Toluene Alkylation with Methanol to p-Xylene over Heteropoly Acids Supported by Clay

The alkylation of toluene with methanol for the selective formation of p-xylene was systematically studied. Very few studies have been reported on the use of superacids such as heteropolyacids on cheap supports, such as clay. This article deals with the use of different heteropoly acids （HPAs）, viz, Dodeca-Tungstophosphoric acid [H3PO4.12WO3.xH2O] （TPA）, Dodeca-Molyhdo phosphoric acid ammonium salt hydrate [H12Mo12N3O40P＋aq] （DMAA）, Dodeca-Molyhdo Phosphoric acid （PMA） on clay （MontmoriUonite, K-10） and as such plain clay. This comparative study reveals that 20%PMA/Clay shows 62% toluene conversion and 100% selectivity toward p-xylene.

Intensified shape selectivity and alkylation reaction for the two-step conversion of methanol aromatization to p-xylene

Two-step conversion of methanol to aromatics via light hydrocarbons can significantly improve the conversion stability compared with direct aromatization of methanol,but it remains a challenge to achieve a high p-xylene(PX)selectivity.Herein,silica coating was firstly used to passivate external acid sites of ZSM-5 catalyst for the aromatization of light hydrocarbons by the chemical liquid deposition method.With the increase of SiO_(2) deposition,the density of the external acid sites of the catalyst was decreased from 0.1 to 0.03 mmol·g^(-1),which inhibited the surface secondary reactions and increased the PX/X from 34.6% to 60.0%.In view of the fact that the aromatization process in the second step was partly inhibited as methanol was consumed in advance in the upper methanol-to-light hydrocarbons catalyst layer,part of methanol was directly introduced into the lower aromatization catalyst layer to promote the alkylation process during the aromatization,which decreased the toluene selectivity from 34.5% to 14.3% but increased the xylene selectivity from 40.0%to 55.3%.It was also found that an appropriate external acid density was needed for aromatization catalyst to strengthen the alkylation process and improve the selectivity of xylene under the conditions of methanol introduction.

Renewable p-Xylene Production by Co-catalytic Pyrolysis of Cellulose and Methanol

This work developed a one-step process for renewable p-xylene production by co-catalytic fast pyrolysis (co-CFP) of cellulose and methanol over the different metal oxides modified ZSM5 catalysts. It has been proven that La2O3-modified ZSM5(80) catalyst was an effective one for the production of biobased p-xylene. The selectivity and yield of p-xylene strongly depended on the acidity of the catalysts, reaction temperature, and methanol content. The highest p-xylene yield of 14.5 C-mol% with a p-xylene/xylenes ratio of 86.8% was obtained by the co-CFP of cellulose with 33wt% methanol over 20%La2O3-ZSM5(80) catalyst. The deactivation of the catalysts during the catalytic pyrolysis process was investigated in detail.The reaction pathway for the formation of p-xylene from cellulose was proposed based on the analysis of products and the characterization of catalysts.

Methanol steam reforming for hydrogen production driven by an atomically precise Cu catalyst

Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can be used as light-harvesting materials in solar energy utilization such as photocatalytic methanol steam reforming.In this work,we report an atomically precise Cu_(13)cluster protected by dual ligands of thiolate and phosphine that can be viewed as the assembly of one top Cu atom and three Cu_(4)tetrahedra.The Cu_(13)H_(10)(SR)_(3)(PR’_(3))_(7)(SR=2,4-dichlorobenzenethiol,PR’_(3)=P(4-FC_(6)H_(4))_(3))cluster can give rise to highly efficient light-driven activity for methanol steam reforming toward H_(2)production.

