A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during ...A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during fabricating the support.Using this strategy,supported CuBr/di-（2-picolyl） amine catalyst with U-shaped fibrillar network was prepared and used in atom transfer radical polymerization of methyl methacrylate.XPS and SEM characterization of the catalyst revealed homogeneous distribution of ligand,sufficient reactive sites,adequate mechanical strength and macroporosity.The polymerization results demonstrated high activity and reusability of such catalyst.This strategy might be extended to other supported catalysts used in column reactors.展开更多
The supported catalysts for propylene polymerization were prepared by milling Mg (OEt)_2 with EB (ethylbenzoate) and treating with TiCl_4 solution. When TiCl_4/(Mg(OEt)_2/EB) (mol.) ratio was increased, decrease in co...The supported catalysts for propylene polymerization were prepared by milling Mg (OEt)_2 with EB (ethylbenzoate) and treating with TiCl_4 solution. When TiCl_4/(Mg(OEt)_2/EB) (mol.) ratio was increased, decrease in contents of-OEt and Ti of the catalysts was observed, while the content of EB increased. It is proved by analyses of IR, X-ray and XPS that during co-milling Mg(OEt)_2 with EB no reactions have taken place. But after treatment with TiCl_4 solution, Mg(OEt)_2 converts into MgCl_2 and EB coordinates on the resulting MgCl_2 carrier, a surface complex forms.The activity of catalysts,isotacticity and vicosimetric molecular weight of polypropylene increase with the decrease of the content of ethoxyl group. The kinetic curves of propene polymerization obtained with present catalysts system display decay curves. It is found from the triad tacticity calculated from the expanded spectra of methyl carbon region that, ethoxyl group in catalyst has an effect on the configuration of polymer chain.展开更多
Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticle...Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.展开更多
Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile...Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds(VOCs).In this work,we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom(Co_(1)Ni_(1)/meso-Cr_(2)O_(3))and bimetallic Co and Ni nanoparticle(Co_(NP)Ni_(NP)/mesoCr_(2)O_(3))catalysts adopting the one-pot polyvinyl pyrrolidone(PVP)-and polyvinyl alcohol(PVA)-protecting approaches,respectively.The results indicate that the Co_(1)Ni_(1)/meso-Cr_(2)O_(3)catalyst exhibited the best catalytic activity for n-hexane(C_(6)H_(14))combustion(T_(50%)and T_(90%)were 239 and 263℃ at a space velocity of 40,000 mL g^(-1)h^(-1);apparent activation energy and specific reaction rate at 260℃ were 54.7 kJ mol^(-1)and 4.3×10^(-7)mol g^(-1)_(cat)s^(-1),respectively),which was associated with its higher(Cr^(5+)+Cr^(6+))amount,large n-hexane adsorption capacity,and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane,in which Ni_(1) was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility,while Co_(1) preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane.n-Hexane combustion takes place via the Mars van Krevelen(MvK)mechanism,and its reaction pathways are as follows:n-hexane→olefins or 3-hexyl hydroperoxide→3-hexanone,2-hexanone or 2,5-dimethyltetrahydrofuran→2-methyloxirane or 2-ethyl-oxetane→acrylic acid→CO_x→CO_(2)and H_(2)O.展开更多
Porous silica nano-flowers(KCC-1)immobilized Pt-Pd alloy NPs(Pt-Pd/KCC-1)with different mass ratios of Pd and Pt were successfully prepared by a facile in situ one-step reduction,using hydrazinium hydroxide as a reduc...Porous silica nano-flowers(KCC-1)immobilized Pt-Pd alloy NPs(Pt-Pd/KCC-1)with different mass ratios of Pd and Pt were successfully prepared by a facile in situ one-step reduction,using hydrazinium hydroxide as a reducing agent.The as-synthesized silica nanospheres possess radial fibers with a distance of 15 nm,exhibiting a high specific surface area(443.56 m^(2)·g^(-1)).Meanwhile,the obtained Pt-Pd alloy NPs are uniformly dispersed on the silica surface with a metallic particle size of 4-6 nm,which exist as metallic Pd and Pt on the surface of monodisperse KCC-1,showing the transfer of electrons from Pd to Pt.The as-synthesized 2.5%Pt-2.5%Pd/KCC-1 exhibited excellent catalytic activity and stability for the continuous dehydrogenation of 2-methoxycyclohexanol to prepare guaiacol.Compared with Pt or Pd single metal supported catalysts,the obtained 2.5%Pt-2.5%Pd/KCC-1 shows 97.2%conversion rate of 2-methoxycyclohexanol and 76.8%selectivity for guaiacol,which attributed to the significant synergistic effect of bimetallic Pt-Pd alloy NPs.Furthermore,turn over frequency value of the obtained 2.5%Pt-2.5%Pd/KCC-1 NPs achieved 4.36 s^(-1),showing higher catalytic efficiency than other two monometallic catalysts.Reaction pathways of dehydro-aromatization of 2-methoxycyclohexanol over the obtained catalyst are proposed.Consequently,the obtained 2.5%Pt-2.5%Pd/KCC-1 NPs prove their potential in the dehydrogenation of 2-methoxycyclohexanol,while the kinetics and mechanistic study of the dehydrogenation reaction over the catalyst in a continuous fixed-bed reactor may provide valuable information for the development of green,outstanding and powerful synthetic pathway of guaiacol.展开更多
