Different efficiency toward the biomimetic aerobic oxidation of benzyl alcohol in microchannel and bubble column reactors: Hydrodynamic characteristics and gas–liquid mass transfer

The selective aerobic oxidation of benzyl alcohol to benzaldehyde has attracted considerable attention because benzaldehyde is a high value-added product. The rate of this typical gas–liquid reaction is significantly affected by mass transfer. In this study, CoTPP-mediated(CoTPP: cobalt(II) mesotetraphenylporphyrin) selective benzyl alcohol oxidation with oxygen was conducted in a membrane microchannel(MMC) reactor and a bubble column(BC) reactor, respectively. We observed that 83% benzyl alcohol was converted within 6.5 min in the MMC reactor, but only less than 10% benzyl alcohol was converted in the BC reactor. Hydrodynamic characteristics and gas–liquid mass transfer performances were compared for the MMC and BC reactors. The MMC reactor was assumed to be a plug flow reactor,and the dimensionless variance was 0.29. Compared to the BC reactor, the gas–liquid mass transfer was intensified significantly in MMC reactor. It could be ascribed to the high gas holdup(2.9 times higher than that of BC reactor), liquid film mass transfer coefficient(8.2 times higher than that of BC reactor), and mass transfer coefficient per unit interfacial area(3.8 times higher than that of BC reactor). Moreover,the Hatta number for the MMC reactor reached up to 0.61, which was about 15 times higher than that of the BC reactor. The computational fluid dynamics calculations for mass fractions in both liquid and gas phases were consistent with the experimental data.

N-hydroxyphthalimide anchored on hexagonal boron nitride as a metal-free heterogeneous catalyst for deep oxidative desulfurization

A metal-free N-hydroxyphthalimide/hexagonal boron nitride(NHPI/h-BN)catalytic system was developed for deep oxidative desulfurization(ODS)of fuel oils.Detailed experiments find that the heterogenization process of loading NHPI on h-BN not only benefits to the dispersion and utilization of NHPI,but also can significantly promote the catalytic performance.By employing NHPI/h-BN as the catalyst,azodiisobutyronitrile(AIBN)as the metal-free initiator,a 95%conversion of dibenzothiophene(DBT)can be acquired under the reaction conditions of 120°C and atmospheric pressure with molecular oxygen(O_(2))as oxidant.Moreover,the heterogenization is convenient for the regeneration of the catalyst with>94%DBT conversion after being recycled seven times.Characterizations illustrate that the promoted catalytic activity along with the regenerability originate from the interactions between NHPI and h-BN.The catalytic mechanism study shows that molecular oxygen is readily activated by the NHPI/h-BN to form a superoxide radical(O_(2)^(·-)),which oxidize DBT to DBTO2 for desulfurization.

Liquid-phase epoxidation of propylene with molecular oxygen by chloride manganese meso-tetraphenylporphyrins

Propylene molecule owns two active sites,the direct epoxidation of propylene by dioxygen is still a challenge due to the limitation of selectivity.In this work,the direct liquid-phase propylene aerobic epoxidation protocol by chloride manganese meso-tetraphenylporphyrin(MnTPPCl)was developed.The conversion of propylene was 12.7%,and the selectivity towards PO(propylene oxide)reached up to 80.5%.The formation of PO was attributed to the mechanism via high-valent Mn species,which was confirmed by means of in situ UV–vis spectrum.

Catalytic oxidation of pentanethiol on basic nitrogen doped carbon hollow spheres derived from waste tires

A series of basic nitrogen doped carbon hollow spheres(p-N-C) catalysts derived from waste tires were prepared by a green, facile and environmental “leavening” strategy for the catalytic oxidation of pentanethiol. Compared to pristine carbon, the p-N-C has a higher surface curvature conducive to the enrichment of substrates, leading to an excellent catalytic performance. This increased surface curvature of p-N-C was fabricated on the synergistic effect of two foaming agents((NH4)2 C2 O4 and NaHCO3), and the released gas also endows the spherical shell of p-N-C with a hierarchical porous structure, promoting the accessibility of active sites with pentanethiol. Pyridine-like and pyrrolic-like nitrogen atoms were investigated as reactive sites on the p-N-C to accelerate the electron transfer from sulfur to active surface oxygen and enhance the adsorption/oxidation process. As a result, the optimal p-N-C catalyst exhibits superior adsorption and oxidation performance(99.9%) of pentanethiol, outperforming the “unleavened”catalyst(20.8%). This work offers a new avenue for the fabrication of highly efficient materials for the desulfurization of fuel.

Controlling hydrogenation of C=C and C=O bonds in cinnamaldehyde using Pt_(1)/Ni and Pt_(1)/Co single-atom alloy catalysts

Selective hydrogenation of C=C and C=O bonds in cinnamaldehyde(CAL)to produce desired products is a challenging task due to the complex conjugate system of the two unsaturated functional groups.In this study,a simple ball milling method is presented for synthesizing Pt-based single-atom alloy catalysts(SAAs)that can function as a control switch for the selective hydrogenation of CAL into highly valuable products.

Cyclohexene Promoted Efficient Biomimetic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by Manganese Porphyrin under Mild Conditions

Selective oxidation of alcohols to corresponding carbonyl compounds is one of the most important processes both in academic and application research.As a kind of biomimetic catalyst,metalloporphyrins-catalyzed aerobic oxidation of alcohols with aldehyde as hydrogen donator is gathering much attention.However,using olefins as another kind hydrogen donator for aerobic oxidation of alcohols has not been reported.In this study,a system comprising managenese porphyrin and cyclohexene for biomimetic aerobic oxidation of alcohols to carbonyl compounds was developed.The catalytic system exhibited excellent catalytic performance and selectivity towards the corresponding products for most primary and secondary alcohols under mild conditions.Based on the results obtained from experiments as well as in situ EPR(electron paramagnetic resonance)and UV-vis spectroscopy,the role of cvclohexene was demonstrated.

