Direct oxidation of the C_(sp3)-H bonds of N-heterocyclic compounds to give the corresponding ketones using a reusable heterogeneous MnO_x-N@C catalyst

Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catalytic system exhibited a broad substrate scope and excellent regi‐oselectivity, as well as being amenable to gram‐scale synthesis. This MnOx‐N@C catalyst also showed good reusability and was successfully recycled six times without any significant loss of activity.

Highly Efficient,Green Oxidation of Alcohols Using Novel Heterogeneous Ruthenium Catalyst

MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Furthermore, this catalyst was also effective towards alcohol oxidation using water as solvent instead of toluene.

Co-salen functionalized on graphene as an efficient heterogeneous catalyst for cyclohexene oxidation

Co-salen functionalized on graphene with an average pore size of 27.7 nm as a heterogeneous catalyst exhibited good catalytic activity and recyclability in cyclohexene oxidation.

Heterogeneous Oxidation of Methylene Blue with Surface-Modified Iron-Amended Activated Carbon

The present study aims to develop effective adsorption and oxidation of synthetic dye in wastewater by using the newly synthesized iron-amended activated carbon. Recently synthetic dye-containing wastewater has gained more attention due to its mass discharge, high toxicity and low biodegradation. For enhancing adsorption of dye and oxidative regeneration of dye-exhausted activated carbon, the novel amendment of iron-deposited granular activated carbon (GAC) was developed. It was to amend ferrous ion onto the acid-pretreated GAC when pH of iron solution was higher than the pH at point of zero charge (pH, pzc) of the GAC. Methylene blue (MB) in water was adsorbed onto the acid-treated iron- amended GAC (Fe-GAC) followed by single or multiple applications of H2O2. Batch experiments were carried out to study the adsorption isotherm and kinetics indicating adsorption of MB onto the Fe-GAC followed Langmuir isotherm and the pseudo-second order kinetics. The Fe-GACshowed the maximum adsorption capacity (qm) of 238.1 ± 0.78 mg/g which was higher than the virgin GAC with qm of 175.4 ± 13.6 mg/g at 20?C, pH 6 and the initial concentration of 20 - 200 mg/L. The heterogeneous Fenton oxidation of MB in the Fe-GAC revealedthat increasing the H2O2 loading from 7 to 140 mmol H2O2/mmol MB led to enhancing the oxidation efficiency of MB in the GAC from 62.6% to 100% due to the increased generation of hydroxyl radicals. Further enhancement of oxidation of MB in the Fe-GAC was made by the multiple application of H2O2 while minimizing OH radical scavenging often occurring at high concentration of H2O2. Therefore, the acid-treated iron-amended GAC would provide excellent adsorption capacity for MB and high oxidation efficiency of MB in the GAC with multiple applications of H2O2 and optimum iron loading.

Fabrication and characterization of tungsten-containing mesoporous silica for heterogeneous oxidative desulfurization

A series of functional,tungsten-containing mesoporous silica materials（W-SiO2） have been fabricated directly from an ionic liquid that contained imidazole and polyoxometalate,which acted as mesoporous template and metal source respectively.These materials were then characterized through X-ray diffraction（XRD）,transmission electron microscopy（TEM）,Raman spectroscopy,Fourier transform infrared spectra（FTIR）,diffuse reflectance spectra（DRS）,and N2 adsorption-desorption,which were found to contain tungsten species that were effectively dispersed throughout the structure.The as-prepared materials W-SiO2 were also found to possess a mesoporous structure.The pore diameters of the respective sample W-SiO2-20 determined from the TEM images ranged from 2 to 4 nm,which was close to the average pore size determined from the nitrogen desorption isotherm（2.9 nm）.The materials were evaluated as catalysts for the heterogeneous oxidative desulfurization of dibenzothiophene（DBT）,which is able to achieve deep desulfurization within 40 min under the optimal conditions（Catalyst（W-SiO2-20）= 0.01 g,temperature = 60℃,oxidant（H2O2）= 20 μL）.For the removal of different organic sulfur compounds within oil,the ability of the catalyst（W-SiO2-20） under the same conditions to remove sulfur compounds decreased in the order：4,6-dimethyldibenzothiophene Dibenzothiophene Benzothiophene 1-dodecanethiol.Additionally,they did not require organic solvents as an extractant in the heterogeneous oxidative desulfurization process.After seven separate catalytic cycles,the desulfurization efficiency was still as high as 90.3%.From the gas chromatography-mass spectrometer analysis,DBT was entirely oxidized to its corresponding sulfone DBTO2 after reaction.A mechanism for the heterogeneous desulfurization reaction was proposed.