Doping heteroatoms on carbon materials could bring some special advantages for using as catalyst support.In this work, a boron doped lamellar porous carbon(B-LPC) was prepared facilely and utilized as carbonbased supp...Doping heteroatoms on carbon materials could bring some special advantages for using as catalyst support.In this work, a boron doped lamellar porous carbon(B-LPC) was prepared facilely and utilized as carbonbased support to construct Cu/B-LPC catalyst for dimethyl oxalate(DMO) hydrogenation. Doping boron could make the B-LPC own more defects on surface and bigger pore size than B-free LPC, which were beneficial to disperse and anchor Cu nanoparticles. Moreover, the interaction between Cu species and B-LPC could be strengthened by the doped B, which not only stabilized the Cu nanoparticles, but also tuned the valence of Cu species to maintain more Cu^(+). Therefore, the B-doped Cu/B-LPC catalyst exhibited stronger hydrogenation ability and obtained higher alcohols selectivity than Cu/LPC, as well as high stability without decrease of DMO conversion and ethylene glycol selectivity even after 300 h of reaction at 240℃.展开更多
Supported metal catalysts,particularly for precious metals,have gained increasing attention in green synthetic chemistry.They can make metal-catalyzed organic synthesis more sustainable and economical due to easy sepa...Supported metal catalysts,particularly for precious metals,have gained increasing attention in green synthetic chemistry.They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue,as well as reusability of the high-cost catalysts.Although great effort has been spent,the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable recyclable catalysts remains challenging.This highlight reveals a“molecular fence”metal stabilization strategy and discloses the metal evolution in Pd-catalyzed C-C bond formation reactions using Nheterocyclic carbene(NHC)-functionalized hypercrosslinked polymer support,wherein the polymeric skeleton isolates or confines the metal species involved in the catalytic reactions,and NHC captures free low-valent metal species in solution and stabilizes them on the support via strong metal-support coordination interaction.This strategy creates a novel route for the development of supported metal catalysts with high stability and provides insights into the reaction mechanism of heterogeneous catalysis.展开更多
Lignin is the world's greatest renewable aromatic biofeedstock,and it has promising applications in high value-added chemical products.Herein,N-Co/ATP-CZO was used as a catalyst for the depolymerization of alkali ...Lignin is the world's greatest renewable aromatic biofeedstock,and it has promising applications in high value-added chemical products.Herein,N-Co/ATP-CZO was used as a catalyst for the depolymerization of alkali lignin in ethanol and isopropanol systems,and explored the effects of formic acid(FA)amount,reaction time,reaction temperature and other factors on the depolymerization of alkali lignin.Among them,formic acid serves as both catalytic and in situ-hydrogen donor.Ultimately,the highest yield of bio-oil(59.28%(mass)),including 30.05%(mass)of monomer,was obtained after a reaction of FA to alkali lignin mass ratio of 4 and 240°C for 8 h.Among the monomers,the yield of Guaiacol was the highest(5.94%(mass)),followed by 2-methoxy-4-methylphenol(5.74%(mass)).This study,the modification of attapulgite was carried out to reduce the acidity while enhancing the catalytic activity for depolymerization,and the selection of hydrogen donor was investigated.A feasible pathway for lignin depolymerization research was opened.展开更多
A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported P...A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported Pd catalyst（Pd/A-45） was highly active and selective under mild conditions（40-100 ℃,0.2-1 MPa）,giving a selectivity of cyclohexanone higher than 89%even at complete conversion of phenol.Experiments with different Pd loadings（or different particle sizes） confirmed that the formation of cyclohexanone was a structure sensitive reaction,and Pd particles of12-14 nm on Amberlyst-45 gave better selectivity and stability.展开更多
Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalys...Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and sup‐ported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excel‐lent catalytic performance was due to their high surface areas, high concentration of adsorbed oxy‐gen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and pro‐posed future work for the removal of VOCs.展开更多
The reductive transformation of furfural （FAL） into furfuryl alcohol （FOL） is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient ...The reductive transformation of furfural （FAL） into furfuryl alcohol （FOL） is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst （Au/TiO2‐R） that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel‐derived H2, our pro‐cess has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.展开更多
Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS a...Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.展开更多
Polyethylene (PE) grafting 4-vinylpyridine copolymers has been produced as powders of different rushes by theirradiation method. After treatment with methylaluminoxane (MAO), the copolymers were used as supports for C...Polyethylene (PE) grafting 4-vinylpyridine copolymers has been produced as powders of different rushes by theirradiation method. After treatment with methylaluminoxane (MAO), the copolymers were used as supports for Cp_2ZrCl_2catalyst Results of X-ray photoelectron spectroscopy, Fourier transforms infrared spectroscopy, ultraviolet spectroscopy andscanning electron microscope measurements show that the catalytic sites have been linked through MAO on the PE-graft-4-vinylpyridine (PEVP). The percentages of grafting 4-vinylpyridine and supported Cp_2ZrCl_2 depend on the size ofpolyethylene powder. The smaller the polyethylene powder, the more percent of 4-vinylpyridine groups and Cp_2ZrCl_2 existon the polyethylene chains, and the PEVP-supported catalyst has a relatively high activity for ethylene polymerization.展开更多
Two types of small iron clusters supported on γ-Al2O3-RT（dehydroxylated at room temperature） and γ-Al2O3-800 （dehydroxylated at 800 ℃） were prepared by solvated metal atom impregnation （SMAI） techniques. The ...Two types of small iron clusters supported on γ-Al2O3-RT（dehydroxylated at room temperature） and γ-Al2O3-800 （dehydroxylated at 800 ℃） were prepared by solvated metal atom impregnation （SMAI） techniques. The iron atom precursor complex, bis（toluene）iron（0） formed in the metal atom reactor, was impregnated into γ-Al2O3 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by TEM, Mǒssbauer, and chemisorption measurements, and the results show that higher concentration of surface hydroxyl groups of γ-Al2O3-RT favors the formation of more positively charged supported iron cluster Fen/γ-Al2O3-RT, and the lower concentration of surface hydroxyl groups of γ-Al2O3-800 favors the formation of basically neutral supported iron cluster Fen/γ-Al2O3-800. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the rapid decomposition of precursor complex, bis（toluene）iron（0）, and favors the formation of relatively large iron cluster. Consequently, these two types of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fen/γ-Al2O3-RT in F-T reaction is similar to that of the unreduced γ-Fe2O3 and that of Fen/γ-Al2O3-800 is similar to that of the reduced α-Fe2O3.展开更多
A supported iron catalyst, which was prepared by anchoring FeCl2/FeCl3 on the cross-linking macroporous polyacrylate ion exchange resin, was evaluated via the controlled radical polymerization. When a small amount of ...A supported iron catalyst, which was prepared by anchoring FeCl2/FeCl3 on the cross-linking macroporous polyacrylate ion exchange resin, was evaluated via the controlled radical polymerization. When a small amount of CuCl2/ Me6TREN was added, the controllability of the polymerization over the iron-mediated catalyst was significantly improved（Mw/Mn = 1.23-1.73 ）, affording a polymer with a low residual metal via a simple catalyst separation procedure. After suitable regeneration, the supported iron catalyst could also he recycled. UV-Vis analysis showed that the additional copper catalyst could facilitate the radical deactivation process.展开更多
