Swelling acidic poly(ionic liquid)s as efficient catalysts for the esterification of cyclohexene and formic acid

Acidic poly(ionic liquid)s(PILs)with swelling ability were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,divinylbenzene(DVB)and sodium acrylate(NaAA),and further acidification by sulfuric acid.The swelling ability of acidic PILs was greatly affected by cross-linker content and chain length of 3-alkyl-substituents on imidazolium.Cross-linked network structures could be observed from the cryogenic scanning electron microscopy(cryo-SEM)images of the swollen acidic PILs in formic acid.Acidic PILs with network structures in swollen state exhibited excellent activities in the esterification of cyclohexene and formic acid,and the catalytic activities were in positive correlation with their swelling abilities.Acidic PIL with 3-octyl-substituent and 2.5 mol%DVB(PIL-C8-2.5DVB-HSO4)had the highest swelling ability in formic acid and exhibited comparable catalytic activities with homogeneous catalysts such as sulfuric acid and p-toluenesulfonic acid.

Hydrothermal synthesis and catalytic performance of bulky titanium silicalite-1 aggregates assembled by bridged organosilane

A facile and effective method to synthesize TS‐1zeolite aggregates has been presented.The crystallization of silanized seeds and nanocrystallites led to large and irregular TS‐1zeolite aggregates ranging from5to40μm in size,based on the special sol‐gel chemistry of bridged organosilane.Epoxidation of1‐hexene and cyclohexene was used as a probe reaction to investigate the catalytic performance of the resulting materials.These TS‐1zeolite aggregates possessed both the conventional nanoparticle properties of TS‐1zeolites and variable surface hydrophilic/hydrophobic features,which enhanced the catalytic properties of hydroperoxides for alkene epoxidation.Moreover,the large aggregates effectively simplified the separation procedure during preparation and catalytic reactions.

Preparation and characterization of amino or carboxyl-functionalized ionic liquids

New functionalized ionic liquids, 1-carboxylmethyl-3-methylimimidazolium hexafluorophosphate or fluoborate and 1-aminoethyl-3-methylimimidazolium hexafluorophosphate or fluoborate have been synthesized and investigated. The obtained amino or carboxyl-functionalized ionic liquids were all characterized by FT-IR, ^1H NMR and MS （ESI） and their properties such as freezing point, viscosity, solubility, specific gravity, surface tension, and interfacial tension were also determined.

Synthesis of Methyl Isopropyl Ketone and Diethyl Ketone over Ni-Na/ZrO_2-MnO_2-ZnO Catalyst

ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.

Structure and Magnetic Properties of a Manganese Complex with 1-Carboxymethylpyridinium-3-carboxylate

One complex with a zwitterionic dicarboxylate ligand, [Mn（L）（N3）]n 1 （L = 1-car- boxymethylpyridinium-3-carboxylate）, was synthesized and structurally characterized. Complex 1 crystallizes in triclinic, space group P1 with a = 7.570（2）, b = 7.808（2）, c = 9.232（3） A, β= 94.450（19）°, V= 489.0（3） A3, Z = 2, Mr = 277.11, Dc = 1.882 g/cm3, F（000） = 278,μ = 1.359 mm-1, S = 1.021, the final R = 0.0509 and wR = 0.1149 for 2236 observed reflections with 1 〉 2σ（I）. Complex 1 consists of two-dimensional coordination layers in which the anionic uniform chains with mixed triple bridges （one end-on （EO） azide and two syn-syn carboxylates） are cross-linked by the flexible cationic N-methylpyridinium spacers. Magnetic studies demonstrated that the triple bridge in 1 transmits antiferromagnetic coupling between the Mn（Ⅱ） ions.

Selective conversion of methanol to propylene over highly dealuminated mordenite:Al location and crystal morphology effects

