The role of NH4^+ ion confinement in the catalytic etherification of HMF(5-hydroxymethylfurfural) with ethanol to biodiesel additives was evidenced by studying the catalytic behavior of NH4^+-Beta zeolites with SiO2/A...The role of NH4^+ ion confinement in the catalytic etherification of HMF(5-hydroxymethylfurfural) with ethanol to biodiesel additives was evidenced by studying the catalytic behavior of NH4^+-Beta zeolites with SiO2/Al2O3 ratios of 25 and 75.In order to affect the strength and distribution of the acidic sites, as well as the mobility of NH4^+ ions in the zeolites cages, a secondary level of porosity was introduced in the NH4^+-Beta, presenting a different stability versus alkaline treatment, by using a thermal or an ultrasound assisted method.By analyzing the catalytic behavior in these two series of samples with respect to the changes in porosity by nonlocal density functional theory, structure by XRD, amount of acid sites by FT-IR and mobility of NH4^+ cations by measurements of reversible NH4^+ exchange capacity, was evidenced a decrease in catalytic performances both in terms of rate of HMF depletion and productivity to the main products, when confinement of the ammonium ions is lost due to the introduction of mesoporosity.The high capability of ammonium ions release, associated to the mono-dentate configuration,and the minor confinement effect inside the zeolite pore system, due to the more opened pores structure of mesoporous zeolites, hinders both the direct etherification of HMF to EMF [5-(ethoxymethyl)furan-2-carbaldehyde] and the parallel reaction pathway via acetalization, favoring the rapid desorption of the HMFDEA [5-(hydroxymethyl)furfural diethyl acetal] product out of the crystal and the consequent inhibition of the consecutive reactions to EMFDEA [5-(ethoxymethyl)furfural diethyl acetal] and EMF.展开更多
Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the pr...Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the preparation of a reusable Pd catalyst for reductive etherification remains to be a great challenge.In this study,a series of Si O_(2)supported Pd catalysts with particle size ranging from 2.2 nm to 28 nm were prepared.Their textural properties and catalytic performance in furfural reductive etherification have been systematically studied.The results herein shed light on the particle size effect on the competition between hydrogenation/hydrogenolysis of C=O in furfural over Pd surface.We found out that Pd nanoparticles larger than 3 nm are preferred for one step reductive etherification.Based on this finding,we prepared a Pd/ZSM-5 bifunctional catalyst comprising Pd nanoparticles larger than 3 nm and decreased acidity in presence of amino organosilane,which served as a bifunctional catalyst succeeding in one-pot synthesis of ether via reductive-etherification and direct-etherification.This strategy showed significant advantage in efficiently converting furfuryl acohol,a major side-product,into ether,while suppressing the undesired side-reactions.展开更多
A new method for the preparation of aminated lignin （AEL） through etherification and amination reaction was presented. Chlorine atoms were ？rstly introduced into lignin through its etheri？cation with epichlo...A new method for the preparation of aminated lignin （AEL） through etherification and amination reaction was presented. Chlorine atoms were ？rstly introduced into lignin through its etheri？cation with epichlorohydrin. Then, hydrophilic amine groups were grafted to the modi？ed lignin structure through amination with ethylenediamine to obtain AEL. Subsequent acidi？cation of AEL led to the ionized aminated lignin （IAEL）. The results of our analyses showed that the nitrogen content of AEL was 6.9%. Foaming and emulsifying experiments indicated that AEL had better foamability and emulsifying properties than IAEL. Surface tension tests showed that AEL and IAEL had similar critical micelle concentration （CMC）. However, IAEL had lower surface tension （36.33 mN/m） than AEL （42.89 mN/m） at CMC. These results demonstrate the promising applicability of AEL as an emulsi？er and that of IAEL as feedstock in the production of detergent and dispersant.展开更多
Isoamylene from the Fischer-Tropsch syncrude can be transformed to valuable fuel oxygenate additives through an equilibrium limited etherification reaction with methanol. A reactive distillation process is established...Isoamylene from the Fischer-Tropsch syncrude can be transformed to valuable fuel oxygenate additives through an equilibrium limited etherification reaction with methanol. A reactive distillation process is established to increase isoamylene conversion. Facing the challenge of improving product purity at the same time, an equilibrium stage model based design methodology is proposed and illustrated step-by-step for converting the Fischer-Tropsch C_5 olefins to tert-amyl methyl ether(TAME) process by using Aspen Plus. Under the guide of the proposed methodology, the design leads to a TAME product purity of higher than 95% and an isoamylene conversion of higher than 90%. The etherification kinetics over Amberlyst 35 is also studied within a temperature range of 60 ℃ to 75 ℃ to shed more light on the feasibility of process development. The methodology provides an effective reactive distillation column design to achieve the target reactant conversion and product purity simultaneously.展开更多