Photosynthetic Characterization of the Plant Dicranopteris dichotoma Bernh. in a Rare Earth Elements Mine

In order to investigate the distribution of rare earth elements （REEs） in the natural hyperaccumulator fern Dicranopteris dichotoma Bernh. and to characterize this plant photosynthetically, concentrations of REEs in D. dichotoma from mines mining heavy and light REEs （HREEs and LREEs, respectively）, as well as in D. dichotoma from an area in which no mining occurred, in southern Jiangxi Province were determined using inductively coupled plasma-mass spectrometry. The REE concentrations in the lamina of D. dichotoma were in the order LREEs mine 〉 HREEs mine 〉 non-mining area. The maximum REE content in the lamina of D. dichotoma from the LREE mine was approximately 2 648 mg/kg dry weight. The photosynthetic activity of D. dichotoma from areas of HREE and LREE mines was improved by the presence of high concentrations of REEs in the lamina compared with D. dichotoma from the non-mining area. However, this enhancement varied according to the concentrations of the REEs, as well as their type. In addition, 77K fluorescence, electron transport rate, and chlorophyll-protein complex studies showed that the enhancement of the photosynthetic activity of D. dichotoma from HREE mines was mainly due to an increase in the chlorophyll-protein complex of the reaction center of photosystem （PS） Ⅰ, whereas the enhancement observed in D. dichotoma from LREE mines was due to an increase in the internal antennae chlorophyll-protein complex of PS Ⅱ and greater light energy distribution to the light-harvesting chlorophyll-protein complex of PS Ⅱ.

Oxygen Atom Transfer Mechanism for Vanadium-Oxo Porphyrin Complexes Mediated Aerobic Olefin Epoxidation

The development of catalytic aerobic epoxidation by numerous metal complexes in the presence of aldehyde as a sacrificial reductant(Mukaiyama epoxidation)has been reported,however,comprehensive examination of oxygen atom transfer mechanism involving free radical and highly reactive intermediates has yet to be presented.Herein,meso-tetrakis(pentafluorophenyl)porphyrinatooxidovanadium(Ⅳ)(VOTPFPP)was prepared and proved to be efficient toward aerobic olefin epoxidation in the presence of isobutyraldehyde.In situ electron paramagnetic resonance spectroscopy(in situ EPR)showed the generation,transfer pathways and ascription of free radicals in the epoxidation.According to the spectral and computational studies,the side-on vanadium-peroxo complexes are considered as the active intermediate species in the reaction process.In the cyclohexene epoxidation catalyzed by VOTPFPP,the kinetic isotope effect value of 1.0 was obtained,indicating that epoxidation occurred via oxygen atom transfer mechanism.The mechanism was further elucidated using isotopically labeled dioxygen experiments and density functional theory(DFT)calculations.

Copper-Mediated and Catalyzed C-H Bond Amination via Chelation Assistance: Scope, Mechanism and Synthetic Applications

Nitrogen-containing compounds are ubiquitously found in the fields of organic chemistry,pharmaceuticals,agrochemicals,medicinal chemistry and functional materials.The C-H bond amination reaction is one of the most straightforward protocols in the CN bond formation,showing"step"and"atomic"economy.As a catalyst for C-H amination reaction,copper exhibits its unique catalytic properties due to easily accessible oxidation states.The research progress of copper-catalyzed C-H amination in recent years is summarized.At the same time,reaction mechanisms are also briefly described in representative aminations to provide insights for the development prospects of highly practical and more environmentally benignprocesses.

Manganese porphyrin-mediated aerobic epoxidation of propylene with isoprene: A new strategy for simultaneously preparing propylene epoxide and isoprene monoxide

The direct epoxidation of propylene by O_(2) is a significant and challenging topic. The key factor for this homogeneous aerobic epoxidation is the activation of molecular oxygen under mild conditions. In this work,the aerobic epoxidation of propylene catalyzed by manganese porphyrins was achieved in the presence of isoprene. Isoprene contains an allyl methyl group, and the α-H can be easily removed to achieve the activation of molecular oxygen. The conversion of propylene was 38% and the selectivity toward propylene oxide(PO) was up to 87%. The role of isoprene was demonstrated, and a plausible mechanism was proposed. The protocol reported herein is expected to provide a strategy for the simultaneous preparation of propylene oxide and isoprene monoxide.

Substrate specificity in the biomimetic catalytic aerobic oxidation of styrene and cyclohexanone by metalloporphyrins: kinetics and mechanistic study

Substrate specificity is a hallmark of enzymatic catalysis.In this work,the biomimetic catalytic oxidation of styrene and cyclohexanone by iron(III)porphyrins and molecular oxygen was carried out,and remarkable differences in efficiency were observed.The specificity of the substrates for biomimetic catalytic oxidation was investigated by kinetics and mechanistic studies.Kinetics studies revealed that the oxidation of styrene followed Michaelis-Menten kinetics with KM=8.99 mol L^(-1),but the oxidation of cyclohexanone followed first-order kinetics with kobs=1.46×10^(-4) s^(-1),indicating that the styrene epoxidation by metalloporphyrins exhibited characteristics of enzyme-like catalysis,while the oxidation of cyclohexanone was in agreement with the general rules of chemical catalysis.Different catalytic mechanisms for the two substrates were discussed by operando electron paramagnetic resonance spectroscopy,operando UV-vis spectroscopy,and KI/starch experiments.Substrate specificity was concluded to be attributed to the stability of high-valence species and oxygen transfer rate.