The simultaneous removal of SO_(2),NO_(x)and Hg^(0)from industrial exhaust flue gas has drawn worldwide attention in recent years.A particularly attractive technique is selective catalytic reduction,which effectively ...The simultaneous removal of SO_(2),NO_(x)and Hg^(0)from industrial exhaust flue gas has drawn worldwide attention in recent years.A particularly attractive technique is selective catalytic reduction,which effectively removes SO_(2),NO_(x)and Hg^(0)at low temperatures.This paper first reviews the simultaneous removal of SO_(2),NO_(x)and Hg^(0)by unsupported and supported catalysts.It then describes and compares the research progress of various carriers,eg.,carbon-based materials,metal oxides,silica,molecular sieves,metal-organic frameworks,and pillared interlayered clays,in the simultaneous removal of SO_(2),NO_(x)and Hg^(0).The effects of flue-gas components(such as O_(2),NH3,HCl,H2 O,SO_(2),NO and Hg^(0))on the removal of SO_(2),NOx,and Hg^(0)are discussed comprehensively and systematically.After summarizing the pollutantremoval mechanism,the review discusses future developments in the simultaneous removal of SO_(2),NOx and Hg^(0)by catalysts.展开更多
A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potenti...A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.展开更多
An ultrasound-assisted heterogeneous catalytic oxidation process was applied to eliminate sulfur from commercial diesel fuel oil.The studied variables were catalyst concentration,type of catalyst(homogeneous or hetero...An ultrasound-assisted heterogeneous catalytic oxidation process was applied to eliminate sulfur from commercial diesel fuel oil.The studied variables were catalyst concentration,type of catalyst(homogeneous or heterogeneous),oxidizing agent concentration,and the application of ultrasound energy.Supported catalysts were prepared by impregnation of coal fly ash with an iron(Ⅱ)sulfate aqueous solution using ultrasound energy.After drying,the catalyst was calcined at 500℃for 4 h.The oxidizing agent was hydrogen peroxide.Ultrasound energy was applied with a frequency of 47 kHz and an intensity of 147 W.Ethanol was employed for extracting the oxidized compounds from the hydrocarbon mixture.Coal fly ash and ethanol were used with the purpose of applying low-cost raw materials in chemical processes.It was found that under the studied conditions,increasing oxidizing agent concentration and the application of ultrasound energy can enhance the sulfur removal from commercial diesel fuel oil.Catalyst concentration did not play a significant role in the process.Similar results were obtained using homogeneous or heterogeneous catalyst,which is important since the heterogeneous catalyst could be recovered,reactivated,and used in many cycles.展开更多
8-Aminoquinoline nickel dichloride and bis(cyclopentadienyl)zirconium dichloride (Cp_2ZrCl_2) were supportedsimultaneously on silica to produce branched polyethylene successfully by combined polymerization. The suppor...8-Aminoquinoline nickel dichloride and bis(cyclopentadienyl)zirconium dichloride (Cp_2ZrCl_2) were supportedsimultaneously on silica to produce branched polyethylene successfully by combined polymerization. The supportedpolymerization results showed that the molecular weight of polyethylene increased while the molecular weight distributionbecame wider and the molecular chains of oligomers remaning in the final solution became shorter as compared to theoligomers obtained in polymerization processes with pure 8-aminoquinoline nickel dichloride catalysis, as well as theCp_2ZrCl_2 and nickel combination system. With decreasing amount of Ni catalyst in the supported catalyst, the molecular chains of oligomers in the resulting solution became shorter, while α-olefin selectivity increased.展开更多
A new supported amorphous catalyst CoP/TiO2 was prepared by chemical reduction and characterized by ICP, XRD, TEM, BET and DSC. Its application in decomposing PH3 to high purity phosphor and its catalytic activity wer...A new supported amorphous catalyst CoP/TiO2 was prepared by chemical reduction and characterized by ICP, XRD, TEM, BET and DSC. Its application in decomposing PH3 to high purity phosphor and its catalytic activity were studied. The decomposition rate is over 95% at 450 ℃. For comparison, unsupported CoP amorphous catalyst was prepared by the same method. The result suggests that CoP/TiO2 exhibits higher thermal stability and catalytic activity than CoP, which is attributed to the high dispersion of CoP alloy particles on the support-TiO2.展开更多
基金support from the National Natural Science Foundation of China(Nos.20574041 and 20874055)Hi-tech Research and Development Program(863 plan) of China(No.2009AA062903)
文摘A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during fabricating the support.Using this strategy,supported CuBr/di-（2-picolyl） amine catalyst with U-shaped fibrillar network was prepared and used in atom transfer radical polymerization of methyl methacrylate.XPS and SEM characterization of the catalyst revealed homogeneous distribution of ligand,sufficient reactive sites,adequate mechanical strength and macroporosity.The polymerization results demonstrated high activity and reusability of such catalyst.This strategy might be extended to other supported catalysts used in column reactors.
