Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Here...Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.展开更多
NiS2 is a promising cocatalyst to improve the photocatalytic performance of g-C3N4 for the production of H2.However,the synthesis of the NiS2 cocatalyst usually requires harsh conditions,which risks destroying the mic...NiS2 is a promising cocatalyst to improve the photocatalytic performance of g-C3N4 for the production of H2.However,the synthesis of the NiS2 cocatalyst usually requires harsh conditions,which risks destroying the microstructures of the g-C3N4 photocatalysts.In this study,a facile and low-temperature(80 ℃) impregnation method was developed to prepare NiS2/g-C3N4 photocatalysts.First,the g-C3N4 powders were processed by the hydrothermal method in order to introduce oxygen-containing functional groups(such as-OH and-C0NH-) to the surface of g-C3N4.Then,the Ni^2+ ions could be adsorbed near the g-C3N4 via strong electrostatic interaction between g-C3N4 and Ni^2+ ions upon the addition of Ni(NO3)2 solution.Finally,NiS2 nanoparticles were formed on the surface of g-C3N4 upon the addition of TAA.It was found that the NiS2 nanoparticles were solidly and homogeneously grafted on the surface of g-C3N4,resulting in greatly improved photocatalytic H2production.When the amount of NiS2 was 3 wt%,the resultant NiS2/g-C3N4 photocatalyst showed the highest H2 evolution rate(116.343 μmol h^-1 g^-1),which is significantly higher than that of the pure g-C3N4(3 μmol h^-1 g^-1).Moreover,the results of a recycling test for the NiS2/g-C3N4(3 wt%)sample showed that this sample could maintain a stable and effective photocatalytic H2-evolution performance under visible-light irradiation.Based on the above results,a possible mechanism of the improved photocatalytic performance was proposed for the presented NiS2/g-C3N4 photocatalysts,in which the photogenerated electrons of g-C3N4 can be rapidly transferred to the NiS2 nanoparticles via the close and continuous contact between them;then,the photogenerated electrons rapidly react with H2O adsorbed on the surface of NiS2,which has a surficial metallic character and high catalytic activity,to produce H2.Considering the mild and facile synthesis method,the presented low-cost and highly efficient NiS2-modified g-C3N4 photocatalysts would have great potential for practical use in photocatalytic H2 production.展开更多
Volatile organic compounds(VOCs) are a major component in air pollutants and pose great risks to both human health and environmental protection. Currently, VOC abatement in industrial applications is through the use...Volatile organic compounds(VOCs) are a major component in air pollutants and pose great risks to both human health and environmental protection. Currently, VOC abatement in industrial applications is through the use of activated carbons as adsorbents and oxide-supported metals as catalysts. Notably, activated carbons easily adsorb water, which strongly hinders the adsorption of VOCs; conventional oxides typically possess relatively low surface areas and random pores, which effectively influence the catalytic conversion of VOCs. Zeolites, in contrast with activated carbons and oxides, can be designed to have very uniform and controllable micropores, in addition to tailored wettability properties, which can favor the selective adsorption of VOCs. In particular, zeolites with selective adsorptive properties when combined with catalytically active metals result in zeolite-supported metals exhibiting significantly improved performance in the catalytic combustion of VOCs compared with conventional oxide-supported catalysts. In this review, recent developments on VOC abatement by adsorptive and catalytic techniques over zeolite-based materials have been briefly summarized.展开更多
Peroxodiphosphate anion (a powerful oxidant) can be formed in a special water-based cleaning agent through an electrochemical reaction on boron-doped diamond electrodes. This electrochemical reaction was applied dur...Peroxodiphosphate anion (a powerful oxidant) can be formed in a special water-based cleaning agent through an electrochemical reaction on boron-doped diamond electrodes. This electrochemical reaction was applied during the oxidation,decomposition, and removal of organic contaminations on a silicon wafer surface, and it was used as the first step in the diamond electrochemical cleaning technique (DECT). The cleaning effects of DECT were compared with the RCA cleaning technique, including the silicon surface chemical composition that was observed with X-ray photoelectron spectroscopy and the morphology observed with atomic force microscopy. The measurement results show that the silicon surface cleaned by DECT has slightly less organic residue and lower micro-roughness,so the new technique is more effective than the RCA cleaning technique.展开更多