Effect of Steam Treatment on the Catalytic Performance of ZSM-5 in the Co-conversion of Methanol and n-Hexane to Aromatics

Steam pretreatment is a widely used method for modifying the acidity and structure of zeolites,thereby enhancing their catalytic properties.This study systematically investigated the effects of steam treatment on ZSM-5 zeolites at varying treatment temperatures and durations.The structural evolution of the catalysts was monitored using N2 adsorptiondesorption,X-ray diffraction,inductively coupled plasma optical emission spectroscopy,scanning electron microscopy,NH3 temperature-programmed desorption,in situ pyridine infrared spectroscopy,and thermogravimetric analysis.The characterization results revealed that mesopores were introduced into the ZSM-5 zeolite catalysts through dealumination induced using steam treatment at moderate temperatures(400 and 500℃).Moreover,compared with the parent catalyst,the steam-treated catalysts exhibited a lower amount of acid sites and relative crystallinity,while the n(Si)/n(Al)ratio increased.In the co-conversion of methanol and n-hexane in a fixed bed reactor at 400℃and 0.5 MPa(N2 atmosphere),with a weight hourly space velocity of 1 h−1 and a stoichiometric ratio of 1:1(CH3OH to n-hexane),the steam-treated catalysts displayed a prolonged catalyst lifetime.Particularly,the parent zeolite had a lifetime of 96 h,while the catalyst treated at 500℃for 12 h had a lifetime of up to 240 h.Additionally,the steam-treated catalysts maintained stable n-hexane conversion and improved aromatic selectivity.Notably,these treated catalysts exhibited a lower deactivation rate than the parent catalyst,and would be conducive to industrial scale-up production.

Modeling and analysis of air combustion and steam regeneration in methanol to olefins processes

Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However,the catalyst deactivation is an inevitable feature in MTO processes,and regeneration,therefore,is one of the key steps in industrial MTO processes.Traditionally the MTO catalyst is regenerated by removing the deposited coke via air combustion,which unavoidably transforms coke into carbon dioxide and reduces the carbon utilization efficiency.Recent study shows that the coke species over MTO catalyst can be regenerated via steam,which can promote the light olefins yield as the deactivated coke species can be essentially transferred to industrially useful synthesis gas,is a promising pathway for further MTO processes development.In this work,we modelled and analyzed these two MTO regeneration methods in terms of carbon utilization efficiency and technology economics.As shown,the steam regeneration could achieve a carbon utilization efficiency of 84.31%,compared to 74.74%for air combustion regeneration.The MTO processes using steam regeneration can essentially achieve the near-zero carbon emission.In addition,light olefins production of the MTO processes using steam regeneration is 12.81%higher than that using air combustion regeneration.In this regard,steam regeneration could be considered as a potential yet promising regeneration method for further MTO processes,showing not only great environmental benefits but also competitive economic performance.

Efficient and stable PtFe alloy catalyst for electrocatalytic methanol oxidation with high resistance to CO

Direct methanol fuel cells(DMFC) are widely considered to be an ideal green energy conversion device but their widespread applications are limited by the high price of the Pt-based catalysts and the instability in terms of surface CO toxicity in long-term operation.Herein,the PtFe alloy nanoparticles(NPs) with small particle size(~4.12 nm) supported on carbon black catalysts with different Pt/Fe atomic ratios(Pt_(1)Fe_(2)/C,Pt_(3)Fe_(4)/C,Pt_(1)Fe_(1)/C,and Pt_(2)Fe_(1)/C) are successfully prepared for enhanced anti-CO poisoning during methanol oxidation reaction(MOR).The optimal atomic ratio of Pt/Fe for the MOR is 1:2,and the mass activity of Pt_(1)Fe_(2)/C(5.40 A mg_(Pt)^(-1)) is 13.5 times higher than that of conventional commercial Pt/C(Pt/C-JM)(0.40 A mg_(Pt)^(-1)).The introduction of Fe into the Pt lattice forms the PtFe alloy phase,and the electron density of Pt is reduced after forming the PtFe alloy.In-situ Fourier transform infrared results indicate that the addition of oxyphilic metal Fe has reduced the adsorption of reactant molecules on Pt during the MOR.The doping of Fe atoms helps to desorb toxic intermediates and regenerate Pt active sites,promoting the cleavage of C-O bonds with good selectivity of CO_(2)(58.1%).Moreover,the Pt_(1)Fe_(2)/C catalyst exhibits higher CO tolerance,methanol electrooxidation activity,and long-term stability than other Pt_(x)Fe_(y)/C catalysts.