文摘The supported catalysts for propylene polymerization were prepared by milling Mg (OEt)_2 with EB (ethylbenzoate) and treating with TiCl_4 solution. When TiCl_4/(Mg(OEt)_2/EB) (mol.) ratio was increased, decrease in contents of-OEt and Ti of the catalysts was observed, while the content of EB increased. It is proved by analyses of IR, X-ray and XPS that during co-milling Mg(OEt)_2 with EB no reactions have taken place. But after treatment with TiCl_4 solution, Mg(OEt)_2 converts into MgCl_2 and EB coordinates on the resulting MgCl_2 carrier, a surface complex forms.The activity of catalysts,isotacticity and vicosimetric molecular weight of polypropylene increase with the decrease of the content of ethoxyl group. The kinetic curves of propene polymerization obtained with present catalysts system display decay curves. It is found from the triad tacticity calculated from the expanded spectra of methyl carbon region that, ethoxyl group in catalyst has an effect on the configuration of polymer chain.
基金support by the National Natural Science Foundation of China(U21A20306,U20A20152)Natural Science Foundation of Hebei Province(B2022202077).
文摘Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.
基金supported by the National Natural Science Committee of China-Liaoning Provincial People's Government Joint Fund(U1908204)National Natural Science Foundation of China(21876006,21976009,and 21961160743)+2 种基金Foundation on the Creative Research Team Construction Promotion Project of Beijing Municipal Institutions(IDHT20190503)Natural Science Foundation of Beijing Municipal Commission of Education(KM201710005004)Development Program for the Youth Outstanding-Notch Talent of Beijing Municipal Commission of Education(CIT&TCD201904019)。
文摘Developing the alternative supported noble metal catalysts with low cost,high catalytic efficiency,and good resistance toward carbon dioxide and water vapor is critically demanded for the oxidative removal of volatile organic compounds(VOCs).In this work,we prepared the mesoporous chromia-supported bimetallic Co and Ni single-atom(Co_(1)Ni_(1)/meso-Cr_(2)O_(3))and bimetallic Co and Ni nanoparticle(Co_(NP)Ni_(NP)/mesoCr_(2)O_(3))catalysts adopting the one-pot polyvinyl pyrrolidone(PVP)-and polyvinyl alcohol(PVA)-protecting approaches,respectively.The results indicate that the Co_(1)Ni_(1)/meso-Cr_(2)O_(3)catalyst exhibited the best catalytic activity for n-hexane(C_(6)H_(14))combustion(T_(50%)and T_(90%)were 239 and 263℃ at a space velocity of 40,000 mL g^(-1)h^(-1);apparent activation energy and specific reaction rate at 260℃ were 54.7 kJ mol^(-1)and 4.3×10^(-7)mol g^(-1)_(cat)s^(-1),respectively),which was associated with its higher(Cr^(5+)+Cr^(6+))amount,large n-hexane adsorption capacity,and good lattice oxygen mobility that could enhance the deep oxidation of n-hexane,in which Ni_(1) was beneficial for the enhancements in surface lattice oxygen mobility and low-temperature reducibility,while Co_(1) preferred to generate higher contents of the high-valence states of chromium and surface oxygen species as well as adsorption and activation of n-hexane.n-Hexane combustion takes place via the Mars van Krevelen(MvK)mechanism,and its reaction pathways are as follows:n-hexane→olefins or 3-hexyl hydroperoxide→3-hexanone,2-hexanone or 2,5-dimethyltetrahydrofuran→2-methyloxirane or 2-ethyl-oxetane→acrylic acid→CO_x→CO_(2)and H_(2)O.
基金supported by Natural Science Foundation of Henan Province of China(162300410253)the Open Research Fund of State Key Laboratory of Coking Coal Exploitation and Comprehensive Utilization,China Pingmei Shen-ma Group(41040220181107-8).
