Environmentally friendly and efficient catalysis of cyclohexane oxidation by iron meso-tetrakis(pentafluorophenyl)porphyrin immobilized on zinc oxide

Huang, Guan; Mo, Lin-Qiang; Cai, Jingli; Cao, Xuan; Yan, Peng; Guo, Yafei; Wei, Su-Juan

doi:10.1016/j.apcatb.2014.07.020

Cited by 51 publications

(36 citation statements)

References 46 publications

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“…For all the solids MnP‐HMS‐Mag (Figure h‐l) the MnP Soret band are blueshifted as compared to the parent non‐immobilized MnP in acetonitrile solution (Figure c‐g), particularly in the case of MnP1 (from 465 nm to 452 nm) and MnP4 (from 513 nm to 485 nm). This behavior can be attributed to steric constraints of the inorganic support, causing macrocycle distortions as reported in the literature; thus blueshift results from increase in the planarity of the porphyrin ring with the immobilization process, stabilizing the orbital HOMO of the porphyrin ring, away from the orbital LUMO increasing the HOMO‐LUMO energy gap. Conversely, the Soret band of the solids MnP4‐HMS‐Mag and MnP5‐HMS‐Mag (Figure k‐l), as well as their corresponding unsupported MnP (Figure f‐g), were redshifted as compared with the Soret band of the supported/unsupported MnP1 , MnP2 and MnP3 systems (Figure h‐j and Figure c‐e).…”

Section: Resultsmentioning

confidence: 61%

Magnetic HMS silica as a Support to Immobilization of Catalysts Based on Cationic Manganese Porphyrins

et al. 2017

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The immobilization of cationic manganese porphyrins (MnP) over the surface of a magnetic hexagonal HMS silica (HMS‐Mag) produced a solid with high surface area and relatively homogeneous pores. Given the presence of the magnetite, the catalysts are easily recovered and reused without loss of mass. The MnP immobilization explored the strong interaction between the positive charges of the cationic MnP and the deprotonated Si‐OH groups on the surface of HMS‐Mag. Soret bands on the UV‐Vis spectra of the MnP‐loaded HMS‐Mag confirmed the presence of MnP on the prepared solids. The catalytic efficiency, robustness, and reusability of the prepared solids were investigated on cis‐cyclooctene and cyclohexane oxidations. The solids showed similar or higher catalytic efficiency than the corresponding MnP under homogeneous catalysis, with selectivity for cyclohexanol in cyclohexane oxidation. Additionally, the solid catalysts showed high resistance against deactivation, confirming the reusability capacity in at least five cycles of cyclooctene oxidation.

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Section: Resultsmentioning

confidence: 61%

Magnetic HMS silica as a Support to Immobilization of Catalysts Based on Cationic Manganese Porphyrins

et al. 2017

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“…[78] Immobilization further protected the catalyst against oxidative degradation which allowed the catalyst to be recycled, after washing and air drying, for atotal of 11 runs and provided an average TOFv alue of 2.6 10 5 h À1 over 2.5 hours.Arather low selectivity and sub-optimal ketone/alcohol ratio (a high ratio is desired for KA oxidation to adipic acid) leave room for improvement. [78] Immobilization further protected the catalyst against oxidative degradation which allowed the catalyst to be recycled, after washing and air drying, for atotal of 11 runs and provided an average TOFv alue of 2.6 10 5 h À1 over 2.5 hours.Arather low selectivity and sub-optimal ketone/alcohol ratio (a high ratio is desired for KA oxidation to adipic acid) leave room for improvement.…”

Section: Heterogeneous Catalysismentioning

confidence: 99%

Catalytic Aerobic Oxidation of C(sp³)−H Bonds

2019

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Oxidation reactions are a key technology to transform hydrocarbons from petroleum feedstock into chemicals of a higher oxidation state, allowing further chemical transformations. These bulk scale oxidation processes usually employ molecular oxygen as the terminal oxidant as at this scale it is typically the only economically viable oxidant. The produced commodity chemicals possess limited functionality and usually show a high degree of symmetry thereby avoiding selectivity issues. In sharp contrast in the production of fine chemicals preference is still given to classical oxidants. Considering the strive for greener production processes the use of O2, the most abundant and greenest oxidant, is a logical choice. Given the rich functionality and complexity of fine chemicals achieving regio/chemoselectivity is a major challenge. This review presents an overview of the most important catalytic systems recently described for aerobic oxidation, and the current insight in their reaction mechanism.

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“…For example, there are several catalysts reported using molecular oxygen asa no xidant, such as Co/ZSM-5 at 120 8Cu nder 1.0 MPa O 2 , [4] Au/ZSM-5 at 150 8Cu nder 1MPa O 2 , [5] mesoporous Ce 0.5 Mn 0.5 O x solid solution at 100 8Cu nder 10 bar O 2 , [6] Mn-Com ixed oxide at 140 8Cu nder 0.5 MPa O 2 , [7] Ce-doped MCM-48 140 8Cu nder 1.0 MPa O 2 , [8] CrCoAPO-5(AFI) at 115 8C under 1MPa O 2 , [9] ZnO-supported tetrakis(pentafluorophenyl)porphyrin-ironc hloride at 150 8Cu nder 0.7 MPa air, [10] and vanadium-substituted tungstophosphoric acids under visiblelight irradiation. For example, there are several catalysts reported using molecular oxygen asa no xidant, such as Co/ZSM-5 at 120 8Cu nder 1.0 MPa O 2 , [4] Au/ZSM-5 at 150 8Cu nder 1MPa O 2 , [5] mesoporous Ce 0.5 Mn 0.5 O x solid solution at 100 8Cu nder 10 bar O 2 , [6] Mn-Com ixed oxide at 140 8Cu nder 0.5 MPa O 2 , [7] Ce-doped MCM-48 140 8Cu nder 1.0 MPa O 2 , [8] CrCoAPO-5(AFI) at 115 8C under 1MPa O 2 , [9] ZnO-supported tetrakis(pentafluorophenyl)porphyrin-ironc hloride at 150 8Cu nder 0.7 MPa air, [10] and vanadium-substituted tungstophosphoric acids under visiblelight irradiation.…”