Precision tuning of highly efficient Pt-based ternary alloys on nitrogen-doped multi-wall carbon nanotubes for methanol oxidation reaction

The electrochemical methanol oxidation is a crucial reaction in the conversion of renewable energy.To enable the widespread adoption of direct methanol fuel cells(DMFCs),it is essential to create and engineer catalysts that are both highly effective and robust for conducting the methanol oxidation reaction(MOR).In this work,trimetallic PtCoRu electrocatalysts on nitrogen-doped carbon and multi-wall carbon nanotubes(PtCoRu@NC/MWCNTs)were prepared through a two-pot synthetic strategy.The acceleration of CO oxidation to CO_(2) and the blocking of CO reduction on adjacent Pt active sites were attributed to the crucial role played by cobalt atoms in the as-prepared electrocatalysts.The precise control of Co atoms loading was achieved through precursor stoichiometry.Various physicochemical techniques were employed to analyze the morphology,element composition,and electronic state of the catalyst.Electrochemical investigations and theoretical calculations confirmed that the Pt_(1)Co_(3)Ru_(1)@NC/MWCNTs exhibit excellent electrocatalytic performance and durability for the process of MOR.The enhanced MOR activity can be attributed to the synergistic effect between the multiple elements resulting from precisely controlled Co loading content on surface of the electrocatalyst,which facilitates efficient charge transfer.This interaction between the multiple components also modifies the electronic structures of active sites,thereby promoting the conversion of intermediates and accelerating the MOR process.Thus,achieving precise control over Co loading in PtCoRu@NC/MWCNTs would enable the development of high-performance catalysts for DMFCs.

Machine learning molecular dynamics simulations of liquid methanol

As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular force fields or ab initio molecular dynamics with semilocal density functionals.Inspired by recent studies on bulk water using increasingly accurate machine learning force fields,we report a new machine learning force field for liquid methanol with a hybrid functional revPBE0 plus dispersion correction.Molecular dynamics simulations on this machine learning force field are orders of magnitude faster than ab initio molecular dynamics simulations,yielding the radial distribution functions,selfdiffusion coefficients,and hydrogen bond network properties with very small statistical errors.The resulting structural and dynamical properties are compared well with the experimental data,demonstrating the superior accuracy of this machine learning force field.This work represents a successful step toward a first-principles description of this benchmark system and showcases the general applicability of the machine learning force field in studying liquid systems.

Realizing methanol synthesis from CO and water via the synergistic effect of Cu^(0)/Cu^(+)over Cu/ZrO_(2) catalyst

The optimizing utilization of ca rbon resources has drawn wide attention all over the world,while exploiting the high-efficiency catalytic routes remains a challenge.Here,a direct methanol synthesis route is realized from pure CO and H_(2)O over 10%Cu/t-ZrO_(2) catalyst,where the time yield of methanol is144.43 mmol mol_(Cu)^(-1)h^(-1)and the methanol selectivity in hydrocarbons is 100%,The Cu species highly dispersed in the t-ZrO_(2) support lead parts of them in the cationic state.The Cu^(+)sites contribute to the dissociation of H_(2)O,providing the H*source for methanol synthesis,while the formed Cu^(0) sites promote the absorption and transfer of H*during the reaction.Moreover,the H_(2)O is even a better H resource than H_(2) due to its better dissociation effectivity in this catalytic system.The present work offers a new approach for methanol synthesis from CO and new insight into the process of supplying H donor.

Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO_(2)and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate(DMC)from CO_(2)and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes.Herein,a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO_(2)and methanol,and the structure-performance relationship was investigated in detail.Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts.In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)studies indicated that the adsorption rate of methanol is slower than that of CO_(2)and the methanol activation state largely influences the formation of key intermediate.Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO_(2),the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation.Moreover,with the use of 2-cyanopyridine as a dehydration reagent,the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.

Interfacial Electronic Modulation of Dual-Monodispersed Pt–Ni_(3)S_(2) as Efficacious Bi-Functional Electrocatalysts for Concurrent H_(2) Evolution and Methanol Selective Oxidation

Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.