Sugarcane bagasse(SCB)is an important by-product in the sugar industry.It is a source of cellulose fibers or cellulose for paper mills and textiles factories.In this study,SCB was ethyl etherified in tetrahydrofuran(T...Sugarcane bagasse(SCB)is an important by-product in the sugar industry.It is a source of cellulose fibers or cellulose for paper mills and textiles factories.In this study,SCB was ethyl etherified in tetrahydrofuran(THF)after alkali pretreatment.The alkali concentration for the pretreatment,the ratio of ethyl bromide(EtBr)to dried SCB in the reaction,reaction time,and temperature were investigated for the etherification of SCB.The ethoxyl content and characterization of the product were determined using headspace gas chromatography(HS-GC),Fourier Transform Infrared(FT-IR)and 13C-NMR spectroscopy,respectively.It was found that SCB was well-etherified with EtBr in alkali-THF.Upon ethylation of SCB,the ethoxyl content of the product was high when the alkali concentration and the ratio of EtBr to dried SCB were controlled from 50%to 75%and 4:1(V/w)to 6:1(V/w),respectively.The reaction occurred optimally when the temperature was controlled below 110℃;above this temperature,the degree of etherification decreased.The thermal stability of ethylated SCB was higher than that of SCB but slightly lower than that of commercial ethyl cellulose.Ethylated SCB has the potential to form composites with many materials because it is soluble in a wide variety of solvents.展开更多
zeolite was synthesized by using tetraethyl ammonium hydroxide as the template reagent andmicrowave radiation as the heat source. The effect of the sol composition and the radiation temperature onzeolite crystallinity...zeolite was synthesized by using tetraethyl ammonium hydroxide as the template reagent andmicrowave radiation as the heat source. The effect of the sol composition and the radiation temperature onzeolite crystallinity was investigated. The zeolite was tested and compared with the commercial product, whichwas produced by conventional hydrothermal synthesis method. The physico-chemical properties of the syn-thesized samples, the specific surface area of the samples synthesized under microwave irradiation and porevolume measured by X-ray diffraction apparatus, were better than the conventional samples. The etherificationexperiment on FCC light naphtha in the presence of transition metals modified Hβ-zeolite, which was synthe-sized firstly under microwave irradiation, was studied in a fixed-bed reactor. The effect of catalyst preparationconditions on its activity, stability and the effect of reaction temperature, methanol/tertiary-carbon olefin molarratio and liquid hourly space velocity on the etherification reaction were discussed. The experimental resultsshowed that the different metals modified Hβ-zeolite had different etherification performances. And theconversion of tertiary carbon-olefins of the molybdenum modified Hβzeolite, which was loaded at a concen-tration of 3 percents, was higher than that on 6.0 percent of Hβzeolite. The modified Hβzeolite catalystspossessed favorable prospects for its higher stability.展开更多
In this paper etherification of the terminal hydroxy group of polyethy-lene glycol monoalkyl ethers is studied and a convenient method for the preporation ofpolyethylene glycol dialkyl ethers is propused. Nine methyl ...In this paper etherification of the terminal hydroxy group of polyethy-lene glycol monoalkyl ethers is studied and a convenient method for the preporation ofpolyethylene glycol dialkyl ethers is propused. Nine methyl , butyl and benzyl deriva-tives are obtained by using Williamson synthetie method. The effect of reaction pa-rameters on the protective ratio is examined by using the optimum seeking method.The protective efficiency is evaluated by cumporing the variation of hydroxy value.The best reaction conditions are found by experiment.It is also found that the protec-tive ratio of methylation is higher than that of butylation while the protective ratio ofbenzylation is the lowest. The protective ratio of AEO9 is equivalant to OP8 and theprotective ratio of AFO3 is much lower.展开更多
The reaction of p- and/ α-subtituted benzyl alcohols in CaY-zeolite produced the corresponding dibenzyl ethers and/or benzyl toluenes as the principal products.