With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide(Vo-ZnO) with graphitic carbon nitride(g-C3N4...With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide(Vo-ZnO) with graphitic carbon nitride(g-C3N4). The resulting g-C3N4/Vo-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure Vo-ZnO and g-C3N4. The hybrid photocatalyst with a g-C3N4 content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation(λ≥ 400 nm). In addition,the g-C3N4/Vo-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation,indicating that it is stable under light irradiation. Finally,a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C3N4/Vo-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C3N4/Vo-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.展开更多
Graphitic carbon nitride(g-C3N4) with efficient photocatalytic activity was synthesized through thermal polymerization of thiourea with the addition of water(CN-W) or ethanol(CN-E) at 550 ℃for 2 h.The physicoch...Graphitic carbon nitride(g-C3N4) with efficient photocatalytic activity was synthesized through thermal polymerization of thiourea with the addition of water(CN-W) or ethanol(CN-E) at 550 ℃for 2 h.The physicochemical properties of the g-C3N4 were investigated by X-ray diffraction,transmission electron microscopy,ultraviolet-visible spectroscopy,photoluminescence spectroscopy,diffuse-reflection spectroscopy,BET and BJH surface area characterization,and elemental analysis.The carbon content was found to have self-doped into the g-C3N4 matrix during the thermal polymerization of thiourea and ethanol.CN-W and CN-E showed considerably enhanced visible-light photocatalytic activity,with NO removal percentages of 37.2%and 48.3%,respectively.Compared with pure g-C3N4,both the short and long lifetimes of the charge carriers in CN-W and CN-E were found to be prolonged.The mechanism of improved visible-light photocatalytic activity was deduced.The present work may provide a facile route to optimize the microstructure of g-C3N4photocatalysts for high-performance environmental and energy applications.展开更多
Significant progress has been made in the development of non-precious metal electrocatalysts (NPMEs) during the past decade. Correspondingly, there is an urgent demand for an appropriate measurement method to be est...Significant progress has been made in the development of non-precious metal electrocatalysts (NPMEs) during the past decade. Correspondingly, there is an urgent demand for an appropriate measurement method to be established for the reliable evaluation of NPMEs. In this study, platinum and graphite counter electrodes were used to investigate the impact of counter electrode material on the accelerated durability testing (ADT) of NPMEs in acidic medium. Platinum used as the coun- ter electrode in a traditional three-electrode electrochemical cell was found to dissolve in acidic medium and re-deposit on NPME coated on the working electrode during ADT. Such re-deposition causes the oxygen reduction reaction (ORR) performance of NPMEs to remarkably improve, and thus will seriously mislead our judgment of NPMEs if we are unaware of it. The phenomenon can be avoided using a graphite counter electrode.展开更多
The present study reports a novel strategy to fabricate nanocrystal-assembled hierarchical MOR zeolites. This is the first demonstration of hierarchical MOR without preferential growth along the c-axis, which facilita...The present study reports a novel strategy to fabricate nanocrystal-assembled hierarchical MOR zeolites. This is the first demonstration of hierarchical MOR without preferential growth along the c-axis, which facilitates mass transfer in the 12-membered ring channels of MOR zeolite for the conversions involving bulky molecules. The facile method involves the combined use of tetraethylammonium hydroxide (TEAOH) and commercial surfactants, in which TEAOH is essential for the construction of nanocrystal assemblies. The surfactant serves as a crystal growth-inhibiting agent to further inhibit nanocrystalline particle growth, resulting in enhanced mesoporosity. The hierarchical MOR assembled particles, constructed of 20-50-nm crystallites, exhibit superior catalytic properties in the alkylation of benzene with benzyl alcohol compared with the control sample, as the hierarchical MOR possesses a larger external surface area and longer c-axis dimension. More importantly, the material shows improved activity and stability in the dimethyl ether carbonylation to methyl acetate reaction, which is a novel route to produce ethanol from syngas.展开更多