Controllable synthesis of CuAlO_(2) via solid-phase method and its catalytic performance for methanol steam reforming to hydrogen

This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.

The Effects of the Geometry of a Current Collector with an Equal Open Ratio on Output Power of a Direct Methanol Fuel Cell

The open ratio of a current collector has a great impact on direct methanol fuel cell(DMFC)performance.Although a number of studies have investigated the influence of the open ratio of DMFC current collectors,far too little attention has been given to how geometry(including the shape and feature size of the flow field)affects a current collector with an equal open ratio.In this paper,perforated and parallel current collectors with an equal open ratio of 50%and different feature sizes are designed,and the corresponding experimental results are shown to explain the geometry effects on the output power of the DMFC.The results indicate that the optimal feature sizes are between 2 and 2.5 mm for both perforated and parallel flow field in the current collectors with an equal open ratio of 50%.This means that for passive methanol fuel cells,to achieve the highest output power,the optimal feature size of the flow field in both anode and cathode current collectors is between 2 and 2.5 mm under the operating mode of this experiment.The effects of rib and channel position are also investigated,and the results indicate that the optimum pattern depends on the feature sizes of the flow field.

CO_(2) hydrogenation to methanol over the copper promoted In_(2)O_(3) catalyst

The metal promoted In_(2)O_(3) catalysts for CO_(2) hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity.However,there was still no experimental confirmation if copper could be a good promoter for In_(2)O_(3).Herein,the Cu promoted In_(2)O_(3) catalyst was prepared using a deposition-precipitation method.Such prepared Cu/In_(2)O_(3) catalyst shows significantly higher CO_(2) conversion and space time yield(STY)of methanol,compared to the un-promoted In_(2)O_(3) catalyst.The loading of Cu facilitates the activation of both H_(2) and CO_(2) with the interface between the Cu cluster and defective In_(2)O_(3) as the active site.The Cu/In_(2)O_(3) catalyst takes the CO hydrogenation pathway for methanol synthesis from CO_(2) hydrogenation.It exhibits a unique size effect on the CO adsorption.At temperatures below 250℃,CO adsorption on Cu/In_(2)O_(3) is stronger than that on In_(2)O_(3),causing higher methanol selectivity.With increasing temperatu res,the Cu catalyst aggregates,which leads to the formation of weak CO adsorption site and causes a decrease in the methanol selectivity.Compared with other metal promoted In_(2)O_(3) catalysts,it can be concluded that the catalyst with stronger CO adsorption possesses higher methanol selectivity.

Pt nanoclusters modified porous g-C_(3)N_(4)nanosheets to significantly enhance hydrogen production by photocatalytic water reforming of methanol

For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.

Chemical profiling of bioactive compounds in the methanolic extract of wild leaf and callus of Vitex negundo using gas chromatographymass spectrometry

BACKGROUND The investigation of plant-based therapeutic agents in medicinal plants has revealed their presence in the extracts and provides the vision to formulate novel techniques for drug therapy.Vitex negundo(V.negundo),a perennial herb belonging to the Varbanaceae family,is extensively used in conventional medication.AIM To determine the existence of therapeutic components in leaf and callus extracts from wild V.negundo plants using gas chromatography-mass spectrometry(GCMS).METHODS In this study,we conducted GC-MS on wild plant leaf extracts and correlated the presence of constituents with those in callus extracts.Various growth regulators such as 6-benzylaminopurine(BAP),2,4-dichlorophenoxyacetic acid(2,4-D),α-naphthylacetic acid(NAA),and di-phenylurea(DPU)were added to plant leaves and in-vitro callus and grown on MS medium.RESULTS The results clearly indicated that the addition of BAP(2.0 mg/L),2,4-D(0.2 mg/mL),DPU(2.0 mg/L)and 2,4-D(0.2 mg/mL)in MS medium resulted in rapid callus development.The plant profile of Vitex extracts by GC-MS analysis showed that 24,10,and 14 bioactive constituents were detected in the methanolic extract of leaf,green callus and the methanolic extract of white loose callus,respectively.CONCLUSION Octadecadienoic acid,hexadecanoic acid and methyl ester were the major constituents in the leaf and callus methanolic extract.Octadecadienoic acid was the most common constituent in all samples.The maximum concentration of octadecadienoic acid in leaves,green callus and white loose callus was 21.93%,47.79%and 40.38%,respectively.These findings demonstrate that the concentration of octadecadienoic acid doubles in-vitro compared to in-vivo.In addition to octadecadienoic acid;butyric acid,benzene,1-methoxy-4-(1-propenyl),dospan,tridecanedialdehyde,methylcyclohexenylbutanol,chlorpyrifos,n-secondary terpene diester,anflunine and other important active compounds were also detected.All these components were only available in callus formed in-vitro.This study showed that the callus contained additional botanical characteristics compared with wild plants.Due to the presence of numerous bioactive compounds,the medical use of Vitex for various diseases has been accepted and the plant is considered an important source of therapeutics for research and development.

