Study on the formation of photoactive species in XPMo 12-n V n O 40 - HCl system and its effect on photocatalysis oxidation of cyclohexane by dioxygens under visible light irradiation

Tang, Senpei; She, Jialuo; Fu, Zaihui; Zhang, Shenyi; Tang, Zeyu; Zhang, Chao; Liu, Yachun; Yin, Dulin; Li, Jianwei

doi:10.1016/j.apcatb.2017.05.027

Cited by 29 publications

(11 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Such an oxygen vacancy is then filled with oxygen from the gas phase, which simultaneously reoxidizes the reduced V of VAlPO 4 catalyst lattice results in the recovery of the VAlPO 4 catalyst. Similarly, both cyclohexanone product and cyclohexyl hydroperoxide (CHHP) intermediate could be resulted from further oxidation cyclohexanol by molecular oxygen in the presence of a VAlPO 4 catalyst [ 24 , 25 ]. Then, additional further oxidation of cyclohexanone would end up in ring-opened acid by-products,which can be esterified by cyclohexanol, generating the ester by-products [ 24 , 25 ].…”

Section: Resultsmentioning

confidence: 99%

“…Similarly, both cyclohexanone product and cyclohexyl hydroperoxide (CHHP) intermediate could be resulted from further oxidation cyclohexanol by molecular oxygen in the presence of a VAlPO 4 catalyst [ 24 , 25 ]. Then, additional further oxidation of cyclohexanone would end up in ring-opened acid by-products,which can be esterified by cyclohexanol, generating the ester by-products [ 24 , 25 ]. It must be noted that the oxidation depth of cyclohexane is closely related to the reaction conditions, especially the reaction temperature.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol over VAlPO4 berlinite by oxygen under atmospheric pressure

Hong

Sun

Fang

2018

Chemistry Central Journal

View full text Add to dashboard Cite

BackgroundThe oxidation of cyclohexane under mild conditions occupies an important position in the chemical industry. A few soluble transition metals were widely used as homogeneous catalysts in the industrial oxidation of cyclohexane. Because heterogeneous catalysts are more manageable than homogeneous catalysts as regards separation and recycling, in our study, we hydrothermally synthesized and used pure berlinite (AlPO4) and vanadium-incorporated berlinite (VAlPO4) as heterogeneous catalysts in the selective oxidation of cyclohexane with molecular oxygen under atmospheric pressure. The catalysts were characterized by means of by XRD, FT-IR, XPS and SEM. Various influencing factors, such as the kind of solvents, reaction temperature, and reaction time were investigated systematically.ResultsThe XRD characterization identified a berlinite structure associated with both the AlPO4 and VAlPO4 catalysts. The FT-IR result confirmed the incorporation of vanadium into the berlinite framework for VAlPO4. The XPS measurement revealed that the oxygen ions in the VAlPO4 structure possessed a higher binding energy than those in V2O5, and as a result, the lattice oxygen was existed on the surface of the VAlPO4 catalyst. It was found that VAlPO4 catalyzed the selective oxidation of cyclohexane with molecular oxygen under atmospheric pressure, while no activity was detected on using AlPO4. Under optimum reaction conditions (i.e. a 100 mL cyclohexane, 0.1 MPa O2, 353 K, 4 h, 5 mg VAlPO4 and 20 mL acetic acid solvent), a selectivity of KA oil (both cyclohexanol and cyclohexanone) up to 97.2% (with almost 6.8% conversion of cyclohexane) was obtained. Based on these results, a possible mechanism for the selective oxidation of cyclohexane over VAlPO4 was also proposed.ConclusionsAs a heterogeneous catalyst VAlPO4 berlinite is both high active and strong stable for the selective oxidation of cyclohexane with molecular oxygen. We propose that KA oil is formed via a catalytic cycle, which involves activation of the cyclohexane by a key active intermediate species, formed from the nucleophilic addition of the lattice oxygen ion with the carbon in cyclohexane, as well as an oxygen vacancy formed at the VAlPO4 catalyst surface. Electronic supplementary materialThe online version of this article (10.1186/s13065-018-0405-6) contains supplementary material, which is available to authorized users.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol over VAlPO4 berlinite by oxygen under atmospheric pressure

Hong

Sun

Fang

2018

Chemistry Central Journal

View full text Add to dashboard Cite

show abstract

“…were reported as recyclable photocatalysts for the HCl-promoted aerobic oxidation of cyclohexane under visible-light irradiation (Tang et al, 2017). 51 V NMR, cyclic voltammetry and UV-Vis spectral studies revealed that the Catalyst combination of TBADT and COPC for the dehydrogenation of alkanes.…”