文摘Porous silica nano-flowers(KCC-1)immobilized Pt-Pd alloy NPs(Pt-Pd/KCC-1)with different mass ratios of Pd and Pt were successfully prepared by a facile in situ one-step reduction,using hydrazinium hydroxide as a reducing agent.The as-synthesized silica nanospheres possess radial fibers with a distance of 15 nm,exhibiting a high specific surface area(443.56 m^(2)·g^(-1)).Meanwhile,the obtained Pt-Pd alloy NPs are uniformly dispersed on the silica surface with a metallic particle size of 4-6 nm,which exist as metallic Pd and Pt on the surface of monodisperse KCC-1,showing the transfer of electrons from Pd to Pt.The as-synthesized 2.5%Pt-2.5%Pd/KCC-1 exhibited excellent catalytic activity and stability for the continuous dehydrogenation of 2-methoxycyclohexanol to prepare guaiacol.Compared with Pt or Pd single metal supported catalysts,the obtained 2.5%Pt-2.5%Pd/KCC-1 shows 97.2%conversion rate of 2-methoxycyclohexanol and 76.8%selectivity for guaiacol,which attributed to the significant synergistic effect of bimetallic Pt-Pd alloy NPs.Furthermore,turn over frequency value of the obtained 2.5%Pt-2.5%Pd/KCC-1 NPs achieved 4.36 s^(-1),showing higher catalytic efficiency than other two monometallic catalysts.Reaction pathways of dehydro-aromatization of 2-methoxycyclohexanol over the obtained catalyst are proposed.Consequently,the obtained 2.5%Pt-2.5%Pd/KCC-1 NPs prove their potential in the dehydrogenation of 2-methoxycyclohexanol,while the kinetics and mechanistic study of the dehydrogenation reaction over the catalyst in a continuous fixed-bed reactor may provide valuable information for the development of green,outstanding and powerful synthetic pathway of guaiacol.
基金financially supported by the National Natural Science Foundation of China (22008166)Natural Science Foundation of Shanxi (201901D211047)Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (2019L0185)。
文摘Doping heteroatoms on carbon materials could bring some special advantages for using as catalyst support.In this work, a boron doped lamellar porous carbon(B-LPC) was prepared facilely and utilized as carbonbased support to construct Cu/B-LPC catalyst for dimethyl oxalate(DMO) hydrogenation. Doping boron could make the B-LPC own more defects on surface and bigger pore size than B-free LPC, which were beneficial to disperse and anchor Cu nanoparticles. Moreover, the interaction between Cu species and B-LPC could be strengthened by the doped B, which not only stabilized the Cu nanoparticles, but also tuned the valence of Cu species to maintain more Cu^(+). Therefore, the B-doped Cu/B-LPC catalyst exhibited stronger hydrogenation ability and obtained higher alcohols selectivity than Cu/LPC, as well as high stability without decrease of DMO conversion and ethylene glycol selectivity even after 300 h of reaction at 240℃.
基金support of the Start-up Research Fund of Dongguan University of Technology(KCYKYQD2017015).
文摘Supported metal catalysts,particularly for precious metals,have gained increasing attention in green synthetic chemistry.They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue,as well as reusability of the high-cost catalysts.Although great effort has been spent,the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable recyclable catalysts remains challenging.This highlight reveals a“molecular fence”metal stabilization strategy and discloses the metal evolution in Pd-catalyzed C-C bond formation reactions using Nheterocyclic carbene(NHC)-functionalized hypercrosslinked polymer support,wherein the polymeric skeleton isolates or confines the metal species involved in the catalytic reactions,and NHC captures free low-valent metal species in solution and stabilizes them on the support via strong metal-support coordination interaction.This strategy creates a novel route for the development of supported metal catalysts with high stability and provides insights into the reaction mechanism of heterogeneous catalysis.
基金financially supported by National Natural Science Foundation of China (21774059)。
文摘Lignin is the world's greatest renewable aromatic biofeedstock,and it has promising applications in high value-added chemical products.Herein,N-Co/ATP-CZO was used as a catalyst for the depolymerization of alkali lignin in ethanol and isopropanol systems,and explored the effects of formic acid(FA)amount,reaction time,reaction temperature and other factors on the depolymerization of alkali lignin.Among them,formic acid serves as both catalytic and in situ-hydrogen donor.Ultimately,the highest yield of bio-oil(59.28%(mass)),including 30.05%(mass)of monomer,was obtained after a reaction of FA to alkali lignin mass ratio of 4 and 240°C for 8 h.Among the monomers,the yield of Guaiacol was the highest(5.94%(mass)),followed by 2-methoxy-4-methylphenol(5.74%(mass)).This study,the modification of attapulgite was carried out to reduce the acidity while enhancing the catalytic activity for depolymerization,and the selection of hydrogen donor was investigated.A feasible pathway for lignin depolymerization research was opened.
