Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism

Daidzein has been widely used in pharmaceuticals,nutraceuticals,cosmetics,feed additives,etc.Its preparation process and related reaction mechanism need to be further investigated.A cost-effective process for synthesizing daidzein was developed in this work.In this article,a two-step synthesis of daidzein(Friedel–Crafts acylation and[5+1]cyclization)was developed via the employment of trifluoromethanesulfonic acid(TfOH)as an effective promoting reagent.The effect of reaction conditions such as solvent,the amount of TfOH,reaction temperature,and reactant ratio on the conversion rate and the yield of the reaction,respectively,was systematically investigated,and daidzein was obtained in 74.0%isolated yield under optimal conditions.Due to the facilitating effect of TfOH,the Friedel–Crafts acylation was completed within 10 min at 90℃ and the[5+1]cyclization was completed within 180 min at 25℃.In addition,a possible reaction mechanism for this process was proposed.The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

Reaction Mechanism,Synthesis and Characterization of Urea-glyoxal(UG) Resin

The reaction mechanism of glyoxal （G） with urea （U） under weak acid condition was theoretically investigated at PW91/DNP/COSMO of quantum chemistry using density functional theory （DFT） method. The results show that the addition reaction of G with U under the conditions mainly involves the reactions of U with protonated glyoxal （p-G）, protonated 2,2-dihy- droxyacetaldehyde （p-G 1） and protonated bis-hemdiol （p-G2） to form two important carbocation reactive intermediates of C-p-UG and C-p-UG1, and two important hydroxyl compounds of UG and UG1. These compounds play important roles in the formation of UG resin. According to the result of quantum chemical calculation, UG resin was synthesized successfully under weak acid conditions. The UG resin was characterized by matrix assisted laser desorption ionization time of flight mass spectrometry （MALDI-TOF-MS）, ultraviolet and visible spectroscopy （UV-vis）, Fourier transform infrared spectroscopy （FT1R） and nuclear magnetic resonance spectroscopy （13CNMR and 1HNMR）. These instrumental analytical results agree with each other and further confirm the addition reaction pathway of glyoxal with urea proposed by quantum chemical calculation.

THE PHOTOCHEMICAL SYNTHESIS OF THE PYRIDINE ADDUCT OF TETRAPHENYLPORPHYRINATORHODIUM(Ⅱ)AND THE MECHANISM OF PHOTOCHEMICAL REACTION

A new rhodium(Ⅱ)porphyrin complex was isolated by chromatography from the photochemical reac- tion of(μ—tetraphenylporphyrinato)bis[dicarbonylrhodium(Ⅰ)]with pyridine in benzene and has been charac- terized.From the results,the reaction mechanism is proposed.

MICROSTRUCTURE AND PROPERTY OF Al/TiC COMPOSITES PREPARED BY REACTION SYNTHESIS

A novel in-situ process-Reaction Synthesis has been used to fabricate Al/TiC compos-ites,the phase constitute,microstructure and mechanical property of the Al/TiC composite have been investigated by the use of XRD and SEM.It has been shown that the reaction synthesized TiC particu-late is submicron in size(about 0.1~0.8μpm),spherical in shape and smooth in surface.In macrostruc-ture the distribution of the TiC particulate in matrix is homogeneous,but in micostructure there is micro-segregation of the TiC particulate at the intergrannular.The cast structure become fine because of the existence of the TiC particulate.In addition«with the increasing of weight percentage of TiC partic-ulate in alloy,the yield strength and ultimate tensile strength of the composite increase significantly«e.g.at 15%TiC,117% and 103% increase respectively,in the same time the elongation of the composite is still more than 4.5%.In the end,the analysis has been done by SEM on the fracture morphology of the composite.The results show that the fracture is ductility,and mainly because of the cluster of TiC particulate to intergrannular and the synthesis of bar morphology Al_(3)Ti.

Synthesis strategies of covalent organic frameworks: An overview from nonconventional heating methods and reaction media

Covalent organic frameworks(COFs), as an emerging class of porous crystalline materials constructed by covalent links between the building monomers, have gained tremendous attention. Over the past 15 years, COFs have made rapid progress and substantial development in the chemistry and materials fields. However, the synthesis of COFs has been dominated by solvothermal methods for a long time and it usually involves high temperature, high pressure and toxic organic solvents, which created many challenges for environmental considerations. Recently,the exploration of new approaches for facile fabrication of COFs has aroused extensive interest. Hence, in this review, we comprehensively describe the synthetic strategies of COFs from the aspects of nonconventional heating methods and reaction media. In addition, the advantages,limitations and properties of the preparation methods are compared. Finally, we outline the main challenges and development prospects of the synthesis of COFs in the future and propose some possible solutions.