Toluene Alkylation to Selective Formation of p-Xylene over Co-Crystalline ZSM-12/ZSM-5 Catalyst

The alkylation of toluene with methanol to selective formation of p-xylene has been systematically studied. ZSM-12 （MTW）/ZSM-5 co-crystalline zeolite in 40：60 proportions have been synthesized by the same molar gel composition, but at different temperatures and periods than that of ZSM-12 and ZSM-5, separately. All the prepared samples are characterized by XRD, SEM, BET, and XRF. The activity of toluene alkylation was investigated with a mixture of toluene and methanol as a feed over the ZSM-12, ZSM-12/ZSM-5 co-crystalline, ZSM-5, and physical mixture of ZSM-12/ZSM-5. From characterization, it is observed that the ZSM-12/ZSM-5 co-crystalline material is different from that of ZSM-12, ZSM-5, and their physical mixture. Further, the ZSM-12/ZSM-5 co-crystalline zeolite produces the highest content of xylene and has better selectivity for p-xylene than ZSM-12, ZSM-5, and their physical mixture.

Isobaric Vapor-Liquid Equilibrium of Binary Systems： p-Xylene ＋ （Acetic Acid, Methyl Acetate and n-Propyl Acetate） and Methyl Acetate ＋ n-Propyl Acetate in an Acetic Acid Dehydration Process

The vapor-liquid equilibrium data of four binary systems (acetic acid +p-xylene, methyl acetate +n-propyl acetate, n-propyl acetate +p-xylene and methyl acetate +p-xylene) are measured at 101.33 kPa with Ellis equilibrium still, and then both the NRTL and UNIQUAC models are used in combination with the HOC model for correlating and estimating the vapor-liquid equilibrium of these four binary systems. The estimated binary VLE results using correlated parameters agree well with the measured data except the methyl acetate +p-xylene system which easily causes bumping and liquid rushing out of the sampling tap due to their dramatically different boiling points. The correlation results by NRTL and UNIQUAC models have little difference on the average absolute deviations of temperature and composition of vapor phase, and the results by NRTL model are slightly better than those by UNIQUAC model except for the methyl acetate +n-propyl acetate system, for which the latter gives more accurate correlations.

Kinetics of Burning Side Reaction in the Liquid-phase Oxidation of p-Xylene

During the liquid-phase oxidation of p-xylene,over-oxidation of reactant,intermediates and solvent to carbon dioxide and carbon monoxide is generally known as the burning side reaction.Batch and semi-continuous experiments were carried out,and the experimental data of the burning side reaction were analyzed and reported in this paper.The results showed that the rates of burning side reactions were proportional to the rates of the main reaction,but decreased with the increasing concentrations of reactant and intermediates.The inter-stimulative and competitive relationship between the burning side reaction and the main reaction was confirmed,and the rates of the burning side reaction could be described with some key indexes of the main reaction.According to the mechanism of the side reactions and the kinetics model of main reaction which were proposed and tested in the previous papers,a kinetic model of the burning side reactions involving some key indexes of the main reaction was developed,and the parameters were determined by data fitting of the COx rate curves.The obtained kinetic model could describe the burning side reactions adequately.