Deep oxidative desulfurization of gas oil based on sandwich-type polysilicotungstate supported β-cyclodextrin composite as an efficient heterogeneous catalyst

In this work,in order to obtain deep clean gas oil,a novel organic–inorganic hybrid(n-C4H9)4N)7H5Si2W18Cd4O68@β-cyclodextrin(abbreviated as TBA-Si WCd@β-CD)composite was synthesized by supporting quaternary ammonium salt of sandwich-type polysilicotungstate onβ-cyclodextrin(TBA-SiWCd@β-CD)as an efficient catalyst for oxidative desulfurization(ODS)of gas oil.The successful composition of the materials explained by the formation of host–guest inclusion complex,which confirmed through FTIR,UV–vis,XRD,SEM,and EDX characterization analyses.Experimental results revealed that the levels of sulfur content and mercaptan compounds of gas oil lowered with 97%removal efficiency.Compared with the ODS treatment of gas oil,the TBA-Si WCd@β-CD composite showed an outstanding catalytic performance for the oxidation of dibenzothiophene(DBT)in the prepared model fuel.The main factors that influence the desulfurization efficiency and the kinetic study of the ODS process were investigated.The prepared heterogeneous catalyst was found to give remarkable reusability for five runs without a discernible decrease in its activity.This study suggested the potential application of the TBA-Si WCd@β-CD catalyst for removal of hazardous sulfur compounds from gas oil fuel.

Polyoxometalate-based silica-supported ionic liquids for heterogeneous oxidative desulfurization in fuels

With the aim of deep desulfurization, silica-supported polyoxometalate-based ionic liquids were successfully prepared by a one-pot hydrothermal process and employed in heterogeneous oxidative desulfurization of various sulfur compounds. The compositions and structures of the hybrid samples were characterized by various methods such as FT-IR, XPS, Raman,UV–Vis, wide-angle XRD and N2adsorption–desorption. The experimental results indicated that the hybrid materials presented a high dispersion of tungsten species and excellent catalytic activity for the removal of 4,6-dimethyldibenzothiophene without any organic solvent as extractant, and the sulfur removal could reach 100.0% under mild conditions.The catalytic performance on various substrates was also investigated in detail. After cycling seven cycles, the sulfur removal of the heterogeneous system still reached 93.0%. The GC-MS analysis results demonstrated that the sulfur compound was first adsorbed by the catalyst and subsequently oxidized to its corresponding sulfone.

Importance, features and uses of metal oxide catalysts in heterogeneous catalysis

This short review paper aims at assembling the present state of the art of the multiuses of metal oxides in heterogeneous catalysis, concerning liquid and gaseous phases of the reactant mixtures on solid catalysts. It includes the description of the main types of metal oxide catalysts, of their various preparation procedures and of the main reactions catalysed by them (acid-base type, selective and total oxidations, bi-functional catalysis, photocatalysis, biomass treatments, environmental catalysis and some of the numerous industrial applications). Challenges and prospectives are also discussed.

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.

Selective oxidation of emerging organic contaminants in heterogeneous Fenton-like systems

Heterogeneous Fenton-like reaction shows great potential for eliminating organic substances (e.g. emerging organic contaminants (EOCs)) in water, which has been widely explored in recent decades. However, the catalytic mechanisms reported in current studies are extremely complicated because multiple mechanisms coexist and contribute to the removal efficiencies. Most importantly, heterogeneous systems show selective oxidation properties, which are crucial for improving the efficiencies in the catalytic elimination of organic substances. Thus, this critical review summarizes and compares the diverse existing mechanisms (non-radical and radical pathways) in heterogeneous catalytic processes based on recent studies. The typical oxidation mechanisms during selective advanced oxidation of EOCs were systematically discussed based on the following sections, including the selective adsorption and generation of reactive oxygen species (ROS) in photo/electron-Fenton and Fenton-like systems. Moreover, the non-radical pathways are discussed in depth by the singlet oxygen, high-valent metal-oxo, electron transfer process, etc. Moreover, the direct oxidative transfer process for the removal of EOCs was introduced in recent studies. Finally, the cost, feasibility as well as the sustainability of heterogeneous Fenton-like catalysts are summarized. This review offers useful guidance for developing suitable strategies to develop materials for decomposing the organic substrates.