The growing consumption of light olefins has stimulated intensive researches on methanol to olefin(MTO)process which possesses great advantages for coal conversion to value‐added chemicals in an environmentally benign way.The catalysts commonly used for MTO process faces several challenges such as poor selectivity control,low hydrothermal stability and short lifetime.In the present study,we prepared a series of mordenite zeolites with variable Al contents(Si/Al molar ratios of 51−436)by a sequential dealumination treatment of air‐calcination and acid leaching.The textural properties,acidity and Al location before and after the dealumination treatment have been systematically studied and their effect on MTO especially the methanol to propylene(MTP)performance was thoroughly investigated.The mordenite zeolites with the Si/Al ratios over 150 selectively catalyzed methanol conversion in the MTP pathway,providing a high propylene selectivity of 63%and propylene/ethylene ratio of>10.Compared to the low‐silica MOR catalysts,highly dealuminated MOR showed much higher stability and longer lifetime,which can be further enhanced via harsh hydrothermal pretreatment.Furthermore,the lifetime was highly related to the crystal size along c‐axis.The excellent performance of highly dealuminated MOR is likely ascribed to the mesopores formed upon dealumination and the scarce Al sites located in the T sites shared by the 8‐member ring(MR)side pockets and 12‐MR pore channels.

Electrocatalytic Synthesis of Propylene Carbonate from CO_2 and Propylene Oxide

The electrocatalytic synthesis of propylene carbonate（PC） from CO2 and propylene oxide（PO） was studied under mild conditions（PCO2=1.01×105 Pa, t=25 ℃）. Influences of solvents, supporting electrolytes, the passed charge, the nature of electrodes and the current density（j） on the yield of PC were investigated to optimize the electrolytic conditions, with the maximal yield to be 46.2%, the selectivity of propylene carbonate is 100%. The reduction of propylene oxide in the absence and presence of CO2 was examined by cyclic voltammetry. The mechanism of the reaction initiated by the synergistic effect of halides ions of supporting electrolytes with nucleophilicity and the metal ions from scarification anode with Lewis acid acidity was proposed on the basis of our results.

[Bmim]OAc Catalyzed Michael Addition of Active Methylene to α,β-Unsaturated Carboxylic Esters and Nitriles

Michael addition of active methylene compounds to α,β-unsaturated carboxylic esters and nitriles was effectively catalyzed by a basic ionic liquid, 1-butyl-3-methylimidazolium acetate（[Bmim]OAc）. The his-addition products were selectively obtained in high yields under mild reaction conditions.

Synthesis and structure determination of pyrazine-containing macrocyclic polyazomethines

Two pyrazine-containing macrocyclic polyazomethines 2 and 3 were synthesized by direct [2 ＋ 2] and [3 ＋ 3] condensation reactions between 2,21-[pyrazine-2,3-diylbis（oxy）]dibenzaldehyde （1） and hydrazine. Both 2 and 3 were characterized by NMR, HRMS, and their structures were determined via X-ray crystal diffraction studies.

Electrochemical Activation of CO_2 for the Synthesis of Ethyl Carbanilate under Mild Conditions

A novel electrochemical procedure for the synthesis of ethyl carbanilate from aniline and carbon dioxide was developed via the selective cathodic reduction of carbon dioxide in CO2-saturated DMF solution containing 0. 1 mol/L TEABr at room temperature, followed by the addition of Eft as an alkylating agent. The synthesis was carried outun der mild[p（CO2） = 1.0×10^5 Pa, t =20 ℃ ] and safe conditions. Influences of the nature of the electrodes, the current densities, the passed charges during electrolysis, temperatures, and supporting electrolytes on the yield of ethyl carbanilate were studied to optimize the electrolytic conditions. The selectivity of ethyl carbanilate is 100%.

Cooperative structure-directing effect of choline cation and *BEA zeolite in the synthesis of aluminogermanosilicate IWR zeolite

In this contribution,we report the cooperative structure-directing effect of choline hydroxide and aluminosilicate*BEA zeolite in the synthesis of aluminogermanosilicate IWR zeolites for the first time.*BEA zeolites,at variance with any other aluminosilicate zeolites,can serve as heterogeneous seeds for the growth of IWR zeolites and play a cooperative structure-directing role.The crystallization process was investigated using multiple techniques to characterize a series of solid products obtained with various crystallization times.The experiments clearly showed the dissolution of the*BEA zeolite and of an intermediate CDO-type structure.A plausible mechanism for the novel cooperative synthesis has been proposed.The crystallization of the IWR zeolite involves several steps,among which the crucial one is believed to be the reassembly of the building units produced from the decomposition of*BEA zeolite seeds,induced by choline molecules.Having similar structure and common building units(four-,five-,and six-membered rings)with the IWR zeolite,the*BEA zeolite is capable of promoting the reassembly of the building units and can thus play a cooperative structure-directing role.By highlighting the cooperative structure-directing effect of organic molecules and heterogeneous seeds,this study opens up new perspectives for the synthesis of target zeolites that are difficult to prepare by traditional methods.This new synthetic route is also expected to shed light on the discovery of novel zeolites.