Evaluation of Reaction Mechanism for Photocatalytic Degradation of Dye with Self-Sensitized TiO₂under Visible Light Irradiation

The dye-sensitized TiO2 method is one of the most promising methods for the visible-light-induced detoxification of pollutants. The reaction mechanism for photocatalytic degradation of orange II (OII) and rhodamine B (RhB) with self-sensitized TiO2 under visible light irradiation (λ > 400 nm) has been evaluated. Radical scavenger studies were carried out to investigate the active species involved in the photodegradation of 5 mg/L of initial concentration of OII and RhB at room temperature. The trapping effects of different scavengers results proved that the oxidation of OII and RhB mainly occurred by the direct oxidization of h+ and ·O2- radicals, while the ·OH radicals played only a relatively minor role in the direct oxidization process.

Reaction mechanism of self-propagating magnesiothermic reduction of ZrB_2 powders

Fine zirconium diboride （ZrB2） powders with high purity were successfully prepared by combustion synthesis through magnesiothermic reduction process in Mg-B2O3-ZrO2 system. The reaction mechanism was investigated by differential thermal analysis and quenching experiment. The results show that the whole magnesio-thermic reduction process includes three stages： first, molten B2O3 and Mg formed above the temperature of 650 ℃, and glassy B2O3 and solid ZrO2 particles were coated on the surface of the molten Mg; thus, the hollow balls can be formed when the molten Mg was exuded under capillary function. Second, ZrO2 particles reacted with molten Mg to form Zr and MgO with dissolution-precip-itation mechanism, which released a large amount of heat to induce the diffusion reaction between B203 and Mg to form B and MgO. Last, Zr reacted with B to form ZrB2 grains. The preparation of ZrB2 by self-propagating syn-thesis in Mg-B2O3-ZrO2 system is a solid-liquid-liquid reaction.

Formation of active radicals and mechanism of photocatalytic degradation of phenol process using eosin sensitized TiO_2 under visible light irradiation

The role of oxygen and the generation of active radicals in the photocatalitic degradation of phenol were investigated using the eosin sensitized TiO2 as photocatalyst under visible light irradiation. Diffuse reflectance spectra show that the absorbancy range of eosin/TiO2 is expanded from 378 nm (TiO2 ) to about 600 nm. The photocatalitic degradation of phenol is almost stopped when the eosin/TiO2 system is saturated with N2 , which indicates the significance of O2 . The addition of NaN 3 (a quencher of single oxygen) causes about a 62% decrease in the phenol degradation. The phenol degradation ratio is dropped from 92% to 75% when the isopropanol (a quencher of hydroxyl radical) is present in the system. The experimental results show that there are singlet oxygen and hydroxyl radical generated in the eosin/TiO2 system under visible light irradiation. The changes of absorbancy indicate that the hydrogen peroxide might be produced. Through the analysis and comparison, it is found that the singlet oxygen is the predominant active radical for the degradation of phenol.

Effect of Mn on the Performance and Mechanism of Catalysts for the Synthesis of (Ce,La)CO₃F