An efficient synthetic method for multi-substituted xanthones was developed. The reaction of diaryliodonium salts and salicylates was employed for the preparation of the xanthones. This method proceeded through an int...An efficient synthetic method for multi-substituted xanthones was developed. The reaction of diaryliodonium salts and salicylates was employed for the preparation of the xanthones. This method proceeded through an intermolecular etherification-acylation to give target heterocycles in good yields（up to 91%）. Multi-substituted xanthones were gained by shifting the substituent of salicylates or diaryliodonium salts展开更多
A reactive C5 olefins and methanol etherification kinetic model based on E-R mechanism was established and three different types of reactors including the adiabatic fixed-bed liquid reactor, the external loop reactor ...A reactive C5 olefins and methanol etherification kinetic model based on E-R mechanism was established and three different types of reactors including the adiabatic fixed-bed liquid reactor, the external loop reactor and the mixedphase reactor were constructed by Aspen Plus. The adaptability of reactive C5 olefins to these reactors was studied and simulated using various gasoline fractions with different olefins content. After the theoretical model was validated by the experimental data of the etherification of three C5 light cut fractions from different gasoline sources in different reactors, the simulated isoamylene conversion with reactive C5 olefin contents increasing from 10% to 60% was studied in the three different types of reactors for etherification with methanol, respectively. Test results show that there is an obvious adaptability of the feedstock composition to the reactor type to achieve a high conversion.展开更多
In the presence of either Pd/C or Pt/C, 4-alkoxybenzyl alcohols, 4-alkoxy-phenylalkyl alcohols and cinnamyl alcohols undergo liquid etherification to bis(4-alkoxybenzyl) ethers, bis[(4-alkoxybenzyl)alkyl] ethers and b...In the presence of either Pd/C or Pt/C, 4-alkoxybenzyl alcohols, 4-alkoxy-phenylalkyl alcohols and cinnamyl alcohols undergo liquid etherification to bis(4-alkoxybenzyl) ethers, bis[(4-alkoxybenzyl)alkyl] ethers and bis(cin-namyl) ethers at temperatures of 100°C - 135°C. In a number of cases, Pt/C and Pd/C as catalysts, also when they are doped with Ru, show distinct differences when the reactions run in air, with an oxidative dehydrogenation of the alcohols as side-reaction, yielding the corresponding ketones and aldehydes as by-products. Also, the reactivity of fluorinated phenylalkenols under these conditions has been investigated. Furthermore, the immobilization of alkyl aryl ethers on silica within a column with passage of hexane as solvent was found to lead to the formation and elution of styrenes from the column in fair yield.展开更多
Several types of solid acid catalysts were prepared based on oxides like (ZrO2, TiO2, HfO2, MCM-41 and SBA-15), using two main preparation methods: the precipitation and the sol-gel methods. Each catalyst was subjecte...Several types of solid acid catalysts were prepared based on oxides like (ZrO2, TiO2, HfO2, MCM-41 and SBA-15), using two main preparation methods: the precipitation and the sol-gel methods. Each catalyst was subjected to two types of impregnations: sulfate ions using sulfuric acid as precursor and niobium using niobium oxalate as precursor. These prepared catalysts were tested in the etherification reaction of 2-naphtol, where the catalysts showed both acidic and redox properties. The acidic character was manifested through the formation of 2-butoxynaphtalene (with moderate yields) when oxide is sulfated, and the redox character (when impregnated with niobium) manifested through the formation of the interesting product 2-ethylnaphtofuran (with low yields) and other products that were a result of oxidative coupling of two 2-naphtol molecules (binol and acetal of binol). However despite the effort, several attempts to increase the yield of 2-ethylnaphtofuran did not work. All products prepared were obtained in pure form and characterized by 1H and 13C NMR, GC and MS.展开更多