Selective Hydrodeoxygenation of Lignin-Derived Vanillin via Hetero-Structured High-Entropy Alloy/Oxide Catalysts

The chemoselective hydrodeoxygenation of natural lignocellulosic materials plays a crucial role in converting biomass into value-added chemicals.Yet their complex molecular structures often require multiple active sites synergy for effective activation and achieving high chemoselectivity.Herein,it is reported that a high-entropy alloy(HEA)on high-entropy oxide(HEO)hetero-structured catalyst for highly active,chemoselective,and robust vanillin hydrodeoxygenation.The heterogenous HEA/HEO catalysts were prepared by thermal reduction of senary HEOs(NiZnCuFeAlZrO_(x)),where exsolvable metals(e.g.,Ni,Zn,Cu)in situ emerged and formed randomly dispersed HEA nanoparticles anchoring on the HEO matrix.This catalyst exhibits excellent catalytic performance:100%conversion of vanillin and 95%selectivity toward high-value 2-methyl-4 methoxy phenol at low temperature of 120℃,which were attributed to the synergistic effect among HEO matrix(with abundant oxygen vacancies),anchored HEA nanoparticles(having excellent hydrogenolysis capability),and their intimate hetero-interfaces(showing strong electron transferring effect).Therefore,our work reported the successful construction of HEA/HEO heterogeneous catalysts and their superior multifunctionality in biomass conversion,which could shed light on catalyst design for many important reactions that are complex and require multifunctional active sites.

Heterogeneous catalytic activation of peroxymonosulfate for efficient degradation of organic pollutants by magnetic Cu^0/Fe_3O_4 submicron composites

Magnetic Cu^0/Fe3O4 submicron composites were prepared using a hydrothermal method and used as heterogeneous catalysts for the activation of peroxymonosulfate（PMS） and the degradation of organic pollutants.The as-prepared magnetic Cu^0/Fe3O4 submicron composites were composed of Cu^0 and Fe3O4 crystals and had an average size of approximately 220 nm.The Cu^0/Fe3O4 composites could efficiently catalyze the activation of PMS to generate singlet oxygen,and thus induced the rapid degradation of rhodamine B,methylene blue,orange Ⅱ,phenol and 4-chlorophenol.The use of0.1 g/L of the Cu^0/Fe3O4 composites induced the complete removal of rhodamine B（20 μmol/L） in15 min,methylene blue（20 μmol/L） in 5 min,orange Ⅱ（20 μmol/L） in 10 min,phenol（0.1mmol/L） in 30 min and 4-chlorophenol（0.1 mmol/L） in 15 min with an initial pH value of 7.0 and a PMS concentration of 0.5 mmol/L.The total organic carbon（TOC） removal higher than 85%for all of these five pollutants was obtained in 30 min when the PMS concentration was 2.5 mmol/L.The rate of degradation was considerably higher than that obtained with Cu^0 or Fe3O4 particles alone.The enhanced catalytic activity of the Cu^0/Fe3O4 composites in the activation of PMS was attributed to the synergistic effect of the Cu^0 and Fe3O4 crystals in the composites.Singlet oxygen was identified as the primary reactive oxygen species responsible for pollutant degradation by electron spin resonance and radical quenching experiments.A possible mechanism for the activation of PMS by Cu^0/Fe3O4 composites is proposed as electron transfer from the organic pollutants to PMS induces the activation of PMS to generate ^1O2,which induces the degradation of the organic pollutants.As a magnetic catalyst,the Cu^0/Fe3O4 composites were easily recovered by magnetic separation,and exhibited excellent stability over five successive degradation cycles.The present study provides a facile and green heterogeneous catalysis method for the oxidative removal of organic pollutants.

A review of the direct oxidation of methane to methanol

This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol （DMTM） with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts.