In accordance with the cerium-lanthanum ratio of fluorocerium ores in the mineralogy of the Baiyun Ebo process, the (Ce,La)CO3F grains were synthesised by hydrothermal method using pure material to simulate bastnaesite minerals, and used as NH3-SCR denitrification catalysts. The activity results showed that the synthetic (Ce,La)CO3F was roasted at 500˚C, and the NOx conversion was 27% at 200˚C. The NH3-SCR catalytic activity of the synthesised (Ce,La)CO3F was improved by loaded transition metal Mn. The best catalyst was found to be produced by impregnating (Ce,La)CO3F with 1 mol/L manganese nitrate solution, with a NOx conversion of 80% at 250˚C. The loading of Mn resulted in the appearance of numerous well-dispersed MnOx species on the catalyst surface, the dispersion of Ce7O12 species was also greatly enhanced, and the reduction in grain size indicated that Mnn+ entered into the (Ce,La)CO3F lattice causing lattice shrinkage. The number of acidic sites on the catalyst surface and the redox capacity were enhanced. The amount of Ce3+ in the catalyst was also enhanced by the introduction of Mnn+, but the proportion of adsorbed oxygen decreased, which indicated that the introduction of Mnn+ was detrimental to the increase in the proportion of adsorbed oxygen. The reaction mechanisms of the (Ce,La)CO3F and Mn/(Ce,La)CO3F catalysts were investigated by in-situ Fourier transform infrared spectroscopy (FTIR). The results showed that catalysts followed the E-R and L-H mechanisms. When loaded with Mn, the main reactive species in the L-H mechanism were the (ad) species on the Brønsted acidic site and the O-Ce3+-O-NO, O-Mn3+-O-NO species. The main reactive species for the E-R mechanism were NH3/ (ad) species and NO. The (ad) species on the Brønsted acidic sites act as the main reactive NH3 (g) adsorbing species, bonded to the Ce4+ in the carrier (Ce,La)CO3F to participate in the acid cycle reaction. The introduction of Mnn+ increases the number of Brønsted acidic sites on the catalyst surface, and acts as an adsorption site for NO, to react with NO to generate more monodentate nitrate species, to participate in the redox cycle reactions. The above results indicated that Mnn+ and (Ce,La)CO3F have a good mutual promotion effect, which makes the loaded catalyst have excellent performance, which provides a theoretical basis for the high value utilization of bastnaesite.

Facile fabrication and enhanced photocatalytic performance of visible light responsive UiO-66-NH2/Ag2CO3 composite

A series of UiO-66-NH2/Ag2CO3 Z-scheme heterojunctions were prepared by a simple ion-exchange-solution method using UiO-66-NH2 and semiconductor Ag2CO3 as precursors.The photocatalytic activities of UAC-X(UAC-20,50,100,150,200)Z-scheme heterojunctions toward the hexavalent chromium(Cr(VI))reduction and UAC-100 toward oxidative degradation of four organic dyes like rhodamine B(RhB),methyl orange(MO),congo red(CR),and methylene blue(MB)under visible light irradiation were investigated.The effects of different pH(pH=2,3,4,6,8),small organic acids(citric acid,tartaric acid,and oxalic acid),and foreign ions(ions in tap water and surface water)on Cr(VI)reduction were explored.The results revealed that the UAC-100 heterojunctions displayed more remarkable Cr(VI)reduction performance than the pristine UiO-66-NH2 and Ag2CO3,resulting from the improved separation of photo-induced electrons and holes.The enhanced photocatalytic activity of UAC-100 was further confirmed by the photoluminescence measurement,electrochemical analysis,and active species trapping experiments.After four cycles’experiments,the photocatalytic Cr(VI)reduction efficiency over UAC-100 was still over 99%,which exhibited that UAC-100 had excellent reusability and stability.Finally,the corresponding photocatalytic reaction mechanism was proposed and tested.

Influence of chloride salts on hydrogen generation via hydrolysis of MgH_2 prepared by hydriding combustion synthesis and mechanical milling

The effects of chloride salts(NaCl,MgCl2and NH4Cl)on the hydrolysis kinetics of MgH2prepared by hydridingcombustion synthesis and mechanical milling(HCS+MM)were discussed.X-ray diffraction(XRD)analyses show that high-purityMgH2was successfully prepared by HCS.Hydrolysis performance test results indicate that the chloride salt added during the millingprocess is favorable to the initial reaction rate and hydrogen generation yield within60min.A MgH2?10%NH4Cl composite exhibitsthe best performance with the hydrogen generation yield of1311mL/g and a conversion rate of85.69%in60min at roomtemperature.It is suggested that the chloride salts not only play as grinding aids in the milling process,but also create fresh surface ofreactive materials,favoring the hydrolysis reaction.

Bandgap engineering of hierarchical network-like SnIn4S8 microspheres through preparation temperature for excellent photocatalytic performance and high stability

The effect of synthesis temperature and reaction time on the visible-light photocatalytic activity of hierarchical network-like SnIn4S8 microspheres was investigated by the low-temperature co-precipitation strategy. The preparation temperature and reaction time have great influence on the photocatalytic activity of SnIn4S8, and the optimal preparation temperature and reaction time are 70℃ and 3 h, respectively.The SnIn4S8 shows good reusability and high stability with no observable decrease of photocatalytic activity in five consecutive cycles.