Mesoporous framework supported metal nanoparticle catalyst represents a promising material platform for creating multiple active sites that drive tandem reactions. In this study, we demonstrate a novel catalyst design...Mesoporous framework supported metal nanoparticle catalyst represents a promising material platform for creating multiple active sites that drive tandem reactions. In this study, we demonstrate a novel catalyst design that involves the encapsulation of CuNi alloy nanoparticles within mesoporous silicon carbide nanofibers (mSiC_(f)) to achieve efficient tandem conversion of furfural (FFA) into 2-(isopropoxymethyl)furan (IPF). The unique one-dimensional (1D) mesoporous structure of mSiC_(f), coupled with abundant oxygen-containing groups, offers a favorable surface microenvironment for the stabilization of bimetallic CuNi active sites. Through carefully optimizing metal to acid sites, we have developed a catalyst containing a total mass ratio of 20 % Cu and Ni, which exhibits a remarkable performance with complete FFA conversion and 92 % IPF selectivity in 4 h. In-depth mechanistic investigations have revealed that the superior activity of this catalyst is attributed to a tandem reaction mechanism. Initially, FFA is hydrogenated at the dual metal active sites to produce furfuryl alcohol (FOL) as an intermediate, which is subsequently etherified at the acid sites with suitable species and strengths on the mSiC_(f) supports. Additionally, the robust 1D mSiC_(f) framework effectively protects the metal sites from agglomeration, resulting in excellent reusability of the catalyst. This study underscores the potential of mesoporous silicon carbide-supported bimetallic active sites for achieving enhanced tandem catalytic functionality.展开更多
文摘The role of NH4^+ ion confinement in the catalytic etherification of HMF(5-hydroxymethylfurfural) with ethanol to biodiesel additives was evidenced by studying the catalytic behavior of NH4^+-Beta zeolites with SiO2/Al2O3 ratios of 25 and 75.In order to affect the strength and distribution of the acidic sites, as well as the mobility of NH4^+ ions in the zeolites cages, a secondary level of porosity was introduced in the NH4^+-Beta, presenting a different stability versus alkaline treatment, by using a thermal or an ultrasound assisted method.By analyzing the catalytic behavior in these two series of samples with respect to the changes in porosity by nonlocal density functional theory, structure by XRD, amount of acid sites by FT-IR and mobility of NH4^+ cations by measurements of reversible NH4^+ exchange capacity, was evidenced a decrease in catalytic performances both in terms of rate of HMF depletion and productivity to the main products, when confinement of the ammonium ions is lost due to the introduction of mesoporosity.The high capability of ammonium ions release, associated to the mono-dentate configuration,and the minor confinement effect inside the zeolite pore system, due to the more opened pores structure of mesoporous zeolites, hinders both the direct etherification of HMF to EMF [5-(ethoxymethyl)furan-2-carbaldehyde] and the parallel reaction pathway via acetalization, favoring the rapid desorption of the HMFDEA [5-(hydroxymethyl)furfural diethyl acetal] product out of the crystal and the consequent inhibition of the consecutive reactions to EMFDEA [5-(ethoxymethyl)furfural diethyl acetal] and EMF.