Section: Introductionmentioning

confidence: 99%

“…Until to now,anumber of different catalysts have been reported for the selective oxidation of cyclohexane to KA oil. For example, there are several catalysts reported using molecular oxygen asa no xidant, such as Co/ZSM-5 at 120 8Cu nder 1.0 MPa O 2 , [4] Au/ZSM-5 at 150 8Cu nder 1MPa O 2 , [5] mesoporous Ce 0.5 Mn 0.5 O x solid solution at 100 8Cu nder 10 bar O 2 , [6] Mn-Com ixed oxide at 140 8Cu nder 0.5 MPa O 2 , [7] Ce-doped MCM-48 140 8Cu nder 1.0 MPa O 2 , [8] CrCoAPO-5(AFI) at 115 8C under 1MPa O 2 , [9] ZnO-supported tetrakis(pentafluorophenyl)porphyrin-ironc hloride at 150 8Cu nder 0.7 MPa air, [10] and vanadium-substituted tungstophosphoric acids under visiblelight irradiation. [11] Although the use of molecular O 2 as an oxidant provides ac heap and green environment, the usual need of high pressure and high temperature, and/or low conversion for most catalysts limit their successful implementation.…”

Section: Introductionmentioning

confidence: 99%

Ce_1−xCr_xO_2−δ Nanocrystals as Efficient Catalysts for the Selective Oxidation of Cyclohexane to KA Oil at Low Temperature under Ambient Pressure

et al. 2018

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The selective oxidation of C−H bonds in saturated hydrocarbons at low temperature with noble‐metal‐free heterogeneous catalysts is a profound challenge for the catalysis community. Here we report the facile synthesis of Ce1−xCrxO2−δ (x=0, 0.1, 0.2, 0.3, and 0.4) nanocrystals through a low‐temperature hydrothermal method. The catalytic activity of the as‐prepared catalysts was evaluated in the selective oxidation of cyclohexane to cyclohexanone/cyclohexanol using H2O2 as an oxidant at room temperature and 45 °C. The activity results were correlated with their phase structure, composition, surface areas, and surface element states with the help of X‐ray diffraction, N2 adsorption, transmission electron microscopy, X‐ray photoelectron spectroscopy, and UV/Vis spectroscopy. It was found that these Ce0.7Cr0.3O2−δ nanocrystals are highly active for the selective oxidation of cyclohexane to cyclohexanone/cyclohexanol using H2O2 as an oxidant at low temperature. In the presence of H2O2 at 45 °C for 5 h using Ce0.7Cr0.3O2−δ as a catalyst, the conversion of cyclohexane reaches 50.3 % and the total selectivity of cyclohexanol/cyclohexanone is 94.4 % with relative good reversibility for at least four cycles. Mechanistic investigation results show that the high activity can be attributed to the high Cr6+ content in the Ce1−xCrxO2−δ solid solutions and the formation of highly oxidative intermediates with H2O2.

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Environmentally friendly and efficient catalysis of cyclohexane oxidation by iron meso-tetrakis(pentafluorophenyl)porphyrin immobilized on zinc oxide

Cited by 51 publications

References 46 publications

Magnetic HMS silica as a Support to Immobilization of Catalysts Based on Cationic Manganese Porphyrins

Magnetic HMS silica as a Support to Immobilization of Catalysts Based on Cationic Manganese Porphyrins

Catalytic Aerobic Oxidation of C(sp³)−H Bonds

Ce_1−xCr_xO_2−δ Nanocrystals as Efficient Catalysts for the Selective Oxidation of Cyclohexane to KA Oil at Low Temperature under Ambient Pressure

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Environmentally friendly and efficient catalysis of cyclohexane oxidation by iron meso-tetrakis(pentafluorophenyl)porphyrin immobilized on zinc oxide

Cited by 51 publications

References 46 publications

Magnetic HMS silica as a Support to Immobilization of Catalysts Based on Cationic Manganese Porphyrins

Magnetic HMS silica as a Support to Immobilization of Catalysts Based on Cationic Manganese Porphyrins

Catalytic Aerobic Oxidation of C(sp3)−H Bonds

Ce1−xCrxO2−δ Nanocrystals as Efficient Catalysts for the Selective Oxidation of Cyclohexane to KA Oil at Low Temperature under Ambient Pressure

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Catalytic Aerobic Oxidation of C(sp³)−H Bonds

Ce_1−xCr_xO_2−δ Nanocrystals as Efficient Catalysts for the Selective Oxidation of Cyclohexane to KA Oil at Low Temperature under Ambient Pressure