Aromatization of methanol over co-impregnated La/Zn/HZSM-5 zeolite catalyst was studied.The selectivity of aromatics and BTX(benzene,toluene,and xylene)reached 64.0%and 56.6%,respectively,using La/Zn/HZSM-5 at 437...Aromatization of methanol over co-impregnated La/Zn/HZSM-5 zeolite catalyst was studied.The selectivity of aromatics and BTX(benzene,toluene,and xylene)reached 64.0%and 56.6%,respectively,using La/Zn/HZSM-5 at 437°C,0.1 MPa and methanol WHSV(weight hourly space velocity)=0.8 h-1.Catalytic results showed that the La species was a very good promoter,increased selectivity of aromatics,and prolonged the catalyst lifetime on stream.The effects of the SiO2/Al2O3 ratio in zeolite,Zn and La loading,WHSV,reaction temperature, water content in the feed and H2 pretreatment of catalysts on the catalytic performance were studied in detail. Characterizations of the catalysts by thermogravimetric analysis(TGA),NH3-TPD(temperature programmed desorption),SEM(scanning electron micrograph),N2 adsorption-desorption,XRD(X-ray diffraction)and XRF (X-ray fluorescence),were carried out to understand the structure and discuss the aromatization performance of La/Zn/HZSM-5 zeolite catalyst.展开更多
Methylation of benzene is an alternative low-cost route to produce xylenes, but selectivity to xylene remains low over conventional zeolitic catalysts. In this work, a combined dry-gel-conversion and steam-assisted- c...Methylation of benzene is an alternative low-cost route to produce xylenes, but selectivity to xylene remains low over conventional zeolitic catalysts. In this work, a combined dry-gel-conversion and steam-assisted- crystallization method is used to synthesize hierarchically porous zeolite ZSM-5 with varied Si/AI malar ratios. X-ray diffraction (XRD), N2 physisorption, NH3-temperature programmed desorption (TPD), scanning electronic microscopic (SEM) measurement and Fourier transform infrared (FT-IR) are employed to characterize the struc- ture and acidity of both hierarchically porous zeolites and their conventional counterparts. The method is found to be applicable to ZSM-5 with molar ratios of Si/A1 from 20 to 180. The ZSM-5 zeolites are used as catalysts for benzene methylation at 460 ℃ to investigate the effect of additional porosity and Si/A1 ratios. At low Si/AI ratios, the benzene conversions over conventional and hierarchical ZSM-5 are close, and selectivity to toluene is high over hierarchical ZSM-5. It is found that hierarchical porosity markedly enhances the utility of zeolite and the se- lectivity towards xylenes via improved mass transport at higher Si/Al ratios. Under an optimized hierarchical ZSM-5 catalvst, xvlene selectivity reaches 34.9% at a Si/AI ratio of 180.展开更多
ZSM-5 zeolite was rapidly synthesized in system containing ethylenediamine from the initial gel: (5?8) Na2O: 44 EDA:Al2O3:100 SiO2:4000 H2O. The crystals were lath-shaped. The effect of pretreatment and alkalinity on...ZSM-5 zeolite was rapidly synthesized in system containing ethylenediamine from the initial gel: (5?8) Na2O: 44 EDA:Al2O3:100 SiO2:4000 H2O. The crystals were lath-shaped. The effect of pretreatment and alkalinity on crystallinity was investigated. The pretreatment of silicate source can cut down the crystallization time. Tuning the system alkalinity and controlling crystallization time can ensure forming of pure crystal.展开更多