基金financial support from the National Natural Science Foundation of China(21773067)the Open Research fund of Shanghai Key Laboratory of Green Chemistry and Chemical Processes。
文摘Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the preparation of a reusable Pd catalyst for reductive etherification remains to be a great challenge.In this study,a series of Si O_(2)supported Pd catalysts with particle size ranging from 2.2 nm to 28 nm were prepared.Their textural properties and catalytic performance in furfural reductive etherification have been systematically studied.The results herein shed light on the particle size effect on the competition between hydrogenation/hydrogenolysis of C=O in furfural over Pd surface.We found out that Pd nanoparticles larger than 3 nm are preferred for one step reductive etherification.Based on this finding,we prepared a Pd/ZSM-5 bifunctional catalyst comprising Pd nanoparticles larger than 3 nm and decreased acidity in presence of amino organosilane,which served as a bifunctional catalyst succeeding in one-pot synthesis of ether via reductive-etherification and direct-etherification.This strategy showed significant advantage in efficiently converting furfuryl acohol,a major side-product,into ether,while suppressing the undesired side-reactions.
基金supported by the Research Project for Hot Tracking Items of Beijing Forestry University(2017BLRD03)the National Natural Science Foundation of China(51603012)+1 种基金the Special Science and Technology Research Program of Beijing Forestry University(2016KJ02)the Fundamental Research Funds for the Central Universities(BLYJ2016-17,BLX2015-06)
文摘A new method for the preparation of aminated lignin （AEL） through etherification and amination reaction was presented. Chlorine atoms were ？rstly introduced into lignin through its etheri？cation with epichlorohydrin. Then, hydrophilic amine groups were grafted to the modi？ed lignin structure through amination with ethylenediamine to obtain AEL. Subsequent acidi？cation of AEL led to the ionized aminated lignin （IAEL）. The results of our analyses showed that the nitrogen content of AEL was 6.9%. Foaming and emulsifying experiments indicated that AEL had better foamability and emulsifying properties than IAEL. Surface tension tests showed that AEL and IAEL had similar critical micelle concentration （CMC）. However, IAEL had lower surface tension （36.33 mN/m） than AEL （42.89 mN/m） at CMC. These results demonstrate the promising applicability of AEL as an emulsi？er and that of IAEL as feedstock in the production of detergent and dispersant.
基金financial support from the National High Technology Research and Development Program 863(2011AA05A204)National Natural Science Foundation of China(U1361202)
文摘Isoamylene from the Fischer-Tropsch syncrude can be transformed to valuable fuel oxygenate additives through an equilibrium limited etherification reaction with methanol. A reactive distillation process is established to increase isoamylene conversion. Facing the challenge of improving product purity at the same time, an equilibrium stage model based design methodology is proposed and illustrated step-by-step for converting the Fischer-Tropsch C_5 olefins to tert-amyl methyl ether(TAME) process by using Aspen Plus. Under the guide of the proposed methodology, the design leads to a TAME product purity of higher than 95% and an isoamylene conversion of higher than 90%. The etherification kinetics over Amberlyst 35 is also studied within a temperature range of 60 ℃ to 75 ℃ to shed more light on the feasibility of process development. The methodology provides an effective reactive distillation column design to achieve the target reactant conversion and product purity simultaneously.
基金The authors are grateful for the financial support from the Science and Technology Program of Guangdong(2019A1515011890)National Key R&D Program of China(2017YFD0601003).
文摘Sugarcane bagasse(SCB)is an important by-product in the sugar industry.It is a source of cellulose fibers or cellulose for paper mills and textiles factories.In this study,SCB was ethyl etherified in tetrahydrofuran(THF)after alkali pretreatment.The alkali concentration for the pretreatment,the ratio of ethyl bromide(EtBr)to dried SCB in the reaction,reaction time,and temperature were investigated for the etherification of SCB.The ethoxyl content and characterization of the product were determined using headspace gas chromatography(HS-GC),Fourier Transform Infrared(FT-IR)and 13C-NMR spectroscopy,respectively.It was found that SCB was well-etherified with EtBr in alkali-THF.Upon ethylation of SCB,the ethoxyl content of the product was high when the alkali concentration and the ratio of EtBr to dried SCB were controlled from 50%to 75%and 4:1(V/w)to 6:1(V/w),respectively.The reaction occurred optimally when the temperature was controlled below 110℃;above this temperature,the degree of etherification decreased.The thermal stability of ethylated SCB was higher than that of SCB but slightly lower than that of commercial ethyl cellulose.Ethylated SCB has the potential to form composites with many materials because it is soluble in a wide variety of solvents.