Al/TiO_(2) SELF-COMBUSTION SYNTHESIS REACTION

Al/TiO_(2) self-combustion synthesis reaction has been studied,including the effect of initial conditions of reactants on combustion temperature,combustion velocity and combustion stability etc.The reaction mechanism of Al/TiO_(2) self-combustion synthesis has been studied emphatically and the dynamic reaction model has been created.

Synthesis and Characterization of Metal-Doped (Ni, Co, Ce, Sb) CdS Catalysts and Their Use in Methylene Blue Degradation under Visible Light Irradiation

Metal doped CdS nanoparticles were synthesized by a simple chemical precipitation route with different metals. The obtained nanoparticles were characterized by XRD and UV-vis reflectance spectroscopy. The results indicated that metal-doped CdS catalysts were successfully obtained with cubic structure and 4.0 - 4.5 nm crystallite size. The band gap energies of metal-doped CdS catalysts were estimated using UV-visible reflectance spectra to be about the range of 2.25 - 2.55 eV. Methylene blue was degraded by using metal doped CdS nanoparticles under a 400 W medium-pressure mercury lamp of visible light irradiation (λ > 420 nm). Higher degradation efficiency was achieved by adding metals to the photocatalyst compared with the single CdS catalyst. In this case, the degradation efficiency of Co-CdS catalyst after 4h irradiation time was about 87%.

Synthesis of condensed polynuclear aromatic resin from furfural extract oil of reduced-pressure route Ⅱ

As an industrial byproduct of oil refining,furfural extract oil from reduced-pressure route Ⅱ with high aromatic content was used to prepare heat-resistant condensed polynuclear aromatic（COPNA） resin for the first time.The basic properties of furfural extract oil and the resultant COPNA resin were characterized by infrared spectroscopy（FT-IR）,nuclear magnetic resonance spectroscopy（1H-NMR）,thermogravimetric analysis（TGA） and elemental analysis（EA）.The result showed that heat treated furfural extract oil was successfully used for the synthesis of heat-resistant COPNA resin.The average structural parameters of raw materials and prepared resin were calculated by the improved Brown-Ladner method,and the averaged molecular structure of the resin was obtained.The reaction mechanism for the synthesis of COPNA resin was suggested as an acid-catalyzed positive ion type polymerization.

Visible Light Induced Photocatalysis of Cerium Ion Modified Titania Sol and Nanocrystallites

The cerium ion(Ce4+) doped titania sol and nanocrystallites were prepared by chemical coprecipitation-peptization and hydrothermal synthesis methods, respectively. The X-ray diffraction pattern shows that Ce4+-TiO2 xerogel powder has semicrystalline structure and thermal sintering sample has crystalline structure. Ce4+-TiO2 nanocrystallites are composed of the major anatase phase titania (88.82 wt pct) and a small amount of crystalline cerium titanate. AFM micrograph shows that primary particle size of well-dispersed ultrafine sol particles is below 15 nm in diameter. The particle sizes are 30 nm for xerogel sample and 70 nm for nanocrystallites sample, which is different from the estimated values (2.41 nm and 4.53 nm) by XRD Scherrer's formula. The difference is mainly due to aggregation of nanocrystallites. The experimental results exhibit that photocatalysts of Ce4+-TiO2 sol and nanocrystallites have the ability to photodegrade reactive brilliant red dye (X-3B ) under visible light irradiation with the ion-TiO2/VIS/dye system. Moreover, Ce4+ doped titania sol has shown higher efficiency than the nanocrystallites sample in respect of potocatalytic activity. Meanwhile, dye photodegradation mechanisms are proposed to different photocatalytic reaction systems, which are dye photosensitization, ion-dye photosensitization and interband photocatalysis & dye photosensitization with respect to TiO2 nanocrystallites, Ce4+-TiO2 sol and Ce4+-TiO2 nanocrystallites system.