The objective of this study is to explore the optimum composition of Y and ZSM-5 zeolites to develop novel catalysts for obtaining lower gasoline olefins content and higher propylene yield. Five composite zeolite cata...The objective of this study is to explore the optimum composition of Y and ZSM-5 zeolites to develop novel catalysts for obtaining lower gasoline olefins content and higher propylene yield. Five composite zeolite catalysts with varying Y zeolite/ZSM-5 zeolite ratios have been prepared in this work to investigate the synergy between the Y zeolite and ZSM-5 zeolite on the selectivity to protolytic cracking, β-scission, oligomerization, and hydrogen transfer reactions using a FCC naphtha feedstock at 480 ℃ in a confined fluidized bed reactor. Experimental results showed that the composite catalyst with a Y zeolite/ZSM-5 zeolite ratio of 1:4 had the highest protolytic cracking and β-scission ability, which was even higher than that of pure ZSM-5 catalyst. On the other hand, the catalyst with a Y zeolite/ZSM-5 zeolite ratio of 3:2 exhibited the strongest hydrogen transfer functionality while the pure Y zeolite based catalyst had the highest oligomerization ability. For all the catalysts tested, increasing conversion enhanced the selectivity to protolytic cracking and hydrogen transfer reactions but reduced the selectivity to β-scission reaction. However, no clear trend was identified for the selectivity to oligomerization when an increased conversion was experienced.展开更多
The influence of operating parameters and type of zeolite catalysts on formation of ethylene and propylene during catalytic pyrolysis of methylcyclohexane (MCH) was studied in a laboratory fixed fluidized bed reactor....The influence of operating parameters and type of zeolite catalysts on formation of ethylene and propylene during catalytic pyrolysis of methylcyclohexane (MCH) was studied in a laboratory fixed fluidized bed reactor. The results indicated that higher reaction temperature and lower WHSV tended to produce more ethylene and propylene, among which the reaction temperature was an important factor influencing the ethylene formation. Compared with the FAU and BEA type zeolites, the MFI structured zeolite catalyst, thanks to more acid sites and smaller pore diameter of the catalyst, was conducive to the formation of ethylene and propylene. The protonation occurred on different C—C bonds and C—H bonds in the carbon chain of MCH led to different product slates, and the protonation on C—C bonds located at naphthenic ring was favorable to the formation of ethylene and propylene.展开更多
The development of highly active DFT catalysts for an electrocatalytic N_(2)reduction reaction(NRR)under mild conditions is a difficult challenge.In this study,a series of atom‐pair catalysts(APCs)for an NRR were fab...The development of highly active DFT catalysts for an electrocatalytic N_(2)reduction reaction(NRR)under mild conditions is a difficult challenge.In this study,a series of atom‐pair catalysts(APCs)for an NRR were fabricated using transition‐metal(TM)atoms(TM=Sc−Zn)doped into g‐CN monolayers.The electrochemical mechanism of APCs for an NRR has been reported by well‐defined density functional theory calculations.The calculated limiting potentials were−0.47 and−0.78 V for the Fe_(2)@CN and Co_(2)@CN catalysts,respectively.Owing to its high suppression of hydrogen evolution reactions,Co_(2)@CN is a superior electrocatalytic material for a N_(2)fixation.Stable Fe_(2)@CN may be a strongly attractive material for an NRR with a relatively low overpotential after an improvement in the selectivity.The two‐way charge transfer affirmed the donation‐acceptance procedure between N_(2)and Fe_(2)@CN or Co_(2)@CN,which play a crucial role in the activation of inert N≡N bonds.This study provides an in‐depth investigation into atom‐pair catalysts and will open up new avenues for highly efficient g‐CN‐based nanostructures for an NRR.展开更多
Reactive distillation could be utilized to produce cyclohexanol through the cyclohexene hydration. By means of highly active zeolite catalyst HZSM-5, the kinetic-thermodynamic analysis of this reactive distillation ha...Reactive distillation could be utilized to produce cyclohexanol through the cyclohexene hydration. By means of highly active zeolite catalyst HZSM-5, the kinetic-thermodynamic analysis of this reactive distillation has been carried out to get the characteristics of the reactive distillation. Results from kinetic and thermodynamic analysis indicate that the optimal pressure of this reactive distillation process should be set to higher pressure such as 0.3 or 0.4 MPa. To avoid the recovery of cyclohexanol at the top of the column, an unreactive section should be allocated at the upper column. In addition, the inert component benzene is more unfavorable to the reactive distillation process in comparison with the inert cyclohexane.展开更多
文摘Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.