文摘zeolite was synthesized by using tetraethyl ammonium hydroxide as the template reagent andmicrowave radiation as the heat source. The effect of the sol composition and the radiation temperature onzeolite crystallinity was investigated. The zeolite was tested and compared with the commercial product, whichwas produced by conventional hydrothermal synthesis method. The physico-chemical properties of the syn-thesized samples, the specific surface area of the samples synthesized under microwave irradiation and porevolume measured by X-ray diffraction apparatus, were better than the conventional samples. The etherificationexperiment on FCC light naphtha in the presence of transition metals modified Hβ-zeolite, which was synthe-sized firstly under microwave irradiation, was studied in a fixed-bed reactor. The effect of catalyst preparationconditions on its activity, stability and the effect of reaction temperature, methanol/tertiary-carbon olefin molarratio and liquid hourly space velocity on the etherification reaction were discussed. The experimental resultsshowed that the different metals modified Hβ-zeolite had different etherification performances. And theconversion of tertiary carbon-olefins of the molybdenum modified Hβzeolite, which was loaded at a concen-tration of 3 percents, was higher than that on 6.0 percent of Hβzeolite. The modified Hβzeolite catalystspossessed favorable prospects for its higher stability.
文摘In this paper etherification of the terminal hydroxy group of polyethy-lene glycol monoalkyl ethers is studied and a convenient method for the preporation ofpolyethylene glycol dialkyl ethers is propused. Nine methyl , butyl and benzyl deriva-tives are obtained by using Williamson synthetie method. The effect of reaction pa-rameters on the protective ratio is examined by using the optimum seeking method.The protective efficiency is evaluated by cumporing the variation of hydroxy value.The best reaction conditions are found by experiment.It is also found that the protec-tive ratio of methylation is higher than that of butylation while the protective ratio ofbenzylation is the lowest. The protective ratio of AEO9 is equivalant to OP8 and theprotective ratio of AFO3 is much lower.
基金the National Natural Science Foundation of China(Grant No.29972018)Foundation for University Key Teacher by Ministry of Education of China for financial support.
文摘The reaction of p- and/ α-subtituted benzyl alcohols in CaY-zeolite produced the corresponding dibenzyl ethers and/or benzyl toluenes as the principal products.
基金supported by the National Natural Science Foundation of China (Nos. 21372138 and 21672120)The National Key Research and Development Program of China (No. 2016YFB0401400)+1 种基金the Fok Ying Tong Education Foundation of China (No. 151014)the Postdoctoral Foundation of the PekingTsinghua Joint Center for Life Sciences
文摘An efficient synthetic method for multi-substituted xanthones was developed. The reaction of diaryliodonium salts and salicylates was employed for the preparation of the xanthones. This method proceeded through an intermolecular etherification-acylation to give target heterocycles in good yields（up to 91%）. Multi-substituted xanthones were gained by shifting the substituent of salicylates or diaryliodonium salts
文摘A reactive C5 olefins and methanol etherification kinetic model based on E-R mechanism was established and three different types of reactors including the adiabatic fixed-bed liquid reactor, the external loop reactor and the mixedphase reactor were constructed by Aspen Plus. The adaptability of reactive C5 olefins to these reactors was studied and simulated using various gasoline fractions with different olefins content. After the theoretical model was validated by the experimental data of the etherification of three C5 light cut fractions from different gasoline sources in different reactors, the simulated isoamylene conversion with reactive C5 olefin contents increasing from 10% to 60% was studied in the three different types of reactors for etherification with methanol, respectively. Test results show that there is an obvious adaptability of the feedstock composition to the reactor type to achieve a high conversion.