Section: Oxidative C-h Bond Activation Of Alkanes/alkenes and Trifluomentioning

confidence: 99%

Recent advances of polyoxometalate-catalyzed selective oxidation based on structural classification

Chen

Shen

2018

Acta Crystallogr C

View full text Add to dashboard Cite

The structural diversity and tenability observed in POMs has encouraged extensive investigations into their catalytic activity. Based on the structural classification of POMs, this review summarizes recent advances relating to POM‐catalyzed selective oxidation and places most emphasis on dynamic developments from 2015 onwards. Work which contributes to comparing the catalytic performance of POMs with delicate structural differences (e.g. the same type of POM structure with differences of the heteroatom, addenda, protonated state or counter‐ion) and in elucidating the origin/distinction of catalytic activity, as well as reasonable mechanisms, are especially highlighted.

show abstract

“…In recent years, light-triggered chemicalr eactions have emergeda sp owerful synthesis techniques for the production of fine chemicals under mild reactionc onditions. [33][34][35] In particular,t he selectiveo xidation of organic compoundsb ydioxygen (O 2 )o ra ir under visible light is believed to be user-and environmentally friendly,and thus, of great academic and practical significance. [36,37] Herein, we report an atom-efficient and ecofriendly photo-oxidation protocol for the synthesis of AQ from DHA withouta ny extra catalysts or additives under ambient temperature and pressure, which can fully meet the requirements ofg reen chemistry principles.…”

Section: Introductionmentioning

confidence: 99%

Visible‐Light‐Triggered Quantitative Oxidation of 9,10‐Dihydroanthracene to Anthraquinone by O₂ under Mild Conditions

Jiang

Chen

et al. 2020

ChemSusChem

Self Cite

View full text Add to dashboard Cite

The development of mild and efficient processes for the selective oxygenation of organic compounds by molecular oxygen (O2) is key for the synthesis of oxygenates. This paper discloses an atom‐efficient synthesis protocol for the photo‐oxygenation of 9,10‐dihydroanthracene (DHA) by O2 to anthraquinone (AQ), which could achieve quantitative AQ yield (100 %) without any extra catalysts or additives under ambient temperature and pressure. A yield of 86.4 % AQ was obtained even in an air atmosphere. Furthermore, this protocol showed good compatibility for the photo‐oxidation of several other compounds with similar structures to DHA. From a series of control experiments, free‐radical quenching, and electron paramagnetic resonance spin‐trapping results, the photo‐oxygenation of DHA was probably initiated by its photoexcited state DHA*, and the latter could activate O2 to a superoxide anion radical (O2.−) through the transfer of its electron. Subsequently, this photo‐oxidation was gradually dominated by the oxygenated product AQ as an active photocatalyst obtained from the oxidation of DHA by O2.−, and was accelerated with the rapid accumulation of AQ. The present photo‐oxidation protocol is a good example of selective oxygenation based on the photoexcited substrate self‐activated O2, which complies well with green chemistry ideals.

show abstract

Study on the formation of photoactive species in XPMo 12-n V n O 40 - HCl system and its effect on photocatalysis oxidation of cyclohexane by dioxygens under visible light irradiation

Cited by 29 publications

References 56 publications

The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol over VAlPO4 berlinite by oxygen under atmospheric pressure

The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol over VAlPO4 berlinite by oxygen under atmospheric pressure

Recent advances of polyoxometalate-catalyzed selective oxidation based on structural classification

Visible‐Light‐Triggered Quantitative Oxidation of 9,10‐Dihydroanthracene to Anthraquinone by O₂ under Mild Conditions

Contact Info

Product

Resources

About

Study on the formation of photoactive species in XPMo 12-n V n O 40 - HCl system and its effect on photocatalysis oxidation of cyclohexane by dioxygens under visible light irradiation

Cited by 29 publications

References 56 publications

The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol over VAlPO4 berlinite by oxygen under atmospheric pressure

The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol over VAlPO4 berlinite by oxygen under atmospheric pressure

Recent advances of polyoxometalate-catalyzed selective oxidation based on structural classification

Visible‐Light‐Triggered Quantitative Oxidation of 9,10‐Dihydroanthracene to Anthraquinone by O2 under Mild Conditions

Contact Info

Product

Resources

About

Visible‐Light‐Triggered Quantitative Oxidation of 9,10‐Dihydroanthracene to Anthraquinone by O₂ under Mild Conditions