基金supported by the National Natural Science Foundation of China(21473155,21273198,21073159)the Natural Science Foundation of Zhejiang Province(LZ12B03001)~~
文摘A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported Pd catalyst（Pd/A-45） was highly active and selective under mild conditions（40-100 ℃,0.2-1 MPa）,giving a selectivity of cyclohexanone higher than 89%even at complete conversion of phenol.Experiments with different Pd loadings（or different particle sizes） confirmed that the formation of cyclohexanone was a structure sensitive reaction,and Pd particles of12-14 nm on Amberlyst-45 gave better selectivity and stability.
基金supported by the National High Technology Research and Development Program (863 Program,2015AA034603)the National Natural Science Foundation of China (21377008,201077007,20973017)+1 种基金Foundation on the Creative Research Team Construction Promotion Project of Beijing Municipal InstitutionsScientific Research Base Construction-Science and Technology Creation Platform National Materials Research Base Construction~~
文摘Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and sup‐ported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excel‐lent catalytic performance was due to their high surface areas, high concentration of adsorbed oxy‐gen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and pro‐posed future work for the removal of VOCs.
基金supported by the National Natural Science Foundation of China (21273044, 21473035, 91545108)the Research Fund for the Doctoral Program of Higher Education (2012007000011)+2 种基金SINOPEC (X514005)Science & Technology Commission of Shanghai Municipality (08DZ2270500)the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-15C02)~~
文摘The reductive transformation of furfural （FAL） into furfuryl alcohol （FOL） is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst （Au/TiO2‐R） that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel‐derived H2, our pro‐cess has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.
基金The Executive Programme for Cooperation between Italy and India (Prot.No.MAE01054762017)。
文摘Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.
基金National Natural Science Foundation of China (No. 20272062)
文摘Polyethylene (PE) grafting 4-vinylpyridine copolymers has been produced as powders of different rushes by theirradiation method. After treatment with methylaluminoxane (MAO), the copolymers were used as supports for Cp_2ZrCl_2catalyst Results of X-ray photoelectron spectroscopy, Fourier transforms infrared spectroscopy, ultraviolet spectroscopy andscanning electron microscope measurements show that the catalytic sites have been linked through MAO on the PE-graft-4-vinylpyridine (PEVP). The percentages of grafting 4-vinylpyridine and supported Cp_2ZrCl_2 depend on the size ofpolyethylene powder. The smaller the polyethylene powder, the more percent of 4-vinylpyridine groups and Cp_2ZrCl_2 existon the polyethylene chains, and the PEVP-supported catalyst has a relatively high activity for ethylene polymerization.
文摘Two types of small iron clusters supported on γ-Al2O3-RT（dehydroxylated at room temperature） and γ-Al2O3-800 （dehydroxylated at 800 ℃） were prepared by solvated metal atom impregnation （SMAI） techniques. The iron atom precursor complex, bis（toluene）iron（0） formed in the metal atom reactor, was impregnated into γ-Al2O3 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by TEM, Mǒssbauer, and chemisorption measurements, and the results show that higher concentration of surface hydroxyl groups of γ-Al2O3-RT favors the formation of more positively charged supported iron cluster Fen/γ-Al2O3-RT, and the lower concentration of surface hydroxyl groups of γ-Al2O3-800 favors the formation of basically neutral supported iron cluster Fen/γ-Al2O3-800. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the rapid decomposition of precursor complex, bis（toluene）iron（0）, and favors the formation of relatively large iron cluster. Consequently, these two types of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fen/γ-Al2O3-RT in F-T reaction is similar to that of the unreduced γ-Fe2O3 and that of Fen/γ-Al2O3-800 is similar to that of the reduced α-Fe2O3.
文摘A supported iron catalyst, which was prepared by anchoring FeCl2/FeCl3 on the cross-linking macroporous polyacrylate ion exchange resin, was evaluated via the controlled radical polymerization. When a small amount of CuCl2/ Me6TREN was added, the controllability of the polymerization over the iron-mediated catalyst was significantly improved（Mw/Mn = 1.23-1.73 ）, affording a polymer with a low residual metal via a simple catalyst separation procedure. After suitable regeneration, the supported iron catalyst could also he recycled. UV-Vis analysis showed that the additional copper catalyst could facilitate the radical deactivation process.