Recent progress in production and usage of hydrogen peroxide

Hydrogen peroxide has attracted increasing interest as an environmentally benign and green oxidant that can also be used as a solar fuel in fuel cells.This review focuses on recent progress in production of hydrogen peroxide by solar-light-driven oxidation of water by dioxygen and its usage as a green oxidant and fuel.The photocatalytic production of hydrogen peroxide is made possible by combining the e^(-)and 4e-oxidation of water with the e^(-)reduction of dioxygen using solar energy.The catalytic control of the selectivity of the e^(-)vs.4e-oxidation of water is discussed together with the selectivity of the e^(-)vs.4e-reduction of dioxygen.The combination of the photocatalytic e^(-)oxidation of water and the e^(-)reduction of dioxygen provides the best efficiency because both processes afford hydrogen peroxide.The solar-light-driven hydrogen peroxide production by oxidation of water and by reduction of dioxygen is combined with the catalytic oxidation of substrates with hydrogen peroxides,in which dioxygen is used as the greenest oxidant.

Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces

Vinyl acetate （VA） synthesis on Pd/Au（111） and Pd/Au（100） surfaces has been systematically investigated through first-principles density functional theory （DFT） calculations. The DFr results showed that for VA synthesis, the ＇Samanos＇ reaction mechanism （i.e., direct coupling of coadsorbed ethylene and acetate species and subsequent/%hydride elimination to form VA） is more favorable than the ＇Moiseev＇ mechanism （i.e., ethylene first dehydrogenates to form vinyl species which then couple with the coadsorbed acetate species to form VA）. More importantly, it was found the surface coverage of acetate has a significant effect on the reactivity of VA synthesis, and the activation energy of the rate- controlling step on Pd/Au（100） surface is smaller than that on Pd/Au（111） surface （0.88 vs. 0.95 eV）, indicating the former is more active than the latter.

Computational Study on Thermodynamic Properties of Fischer-Tropsch Synthesis Process

Using the highly accurate G4 method, we computed the thermodynamic data of 1287 possible reaction products under a wide range of reaction conditions in the Fischer-Tropcsh synthesis (FTS) process. These accurate thermodynamic data provide basic thermodynamic quantities for the actual chemical engineering process and are useful in analyzing product distribution because FTS demonstrates many features of an equilibrium-controlled system. Our results show that the number of thermodynamically allowed products to increase when lowering temperature, raising pressure, and raising H2/CO ratio. At low temperature, high pressure and high H2/CO ratio, many products are thermodynamically allowed and the selectivity of product has to be controlled by kinetic factors. On the other hand, high selectivity of lighter products can be realized in thermodynamics by raising temperature and lowering pressure. We found that the equilibrium product yield will reach a maximum and remain unchanged when lowering temperature, raising pressure, and raising H2/CO ratio to some limits, implying that optimizing reaction conditions has no effect on equilibrium product yields beyond these limits. The thermodynamic analysis is also useful in designing and evaluating FTS reaction mechanisms. We found that reaction pathways through formaldehyde should be discarded because of its extremely low equilibrium yield. Recently, in the FTS process using metal-oxide-zeolite catalysts for the highly selective production of C2-C4 olefins and aromatic hydrocarbons, there are several guesses on the possible reaction intermediates entering the zeolite channel. Our results show that ketene, methanol, and dimethyl ether are three possible reaction intermediates.

A review on direct synthesis of dimethoxymethane

Polyoxymethylene dimethyl ethers are recognized as the prospective diesel additive to decrease the pollutant emission from the light-duty vehicles,which can be polymerize form the monomer of dimethoxymethane(DMM).The industrial synthesis of DMM is mainly involved two-step process:methanol is oxidized to form the formaldehyde in fixed bed reactor and then reacted with the generated formaldehyde through acetalization in continuous stirred-tank reactor.Due to huge energy consumption,this typical synthesis route of DMM needs to be upgraded and more green routes should be determined.In this review,four state-of-the-art one-step direct synthetic routes,including two upgrading routes(methanol direct oxidation and direct dehydrogenation)and two green routes(methanol diethyl ether direct oxidation and carbon oxides direct hydrogenation),have been summarized and compared.Combination with the reaction mechanism and catalytic performance on the different catalysts,the challenges and opportu nities for every synthetic route are proposed.The relationships between catalyst structu re and property in different synthesis strategy are also investigated and then the suggestions of the design of catalyst are given about future research directions that efforts should be made in.Hopefully,this review can bridge the gap between newly developed catalysts and synthesis technology to realize their commercial applications in the near future.