Enhanced catechol oxidation by heterogeneous biomimetic catalysts immobilized on clay minerals

Nuzzo, Assunta; Piccolo, Alessandro

doi:10.1016/j.molcata.2013.01.021

Cited by 25 publications

(24 citation statements)

References 34 publications

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“…23 It was found that the reaction between the spacer ethoxyl groups and silanol and aluminol groups on the clay mineral surface had occurred, and the Imi-APTS spacer ended up covalently bound to kaolinite.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In fact, a Mn−porphyrin immobilized on both spacer-functionalized kaolinite and montmorillonite showed a significantly larger rate of oxidative coupling of catechol than the free catalyst. 23 The aim of this work was to oxidatively polymerize a humic acid (HA) isolated from lignin by heterogeneous catalysis. The catalytic activity was exerted by a Mn−porphyrin immobilized on a kaolinite support previously functionalized with a molecular spacer, and the humic polymerization was induced by either H 2 O 2 or photo-oxidation.…”

Section: ■ Introductionmentioning

confidence: 99%

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Oxidative and Photoxidative Polymerization of Humic Suprastructures by Heterogeneous Biomimetic Catalysis

Nuzzo¹,

Piccolo²

2013

Biomacromolecules

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The meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate of manganese(III) chloride [Mn-(TDCPPS)Cl] biomimetic catalyst immobilized on spacer-functionalized kaolinite clay mineral was employed in the oxidative coupling reaction of a dissolved humic acid (HA) suprastructure with either chemical (H2O2) or UV-light oxidation. The changes in molecular size of humic matter subjected to catalyzed oxidative reaction were followed by high-performance size exclusion chromatography (HPSEC) with UV-vis and refractive index (RI) detectors in series, and by thermogravimetric (TGA) analysis. Both the enhanced molecular size shown by differences between HPSEC chromatograms of humic reaction mixtures at either pH 6 or 3.5 and the increase of thermogravimetric stability suggest that the heterogeneous biomimetic catalysis promoted the stabilization of humic conformations by new intermolecular covalent bonds during oxidative coupling. The similarity between chemical and light-induced oxidation results suggests potential multiple applications of the kaolinite-supported heterogeneous catalyst in controlling the reactivity of natural organic matter within biogeochemical cycles and environmental reactions.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Oxidative and Photoxidative Polymerization of Humic Suprastructures by Heterogeneous Biomimetic Catalysis

Nuzzo¹,

Piccolo²

2013

Biomacromolecules

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“…The support can behave like an electron-withdrawing substituent, that is, the electronic density of cobalt ions in supported metalloporphyrins changes with the support 28 . Different supports can provide a different micro-environment in cyclohexane oxidation reactions, which change the ability of activating oxygen molecules 20,26,29 . Different supports can provide a different micro-environment in cyclohexane oxidation reactions, which change the ability of activating oxygen molecules 20,26,29 .…”

Section: Catalytic Performancementioning

confidence: 99%

“…In addition, much efforts have been devoted to develop heterogeneous metalloporphyrin catalysts on various supports [14][15][16][17][18][19][20][21][22][23][24][25] . In addition, much efforts have been devoted to develop heterogeneous metalloporphyrin catalysts on various supports [14][15][16][17][18][19][20][21][22][23][24][25] .…”

Section: Introductionmentioning

confidence: 99%

Zinc Oxide Supported trans-CoD(p-Cl)PPCl-Type Metalloporphyrins Catalyst for Cyclohexane Oxidation to Cyclohexanol and Cyclohexanone with High Yield

Xie

Zhang

Liu

et al. 2015

Ind. Eng. Chem. Res.

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Direct functionalization of saturated C-H bonds by metalloporphyrin catalysts is among the topical and challenging areas within the chemical industry and the synthetic chemistry. In this work, supported CoD(p-Cl)PPCl metalloporphyrin catalysts were prepared and characterized. It has been found that the CoD(p-Cl)PPCl/ZnO catalyst shows better catalytic activity than the supported catalyst (ZrO 2 , MCM-41, kaolin, Zr(OH) 2 and BM) in cyclohexane oxidation with dioxygen. The effects of the reaction pressure, reaction temperature and reaction time on the catalytic activity were considered by the supported CoD(p-Cl)PPCl/ZnO catalyst. The CoD(p-Cl)PPCl/ZnO catalyst can be facilely recovered and was recycled up to seven times without significant decrease in catalytic performance. The average cyclohexane conversion and selectivity to KA oil are 10.98% and 84.34% respectively, and the turnover number is 2.10 x 10 7 .

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“…As a more convenient alternative to fragile enzymes, synthetic biomimetic metal‐porphyrin catalysts that mimic the activity of oxidative enzymes, were found to produce larger and chemically stable humic molecules during oxidative (H 2 O 2 ) treatments of soluble humus (Piccolo, Conte, & Tagliatesta, ; Smejkalova & Piccolo, ; Smejkalova, Piccolo, & Spiteller, ). Being more suitable for soil applications than H 2 O 2 , dioxygen molecules under solar irradiation and in the presence of both homogeneous and heterogeneous metal‐porphyrin catalysts provide the highly oxidizing singlet oxygen that induces the photo‐oxidative formation, via a free radical mechanism, of intermolecular C–C and C–O–C bonds among humic phenolic molecules (Nuzzo & Piccolo, , ; Smejkalova & Piccolo, ).…”

Section: Introductionmentioning

confidence: 99%

Effective carbon sequestration in Italian agricultural soils by in situ polymerization of soil organic matter under biomimetic photocatalysis

et al. 2018

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Facing an exploding population growth with consequent increase of agriculture intensification, new chemical technologies are being sought to limit organic matter losses and reduce land degradation. Here, we report that an effective organic carbon sequestration in different cropped soils of Italy is obtained by an in situ photo‐oxidative coupling among soil humic molecules, when catalyzed under solar irradiation by a water‐soluble biomimetic iron‐porphyrin catalyst amended to field soils. A 3‐year long field study showed that the catalyst‐assisted in situ photochemical polymerization of humic matter enabled a yearly sequestration of soil organic carbon that ranged from 2.2 to 3.9 t ha−1 y−1, despite the periodical soil disturbance due to a conventional tillage management. This significant stabilization of organic matter was observed not only in bulk soils but also in water‐stable aggregates, whose loss of organic carbon during separation was limited in catalyst‐treated soils. Although crop yields were the same in treated and control soils, measurements of phospholipids fatty acids and soil enzyme activities indicated that the catalyzed in situ photo‐oxidative coupling of humic molecules did not alter the structure and activity of microbial communities and the biological functions of soils. This innovative and ecologically safe catalytic technology may be developed as a useful soil management practice to stabilize organic matter in situ in arable soils, while concomitantly ensuring soil functions and sustainability of crop production.

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Enhanced catechol oxidation by heterogeneous biomimetic catalysts immobilized on clay minerals

Cited by 25 publications

References 34 publications

Oxidative and Photoxidative Polymerization of Humic Suprastructures by Heterogeneous Biomimetic Catalysis

Oxidative and Photoxidative Polymerization of Humic Suprastructures by Heterogeneous Biomimetic Catalysis

Zinc Oxide Supported trans-CoD(p-Cl)PPCl-Type Metalloporphyrins Catalyst for Cyclohexane Oxidation to Cyclohexanol and Cyclohexanone with High Yield

Effective carbon sequestration in Italian agricultural soils by in situ polymerization of soil organic matter under biomimetic photocatalysis

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