基金supported by the National Natural Science Foundation of China(Nos.52000093,51968034,41807373 and21667015)National Key R&D Program of China(No.2018YFC0213400)+1 种基金China Postdoctoral Science Foundation(Nos.2020T130271,2019M663911XB)Open Fund of National Engineering Laboratory for Mobile Source Emission Control Technology(No.NELMS2019B03)。
文摘The simultaneous removal of SO_(2),NO_(x)and Hg^(0)from industrial exhaust flue gas has drawn worldwide attention in recent years.A particularly attractive technique is selective catalytic reduction,which effectively removes SO_(2),NO_(x)and Hg^(0)at low temperatures.This paper first reviews the simultaneous removal of SO_(2),NO_(x)and Hg^(0)by unsupported and supported catalysts.It then describes and compares the research progress of various carriers,eg.,carbon-based materials,metal oxides,silica,molecular sieves,metal-organic frameworks,and pillared interlayered clays,in the simultaneous removal of SO_(2),NO_(x)and Hg^(0).The effects of flue-gas components(such as O_(2),NH3,HCl,H2 O,SO_(2),NO and Hg^(0))on the removal of SO_(2),NOx,and Hg^(0)are discussed comprehensively and systematically.After summarizing the pollutantremoval mechanism,the review discusses future developments in the simultaneous removal of SO_(2),NOx and Hg^(0)by catalysts.
基金This work is supported by the National Natural Science Foundation of China （No.51372248, No.51432009 and No.51502297）, Instrument Developing Project of the Chinese Academy of Sciences （No.yz201421）, the CAS/SAFEA International Partnership Program for Creative Research Teams of Chinese Academy of Sciences, China.
文摘A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.
文摘An ultrasound-assisted heterogeneous catalytic oxidation process was applied to eliminate sulfur from commercial diesel fuel oil.The studied variables were catalyst concentration,type of catalyst(homogeneous or heterogeneous),oxidizing agent concentration,and the application of ultrasound energy.Supported catalysts were prepared by impregnation of coal fly ash with an iron(Ⅱ)sulfate aqueous solution using ultrasound energy.After drying,the catalyst was calcined at 500℃for 4 h.The oxidizing agent was hydrogen peroxide.Ultrasound energy was applied with a frequency of 47 kHz and an intensity of 147 W.Ethanol was employed for extracting the oxidized compounds from the hydrocarbon mixture.Coal fly ash and ethanol were used with the purpose of applying low-cost raw materials in chemical processes.It was found that under the studied conditions,increasing oxidizing agent concentration and the application of ultrasound energy can enhance the sulfur removal from commercial diesel fuel oil.Catalyst concentration did not play a significant role in the process.Similar results were obtained using homogeneous or heterogeneous catalyst,which is important since the heterogeneous catalyst could be recovered,reactivated,and used in many cycles.
基金This work was also supported by the Core Research for Engineering Innovation KGCX2-203 of the Chinese Academy of Sciences, National Natural Science Foundation of China (No. 20272062) and the "One Hundred Talents" Fund foWen-Hua Sun.
文摘8-Aminoquinoline nickel dichloride and bis(cyclopentadienyl)zirconium dichloride (Cp_2ZrCl_2) were supportedsimultaneously on silica to produce branched polyethylene successfully by combined polymerization. The supportedpolymerization results showed that the molecular weight of polyethylene increased while the molecular weight distributionbecame wider and the molecular chains of oligomers remaning in the final solution became shorter as compared to theoligomers obtained in polymerization processes with pure 8-aminoquinoline nickel dichloride catalysis, as well as theCp_2ZrCl_2 and nickel combination system. With decreasing amount of Ni catalyst in the supported catalyst, the molecular chains of oligomers in the resulting solution became shorter, while α-olefin selectivity increased.
基金Natural Science Foundation of Tianjin(No.043801311)
文摘A new supported amorphous catalyst CoP/TiO2 was prepared by chemical reduction and characterized by ICP, XRD, TEM, BET and DSC. Its application in decomposing PH3 to high purity phosphor and its catalytic activity were studied. The decomposition rate is over 95% at 450 ℃. For comparison, unsupported CoP amorphous catalyst was prepared by the same method. The result suggests that CoP/TiO2 exhibits higher thermal stability and catalytic activity than CoP, which is attributed to the high dispersion of CoP alloy particles on the support-TiO2.