基金supported by the National Natural Science Foundation of China (21277107, 21477094, 51672203, 51472192)the Program for New Century Excellent Talents in University (NCET-13-0944)the Fundamental Research Funds for the Central Universities (WUT 2015IB002)~~
文摘NiS2 is a promising cocatalyst to improve the photocatalytic performance of g-C3N4 for the production of H2.However,the synthesis of the NiS2 cocatalyst usually requires harsh conditions,which risks destroying the microstructures of the g-C3N4 photocatalysts.In this study,a facile and low-temperature(80 ℃) impregnation method was developed to prepare NiS2/g-C3N4 photocatalysts.First,the g-C3N4 powders were processed by the hydrothermal method in order to introduce oxygen-containing functional groups(such as-OH and-C0NH-) to the surface of g-C3N4.Then,the Ni^2+ ions could be adsorbed near the g-C3N4 via strong electrostatic interaction between g-C3N4 and Ni^2+ ions upon the addition of Ni(NO3)2 solution.Finally,NiS2 nanoparticles were formed on the surface of g-C3N4 upon the addition of TAA.It was found that the NiS2 nanoparticles were solidly and homogeneously grafted on the surface of g-C3N4,resulting in greatly improved photocatalytic H2production.When the amount of NiS2 was 3 wt%,the resultant NiS2/g-C3N4 photocatalyst showed the highest H2 evolution rate(116.343 μmol h^-1 g^-1),which is significantly higher than that of the pure g-C3N4(3 μmol h^-1 g^-1).Moreover,the results of a recycling test for the NiS2/g-C3N4(3 wt%)sample showed that this sample could maintain a stable and effective photocatalytic H2-evolution performance under visible-light irradiation.Based on the above results,a possible mechanism of the improved photocatalytic performance was proposed for the presented NiS2/g-C3N4 photocatalysts,in which the photogenerated electrons of g-C3N4 can be rapidly transferred to the NiS2 nanoparticles via the close and continuous contact between them;then,the photogenerated electrons rapidly react with H2O adsorbed on the surface of NiS2,which has a surficial metallic character and high catalytic activity,to produce H2.Considering the mild and facile synthesis method,the presented low-cost and highly efficient NiS2-modified g-C3N4 photocatalysts would have great potential for practical use in photocatalytic H2 production.
基金supported by the Fundamental Research Funds for the Central Universities(2015XZZX004-04)Zhejiang Provincial Natural Science Foundation(LR15B030001)~~
文摘Volatile organic compounds(VOCs) are a major component in air pollutants and pose great risks to both human health and environmental protection. Currently, VOC abatement in industrial applications is through the use of activated carbons as adsorbents and oxide-supported metals as catalysts. Notably, activated carbons easily adsorb water, which strongly hinders the adsorption of VOCs; conventional oxides typically possess relatively low surface areas and random pores, which effectively influence the catalytic conversion of VOCs. Zeolites, in contrast with activated carbons and oxides, can be designed to have very uniform and controllable micropores, in addition to tailored wettability properties, which can favor the selective adsorption of VOCs. In particular, zeolites with selective adsorptive properties when combined with catalytically active metals result in zeolite-supported metals exhibiting significantly improved performance in the catalytic combustion of VOCs compared with conventional oxide-supported catalysts. In this review, recent developments on VOC abatement by adsorptive and catalytic techniques over zeolite-based materials have been briefly summarized.