Oxidative coupling of methane:MO_x-modified (M=Ti,Mg,Ga,Zr) Mn_2O_3-Na_2WO_4/SiO_2 catalysts and effect of MO_x modification

Mn_2O_3-Na_2WO_4/SiO_2 is considered as the most promising catalyst for the oxidative coupling of methane（OCM） process; however, it only has a better catalytic performance over 800 °C. To improve its low-temperature performance, an attempt has been made to modify the Mn_2O_3-Na_2WO_4/SiO_2 catalyst using TiO_2, MgO, Ga_2O_3, and ZrO_2. Among the synthesized catalysts, the TiO_2-modified Mn_2O_3-Na_2WO_4/SiO_2 catalyst shows markedly improved low-temperature OCM performance,achieving a high CH_4 conversion of ~23% and a good C_2-C_3 selectivity of ~73% at 700 °C（the catalyst bed temperature）, along with promising stability for at least 300 h without signs of deactivation.In comparison with the unmodified Mn_2O_3-Na_2WO_4/SiO_2 catalyst, the TiO_2 modification results in significant improvement in the low-temperature activity/selectivity, whereas the MgO modification has almost no impact and the Ga_2O_3 and ZrO_2 modifications have a negative effect. The X-ray diffraction（XRD） and Raman results reveal that the formation of a MnTiO_3 phase and a MnTiO_3-dominated catalyst surface is crucial for the improvement of the low-temperature activity/selectivity in the OCM process.

Synthesis and application of an IL-supported diol as protecting group for aldehydes

A new IL-supported diol, 1-（2,3-dihydroxypropyl）-3-methylimidazolium hexafluorophosphate has been synthesized and characterized by Fr-IR, ^1H NMR, ^13C NMR and MS （ESI）. Its physical properties such as freezing point, solubility and specific gravity and thermal stability were determined. Synthetic utilities of the resultant diol as a protecting group for aldehydes were also investigated.

BrФnsted Acidic Ionic Liquids as Efficient Catalysts and Mediums for the Synthesis of Half-esters: Structure-catalytic Selectivity Relationship

Bronsted acidic ionic liquids based on imidazolium cation were employed as efficient catalysts and mediums for the ring opening of phthalic anhydride to synthesize half-esters. Good yields, short reaction time and mild reaction condition were achieved. Lower acidity of ionic liquid resulted in higher catalytic selectivity in the synthesis of half-esters. The minimum-energy geometries of sulfonic acid-functionalized ionic liquids based on imidazolium cation revealed that their acidities and catalytic selectivity in the synthesis of half-esters were related to their structures.

Molecular and Supramolecular Structures of Manganese(Ⅱ) and Cobalt(Ⅱ) Complexes with 1-Carboxymethylpyridinium-4-carboxylate

Two complexes with a zwitterionic dicarboxylate ligand,Mn（L）2（H2O）4 1 and Co（L）2（H2O）4 2（L = 1-carboxymethylpyridinium-4-carboxylate）,were synthesized and structurally characterized.Complex 1 crystallizes in monoclinic,space group P21 with a = 6.490（2）,b = 19.210（7）,c = 7.813（3） ,β = 92.716（5）o,V = 972.9（6） 3,Z = 2,Mr = 487.28,Dc = 1.663 g/cm3,F（000） = 502,μ = 0.749 mm-1,S = 1.060,the final R = 0.0377 and wR = 0.0893 for 3292 observed reflections with I 2σ（I）.Complex 2 is isomorphous with 1,with a = 6.478（2）,b = 19.052（7）,c = 7.742（3） ,β = 92.690（4）o,V = 954.6（6） 3,Z = 2,Mr = 491.28,Dc = 1.709 g/cm3,F（000） = 506,μ = 0.971 mm-1,S = 1.035,the final R = 0.0425 and wR = 0.0809 for 3289 observed reflections with I 2σ（I）.In the compounds,the mononuclear [M（L）2（H2O）4] units with trans-octahedral coordination geometry are linked into 3D architectures via hydrogen bonding（or second-sphere coordination） involving carboxylate groups and coordinated water molecules.The 3D networks illustrate a 3,8-connected net with Schlfli symbol（4·62）2（42·623·83）.