Iron-glutamate-silicotungstate ternary complex as highly active heterogeneous Fenton-like catalyst for 4-chlorophenol degradation

A novel iron-glutamate-silicotungstate ternary complex（FeШGluS iW） was synthesized from ferric chloride（FeI II）,glutamic acid（Glu）,and silicotungstic acid（SiW）,and used as a heterogeneous Fenton-like catalyst for 4-chlorophenol（4-CP） degradation at neutral pH value. The prepared FeШGluS iW was characterized using inductively coupled plasma atomic emission spectroscopy,thermogravimetry,Fourier-transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,X-ray diffraction,and field-emission scanning electron microscopy. The results showed that FeШGluS iW has the formula [Fe（C5H8NO4）（H2O）]2SiW 12O40？13H2O,with glutamate moiety and Keggin-structured SiW 12O404- heteropolyanion. The catalyst showed high catalytic activity in 4-CP degradation in the dark and under irradiation. Under the conditions of 4-CP 100 mg/L,FeШGluS iW 1.0 g/L,H2O2 20 mmol/L,and pH = 6.5,4-CP was completely decomposed in 40 min in the dark and in 15 min under irradiation. When the reaction time was prolonged to 2 h,the corresponding total organic carbon removals under dark and irradiated conditions were ca. 27% and 72%,respectively. The high catalytic activity of FeI IIGluS iW is resulted from hydrogen bonding of H2O2 on the FeI IIGluS iW surface. The enhanced degradation of 4-CP under irradiation arises from simultaneous oxidation of 4-CP through Fenton-like and photocatalytic processes respectively catalyzed by ferric iron and the SiW 12O404- hetropolyanion in FeШGluS iW.

Ni-based catalysts derived from a metal-organic framework for selective oxidation of alkanes

Ni nanoparticles embedded in nitrogen-doped carbon（Ni@C-N） materials were prepared by ther-molysis of a Ni-containing metal-organic framework （Ni-MOF） under inert atmosphere. The as-synthesized Ni@C-N materials were characterized by powder X-ray diffraction, N_2 adsorp-tion-desorption analysis, scanning electron microscopy, transmission electron microscopy, atomic absorption spectroscopy, and X-ray photoelectron spectroscopy. The MOF-derived Ni-based mate-rials were then examined as heterogeneous catalysts for the oxidation of alkanes under mild reac-tion conditions. The Ni@C-N composites displayed high activity and selectivity toward the oxidation of a variety of saturated C–H bonds, affording the corresponding oxidation products in good-to-excellent yields. Furthermore, the catalysts could be recycled and reused for at least four times without any significant loss in activity and selectivity under the investigated conditions.

Mechanical properties and friction-wear characteristics of VN/Ag multilayer coatings with heterogeneous and transition interfaces

The heterogeneous multilayer interface of VN/Ag coatings and transition multilayer interface of VN/Ag coatings were prepared on Inconel 781 and Si(100),and the microstructures,mechanical and tribological properties were investigated from 25 to 700℃.The results showed that the surface roughness and average grain size of VN/Ag coatings with transition multilayer interface are obviously larger than those of VN/Ag coatings with heterogeneous multilayer interface.The coatings with transition multilayer interface have higher adhesion force and hardness than the coatings with heterogeneous multilayer interface,and both coatings can effectively restrict the initiation and propagation of microcracks.Both coatings have excellent self-adaptive lubricating properties with a decrease of friction coefficient as the temperature increases,but their wear rates reveal a drastic increase.The phase composition of the worn area of both coatings was investigated,which indicates that a smooth Ag,Magnéli phase(V2O5)and bimetallic oxides(Ag3VO4 and AgVO3)can be responsible to the excellent lubricity of both coatings.To sum up,the coatings with transition multilayer interface have excellent adaptive lubricating properties and can properly control the diffusion rate and release rate of the lubricating phase,indicating that they have great potential in solving the problem of friction and wear of mechanical parts.

Membrane enhanced COD degradation of pulp wastewater using Cu_2O/H_2O_2 heterogeneous Fenton process

Both activity and stability of the catalyst can be improved in heterogeneous Fenton reaction,in particular,with no limitation for the working p H and no production of the sludge.In this work,a combination of catalyst Cu_2O and pore-channel-dispersed H_2O_2is proposed to treat the pulp wastewater.Degradation degree of CODs in the wastewater was up to 77%in the ceramic membrane reactor using Cu_2O powder(2.0 g·L^(-1))and membranefeeding H_2O_2(0.8 ml·L^(-1))within 60 min.Evolution of·OH radical formation in the advanced oxidation process was analyzed with a fluorescent method.Utilization efficiency of H_2O_2was successfully enhanced by 10%with the membrane distributor.Further on,the catalyst recyclability was evaluated in a five-cycle test.The concentration of copper ions being dissolved in the treated water was monitored with ICP.After Cu_2O/H_2O_2(membrane)treatment the effluent is qualified to discharge with COD concentration lower than 15 mg·L^(-1)with regard to the national standard GB25467-2010.

