Regulating effects of anthraquinone substituents and additives in photo-catalytic oxygenation of p-xylene by molecular oxygen under visible light irradiation

Jiang, Dabo; Zhang, Qiao; Yang, Long; Deng, Yuan; Yang, Bo; Liu, Yachun; Zhang, Chao; Fu, Zaihui

doi:10.1016/j.renene.2021.04.100

Cited by 14 publications

(13 citation statements)

References 69 publications

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“…The ligand H 2 AQ showed a narrow peak after photoexcitation, which could be assigned to the generation of ketyl radical (Figure S14). 40 Nevertheless, the EPR spectrum of Ce−AQ exhibited two new peaks that differ from that of the ligand H 2 AQ under identical irradiation conditions (Figure 4a). We speculated that the illumination of Ce−AQ caused an LMCT behavior to possibly form oxygen bridge radicals (Ce−O • −Ce).…”

Section: ■ Results and Discussionmentioning

confidence: 96%

“…The ligand H 2 AQ showed a narrow peak after photoexcitation, which could be assigned to the generation of ketyl radical (Figure S14). Nevertheless, the EPR spectrum of Ce– AQ exhibited two new peaks that differ from that of the ligand H 2 AQ under identical irradiation conditions (Figure a). We speculated that the illumination of Ce– AQ caused an LMCT behavior to possibly form oxygen bridge radicals (Ce–O · –Ce). , Importantly, in the presence of excess cyclohexane, irradiation of Ce– AQ in the argon atmosphere for 1 h result in a puniness but an obvious increase of Ce III content (Figure c), whereas individual Ce– AQ had no obvious change under the same measurement time.…”

Section: Results and Discussionmentioning

confidence: 98%

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A Binuclear Cerium-Based Metal–Organic Framework as an Artificial Monooxygenase for the Saturated Hydrocarbon Aerobic Oxidation with High Efficiency and High Selectivity

Zhao

Wang

et al. 2022

ACS Catal.

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Artificial enzymatic systems have emerged in the field of biomimetic catalysis by constructing specific catalytic centers of enzymes. Inspired by the high activity of natural monooxygenase for the oxidation transformation, several binuclear Cu/Fe-based metal−organic frameworks (MOFs) have been frequently used as oxidation catalysts, yet rarely reports of MOFs with other metals nodes have been reported to date. In this work, by the ingenious decoration of binuclear Ce−O−Ce moieties and anthraquinone groups with good oxygen activation ability in one framework, an MOF-supported artificial binuclear cerium monooxygenase was obtained for the highly selective oxidation of inert C(sp 3 )−H bonds. The single-crystal structural study reveals that the molecule-level modularity with a binuclear Ce−O−Ce moiety design in the MOF creates a confined microenvironment to offer the ordered distribution of highly dense substrate-accessible active sites throughout the architecture. After photoexcitation, the Ce−O−Ce moieties trigger a ligand-to-metal charge-transfer (LMCT) event to form an oxygen bridge radical, which abstracts a hydrogen atom from the C(sp 3 )−H bond to generate a carbon-centered radical through a typical hydrogen atom transfer (HAT) process. These carbon-centered radicals rapidly combine the reactive oxygen species (ROS) produced by the anthraquinone groups via an energy transfer (EnT) process to generate the alkyl peroxy radical intermediates, which are easily trapped by another unsaturated coordinated cerium ions to further facilitate their hydrolysis for the selective formation of carbonyl products. This anthraquinone-functionalized metal−organic framework containing binuclear cerium catalytic centers resembling the active sites of natural monooxygenase exhibits the unique catalytic selectivity (>97%) and high activity, which represent the first example of the MOF constructed from metals different from that of natural monooxygenase for applying to the oxidation of alkanes, expanding the selection range of metal centers in the artificial monooxygenase. Taking advantage of the heterogeneity of the MOF, the Ce−MOF was recycled five times without a decrease in its selectivity and activity and possessed broader applicability for the substrate with inert C−H bonds, providing a blueprint for designing new artificial monooxygenase for the inert alkane oxidation.