文摘Peroxodiphosphate anion (a powerful oxidant) can be formed in a special water-based cleaning agent through an electrochemical reaction on boron-doped diamond electrodes. This electrochemical reaction was applied during the oxidation,decomposition, and removal of organic contaminations on a silicon wafer surface, and it was used as the first step in the diamond electrochemical cleaning technique (DECT). The cleaning effects of DECT were compared with the RCA cleaning technique, including the silicon surface chemical composition that was observed with X-ray photoelectron spectroscopy and the morphology observed with atomic force microscopy. The measurement results show that the silicon surface cleaned by DECT has slightly less organic residue and lower micro-roughness,so the new technique is more effective than the RCA cleaning technique.
基金supported by the National Basic Research Program of China(2011CB933700)the National Natural Science Foundation of China(21271165)~~
文摘With the objectives of enhancing the stability,optical properties and visible-light photocatalytic activity of photocatalysts,we modified oxygen vacancy-rich zinc oxide(Vo-ZnO) with graphitic carbon nitride(g-C3N4). The resulting g-C3N4/Vo-ZnO hybrid photocatalysts showed higher visible-light photocatalytic activity than pure Vo-ZnO and g-C3N4. The hybrid photocatalyst with a g-C3N4 content of 1 wt% exhibited the highest photocatalytic degradation activity under visible-light irradiation(λ≥ 400 nm). In addition,the g-C3N4/Vo-ZnO photocatalyst was not deactivated after five cycles of methyl orange degradation,indicating that it is stable under light irradiation. Finally,a Z-scheme mechanism for the enhanced photocatalytic activity and stability of the g-C3N4/Vo-ZnO hybrid photocatalyst was proposed. The fast charge separation and transport within the g-C3N4/Vo-ZnO hybrid photocatalyst were attributed as the origins of its enhanced photocatalytic performance.
基金supported by the China Postdoctoral Science Foundation Funded Project (2016M592642)Project from Chongqing Education Commission (KJ1600305)+3 种基金Chongqing Basic Science and Advanced Technology Research (cstc2016jcyjAX0003)the Start-up Foundation for Doctors of Chongqing Normal University (15XLB010, 15XLB014)the National Natural Science Foundation of China (51478070, 51108487)the Innovative Research Team of Chongqing (CXTDG201602014)~~
文摘Graphitic carbon nitride(g-C3N4) with efficient photocatalytic activity was synthesized through thermal polymerization of thiourea with the addition of water(CN-W) or ethanol(CN-E) at 550 ℃for 2 h.The physicochemical properties of the g-C3N4 were investigated by X-ray diffraction,transmission electron microscopy,ultraviolet-visible spectroscopy,photoluminescence spectroscopy,diffuse-reflection spectroscopy,BET and BJH surface area characterization,and elemental analysis.The carbon content was found to have self-doped into the g-C3N4 matrix during the thermal polymerization of thiourea and ethanol.CN-W and CN-E showed considerably enhanced visible-light photocatalytic activity,with NO removal percentages of 37.2%and 48.3%,respectively.Compared with pure g-C3N4,both the short and long lifetimes of the charge carriers in CN-W and CN-E were found to be prolonged.The mechanism of improved visible-light photocatalytic activity was deduced.The present work may provide a facile route to optimize the microstructure of g-C3N4photocatalysts for high-performance environmental and energy applications.
基金supported by the Fundamental Research Funds for the Central Universities(DUT15RC(3)001,DUT15ZD225)the Program for Liao-ning Excellent Talents in University(LR2015014)+1 种基金the Liaoning BaiQianWan Talents Program(201519)Dalian Excellent Young Scientific and Technological Talents(2015R006)
文摘Significant progress has been made in the development of non-precious metal electrocatalysts (NPMEs) during the past decade. Correspondingly, there is an urgent demand for an appropriate measurement method to be established for the reliable evaluation of NPMEs. In this study, platinum and graphite counter electrodes were used to investigate the impact of counter electrode material on the accelerated durability testing (ADT) of NPMEs in acidic medium. Platinum used as the coun- ter electrode in a traditional three-electrode electrochemical cell was found to dissolve in acidic medium and re-deposit on NPME coated on the working electrode during ADT. Such re-deposition causes the oxygen reduction reaction (ORR) performance of NPMEs to remarkably improve, and thus will seriously mislead our judgment of NPMEs if we are unaware of it. The phenomenon can be avoided using a graphite counter electrode.