文摘In the presence of either Pd/C or Pt/C, 4-alkoxybenzyl alcohols, 4-alkoxy-phenylalkyl alcohols and cinnamyl alcohols undergo liquid etherification to bis(4-alkoxybenzyl) ethers, bis[(4-alkoxybenzyl)alkyl] ethers and bis(cin-namyl) ethers at temperatures of 100°C - 135°C. In a number of cases, Pt/C and Pd/C as catalysts, also when they are doped with Ru, show distinct differences when the reactions run in air, with an oxidative dehydrogenation of the alcohols as side-reaction, yielding the corresponding ketones and aldehydes as by-products. Also, the reactivity of fluorinated phenylalkenols under these conditions has been investigated. Furthermore, the immobilization of alkyl aryl ethers on silica within a column with passage of hexane as solvent was found to lead to the formation and elution of styrenes from the column in fair yield.
文摘Several types of solid acid catalysts were prepared based on oxides like (ZrO2, TiO2, HfO2, MCM-41 and SBA-15), using two main preparation methods: the precipitation and the sol-gel methods. Each catalyst was subjected to two types of impregnations: sulfate ions using sulfuric acid as precursor and niobium using niobium oxalate as precursor. These prepared catalysts were tested in the etherification reaction of 2-naphtol, where the catalysts showed both acidic and redox properties. The acidic character was manifested through the formation of 2-butoxynaphtalene (with moderate yields) when oxide is sulfated, and the redox character (when impregnated with niobium) manifested through the formation of the interesting product 2-ethylnaphtofuran (with low yields) and other products that were a result of oxidative coupling of two 2-naphtol molecules (binol and acetal of binol). However despite the effort, several attempts to increase the yield of 2-ethylnaphtofuran did not work. All products prepared were obtained in pure form and characterized by 1H and 13C NMR, GC and MS.
基金supported by the National Natu-ral Science Foundation of China(Nos.52225204,52173233,and 52202085)the Innovation Program of Shanghai Municipal Edu-cation Commission(No.2021-01-07-00-03-E00109)+4 种基金Natural Sci-ence Foundation of Shanghai(No.23ZR1479200)the Shanghai Sci-entific and Technological Innovation Project(No.24520712800)“Shuguang Program”Supported by the Shanghai Education Devel-opment Foundation and Shanghai Municipal Education Commis-sion(No.20SG33)the Fundamental Research Funds for the Central Universities(No.2232024Y-01)the DHU Distinguished Young Professor Program(Nos.LZA2022001and LZB2023002).
文摘Mesoporous framework supported metal nanoparticle catalyst represents a promising material platform for creating multiple active sites that drive tandem reactions. In this study, we demonstrate a novel catalyst design that involves the encapsulation of CuNi alloy nanoparticles within mesoporous silicon carbide nanofibers (mSiC_(f)) to achieve efficient tandem conversion of furfural (FFA) into 2-(isopropoxymethyl)furan (IPF). The unique one-dimensional (1D) mesoporous structure of mSiC_(f), coupled with abundant oxygen-containing groups, offers a favorable surface microenvironment for the stabilization of bimetallic CuNi active sites. Through carefully optimizing metal to acid sites, we have developed a catalyst containing a total mass ratio of 20 % Cu and Ni, which exhibits a remarkable performance with complete FFA conversion and 92 % IPF selectivity in 4 h. In-depth mechanistic investigations have revealed that the superior activity of this catalyst is attributed to a tandem reaction mechanism. Initially, FFA is hydrogenated at the dual metal active sites to produce furfuryl alcohol (FOL) as an intermediate, which is subsequently etherified at the acid sites with suitable species and strengths on the mSiC_(f) supports. Additionally, the robust 1D mSiC_(f) framework effectively protects the metal sites from agglomeration, resulting in excellent reusability of the catalyst. This study underscores the potential of mesoporous silicon carbide-supported bimetallic active sites for achieving enhanced tandem catalytic functionality.