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Section: ■ Results and Discussionmentioning

confidence: 96%

Section: Results and Discussionmentioning

confidence: 98%

A Binuclear Cerium-Based Metal–Organic Framework as an Artificial Monooxygenase for the Saturated Hydrocarbon Aerobic Oxidation with High Efficiency and High Selectivity

Zhao

Wang

et al. 2022

ACS Catal.

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“…The composition of the organic and water layers was analyzed by HPLC to understand the material balance in this reaction and if the water layer was free of organic impurities. Contained in the toluene layer of the reaction after 2 h of photolysis were benzaldehyde, benzyl alcohol, and benzoic acid, a result which has literature precedent (we have also explored the mechanism that results in the production of oxidized organics by this process with Density Functional Theory, vide infra ). ,,− …”

Section: Resultsmentioning

confidence: 97%

“…A less explored but promising approach that can complement the AO process is to use the excited-state properties of anthraquinones (or other chromophores) − to catalyze the production of H 2 O 2 from air. Anthraquinones are highly useful in organic photoredox catalysis, , having been used to initiate the photooxidation of benzylic substituents, , 1,3-diketones, alcohols, and to epoxidize enones . They have also successfully been employed in arene hydrodehalogenations .…”

Section: Introductionmentioning

confidence: 99%

On-Demand Photochemical Synthesis of Hydrogen Peroxide from Alkylated Anthraquinones

Vibbert

Bendel

Norton

et al. 2022

ACS Sustainable Chem. Eng.

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Direct illumination of anthraquinones with light, in air, to produce H 2 O 2 reliably and robustly has been developed for aqueous, electrolyte-free, highly pure H 2 O 2 production. Effects of chromophore, solvent, air saturation, and light source have been investigated to understand the mechanism of this transformation. Upon photosensitization of an air-saturated, biphasic solution consisting of an organic solvent and water, H 2 O 2 can be quickly and linearly produced with the oxidized solvent remaining in the organic phase. The mechanism of this transformation has been probed using computational methods, suggesting that proton-coupled electron transfer from an organic solvent to an anthraquinone catalyst is the most likely mechanistic pathway. Commercially relevant H 2 O 2 concentrations, as high as 2.34% (w/w), have been produced in 3 h, among the fastest photochemical H 2 O 2 production reaction reported.

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“…Jiang et al [ 32 ] explored the photo-catalytic oxidation of p- xylene using substituted anthraquinones as catalysts. 2-carboxyanthraquinone was the best catalyst in the study, being active under visible light (35 W tungsten-bromine lamp) and with 1 atm of O 2 at r.t., achieving 70.9% conversion and 88.2% selectivity for p- toluic acid after 12 h of reaction.…”

Section: Catalytic Advancesmentioning

confidence: 99%

p-Xylene Oxidation to Terephthalic Acid: New Trends

Lapa

Martins

2023

Molecules

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Large-scale terephthalic acid production from the oxidation of p-xylene is an especially important process in the polyester industry, as it is mainly used in polyethylene terephthalate (PET) manufacturing, a polymer that is widely used in fibers, films, and plastic products. This review presents and discusses catalytic advances and new trends in terephthalic acid production (since 2014), innovations in terephthalic acid purification processes, and simulations of reactors and reaction mechanisms.

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Regulating effects of anthraquinone substituents and additives in photo-catalytic oxygenation of p-xylene by molecular oxygen under visible light irradiation

Cited by 14 publications

References 69 publications

A Binuclear Cerium-Based Metal–Organic Framework as an Artificial Monooxygenase for the Saturated Hydrocarbon Aerobic Oxidation with High Efficiency and High Selectivity

A Binuclear Cerium-Based Metal–Organic Framework as an Artificial Monooxygenase for the Saturated Hydrocarbon Aerobic Oxidation with High Efficiency and High Selectivity

On-Demand Photochemical Synthesis of Hydrogen Peroxide from Alkylated Anthraquinones

p-Xylene Oxidation to Terephthalic Acid: New Trends

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