Efficient and recyclable Rh-catalytic system with involvement of phosphine-functionalized phosphonium-based ionic liquids for tandem hydroformylation—acetalization

The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.

The influence of pore structures and Lewis acid sites on selective hydrogenolysis of guaiacol to benzene over Ru/TS-1

Here,we report a Ru/TS-1 catalyst for selective hydrogenolysis of guaiacol to benzene in the aqueous phase at conditions of 240℃ and 0.2 MPa H2,achieving a benzene yield of 86% with a hydrogenolysis rate of 103.1 mmol g^(-1) h^(-1).It was found that Silicalite-1(MFI type) with suitable pore sizes supported Ru nanoparticles(NPs) favored for hydrogenolysis of guaiacol,whereas de-aluminated Ru/HBEA,Ru/HY and Ru/MWW(without acidic sites) accelerated the parallel reactions of hydrogenation of aromatics.In addition,Ru NPs located at the orifice of Silicalite-1 was proved to be more electron-deficient and active than Ru NPs on the outer surface,as evidenced by CO-IR characterization and activity tests on Ru/Silicalite-1(with and without templates).Moreover,Br?nsted acid sites(BAS) on Ru/MFI highly promoted the hydrogenation rates of aromatics,while Lewis acid sites(LAS) on Ru/TS-1 and Ru/MFI led to a linear increase of guaiacol hydrogenolysis rate to benzene,probably due to the enhanced absorbance capability of guaiacol and phenol on the LAS of MFI.Thus,pore structure properties of MFI coupled with abundant LAS(TS-1) as well as Ru NPs on the orifice of pores of TS-1 construct a promising catalyst for achieving efficient aromatic hydrocarbons from selective hydrogenolysis of lignin.

Ti_(3)C_(2)T_(x) MXene/carbon composites for advanced supercapacitors:Synthesis,progress,and perspectives

MXenes are a family of two-dimensional(2D)layered transition metal carbides/nitrides that show promising potential for energy storage applications due to their high-specific surface areas,excellent electron conductivity,good hydrophilicity,and tunable terminations.Among various types of MXenes,Ti_(3)C_(2)T_(x) is the most widely studied for use in capacitive energy storage applications,especially in supercapacitors(SCs).However,the stacking and oxidation of MXene sheets inevitably lead to a significant loss of electrochemically active sites.To overcome such challenges,carbon materials are frequently incorporated into MXenes to enhance their electrochemical properties.This review introduces the common strategies used for synthesizing Ti_(3)C_(2)T_(x),followed by a comprehensive overview of recent developments in Ti_(3)C_(2)T_(x)/carbon composites as electrode materials for SCs.Ti_(3)C_(2)T_(x)/carbon composites are categorized based on the dimensions of carbons,including 0D carbon dots,1D carbon nanotubes and fibers,2D graphene,and 3D carbon materials(activated carbon,polymer-derived carbon,etc.).Finally,this review also provides a perspective on developing novel MXenes/carbon composites as electrodes for application in SCs.

Temperature and excitation dependence of stimulated emission and spontaneous emission in InGaN epilayer

Temperature and excitation dependent photoluminescence(PL) of InGaN epilayer grown on c-plane Ga N/sapphire template by molecular beam epitaxy(MBE) has been systematically investigated. The emission spectra of the sample consisted of strong multiple peaks associated with one stimulated emission(SE) located at 430 nm and two spontaneous emissions(SPE) centered at about 450 nm and 480 nm, indicating the co-existence of shallow and deep localized states.The peak energy of SE exhibiting weak s-shaped variation with increasing temperature revealed the localization effect of excitons. Moreover, an abnormal increase of the SPE intensity with increasing temperature was also observed, which indicated that the carrier transfer between the shallow and deeper localized states exists. Temperature dependent time-resolved PL(TRPL) demonstrated the carrier transfer processes among the localized states. In addition, a slow thermalization of hot carriers was observed in InGaN film by using TRPL and transient differential reflectivity, which is attributed to the phonon bottleneck effect induced by indium aggregation.

Preparation and Sensitivity of SnO2 Grafted MCM-41 Sensor

SnO2 grafted MCM-41 sensor was prepared by MOCVD in the pore of MCM-41. The sensor has high sensitivity for carbon monoxide at low temperature compared with commercially available low-surface-area tin dioxide.