New insights for the catalytic oxidation of cyclohexane to K-A oil

Au-based catalysts have been reported to be active in the cyclohexane oxidation to K-A oil, but they showed some limitiations in terms of productivity, selectivity and required reaction conditions. The possibility to overcome some of these limits has been explored coupling Au with Cu, which can be suitable for undergoing the electron-switch in the initial step of the cyclohexane oxidation. Hence, a bimetallic 2 wt% Au Cu/Al_(2)O_(3) catalyst was tested in the oxidation of cyclohexane, working at mild conditions of 120 ℃ and 4 bar of O_(2). The combination of the catalyst with a very small amount of benzaldehyde used as cheaper and non-toxic radical initiator allowed to obtain a very high productivity of cyclohexanol and cyclohexanone(45 mmol*m L/mgmet*h) with a selectivity of 94%. Moreover, comparing the catalysed reaction with the non-catalysed one, the role of the catalyst has been disclosed.

Preparation of gold nanoparticles supported on Nb_2O_5 by deposition precipitation and deposition reduction methods and their catalytic activity for CO oxidation

Nanoparticulate gold catalysts supported on niobium oxides （Nb2O5） were prepared by different deposition methods. The deposition precipitation （DP） method, DP method with urea, deposition reduction （DR） method and one‐pot method were used to prepare a 1 wt%Au/Nb2O5 catalyst. Lay‐ered‐type Nb2O5 synthesized by a hydrothermal method （Nb2O5（HT）） was the most suitable as a support among various types of Nb2O5 including commercially available Nb2O5 samples. It appeared that the large BET surface area of Nb2O5（HT） enabled the dispersion of gold as nanoparticles （NPs）. Gold NPs with a mean diameter of about 5 nm were deposited by both the DP method and DR method on Nb2O5（HT） under an optimized condition. The temperature for 50%CO conversion for Au/Nb2O5（HT） prepared by the DR method was 73 ＆#176;C. Without deposition of gold, Nb2O5（HT） showed no catalytic activity for CO oxidation even at 250 ＆#176;C. Therefore, the enhancement of the activity by deposition of gold was remarkable. This simple Au/Nb2O5 catalyst will expand the types of gold catalysts to acidic supports, giving rise to new applications.

Catalytic ativities of single-atom catalysts for CO oxidation: Pt_1/FeO_x vs. Fe_1/FeO_x

An FeOx‐based Pt single‐atom catalyst(SAC),Pt1/FeOx,has stimulated significant recent interest owing to its extraordinary activity toward CO oxidation.The concept of SAC has also been successfully extended to other FeOx supported transition metal systems both experimentally and theoretically.However,the FeOx substrate itself(denoted by Fe1/FeOx following the same nomenclature of Pt1/FeOx)as a typical transition metal oxide possesses a very low catalytic activity toward CO oxidation,although it can be viewed as Fe1/FeOx SAC.Here,to understand the catalytic mechanism of FeOx‐based SACs for CO oxidation,we have performed density functional theory calculations on Pt1/FeOx and Fe1/FeOx for CO oxidation to address the differences between these two SACs in terms of the catalytic mechanism of CO oxidation and the chemical behavior of the catalysts.Our calculation results indicated that the catalytic cycle of Fe1/FeOx is much more difficult to accomplish than that of SAC Pt1/FeOx because of a high activation barrier(1.09eV)for regeneration of the oxygen vacancy formed when the second CO2molecule desorbs from the surface.Moreover,density of states and Bader charge analysis revealed differences in the catalytic performance for CO oxidation by the SACs Fe1/FeOx and Pt1/FeOx.This work provides insights into the fundamental interactions between the single‐atom Pt1and FeOx substrate,and the exceptional catalytic performance of this system for CO oxidation.