second, the type of the coordinated ligand and its coordinated center …”