基金supported by the National Natural Science Foundation of China(21101150,21476228,21473182)~~
文摘The present study reports a novel strategy to fabricate nanocrystal-assembled hierarchical MOR zeolites. This is the first demonstration of hierarchical MOR without preferential growth along the c-axis, which facilitates mass transfer in the 12-membered ring channels of MOR zeolite for the conversions involving bulky molecules. The facile method involves the combined use of tetraethylammonium hydroxide (TEAOH) and commercial surfactants, in which TEAOH is essential for the construction of nanocrystal assemblies. The surfactant serves as a crystal growth-inhibiting agent to further inhibit nanocrystalline particle growth, resulting in enhanced mesoporosity. The hierarchical MOR assembled particles, constructed of 20-50-nm crystallites, exhibit superior catalytic properties in the alkylation of benzene with benzyl alcohol compared with the control sample, as the hierarchical MOR possesses a larger external surface area and longer c-axis dimension. More importantly, the material shows improved activity and stability in the dimethyl ether carbonylation to methyl acetate reaction, which is a novel route to produce ethanol from syngas.
基金Supported by the Fundamental Research Funds for the Central Universities,HUST(Z2009008)the National Natural Science Foundation of China(20973068)
文摘Aromatization of methanol over co-impregnated La/Zn/HZSM-5 zeolite catalyst was studied.The selectivity of aromatics and BTX(benzene,toluene,and xylene)reached 64.0%and 56.6%,respectively,using La/Zn/HZSM-5 at 437°C,0.1 MPa and methanol WHSV(weight hourly space velocity)=0.8 h-1.Catalytic results showed that the La species was a very good promoter,increased selectivity of aromatics,and prolonged the catalyst lifetime on stream.The effects of the SiO2/Al2O3 ratio in zeolite,Zn and La loading,WHSV,reaction temperature, water content in the feed and H2 pretreatment of catalysts on the catalytic performance were studied in detail. Characterizations of the catalysts by thermogravimetric analysis(TGA),NH3-TPD(temperature programmed desorption),SEM(scanning electron micrograph),N2 adsorption-desorption,XRD(X-ray diffraction)and XRF (X-ray fluorescence),were carried out to understand the structure and discuss the aromatization performance of La/Zn/HZSM-5 zeolite catalyst.
基金Supported by the National Natural Science Foundation of China(21006024)the CNPC Innovation Foundation(2011D-5006-0507)+2 种基金the Shanghai Pujiang Program(11PJ1402600)the New Century Excellent Talents in University(NCET-11-0644)the Fundamental Research Funds for the Central Universities(WB1213004-1)
文摘Methylation of benzene is an alternative low-cost route to produce xylenes, but selectivity to xylene remains low over conventional zeolitic catalysts. In this work, a combined dry-gel-conversion and steam-assisted- crystallization method is used to synthesize hierarchically porous zeolite ZSM-5 with varied Si/AI malar ratios. X-ray diffraction (XRD), N2 physisorption, NH3-temperature programmed desorption (TPD), scanning electronic microscopic (SEM) measurement and Fourier transform infrared (FT-IR) are employed to characterize the struc- ture and acidity of both hierarchically porous zeolites and their conventional counterparts. The method is found to be applicable to ZSM-5 with molar ratios of Si/A1 from 20 to 180. The ZSM-5 zeolites are used as catalysts for benzene methylation at 460 ℃ to investigate the effect of additional porosity and Si/A1 ratios. At low Si/AI ratios, the benzene conversions over conventional and hierarchical ZSM-5 are close, and selectivity to toluene is high over hierarchical ZSM-5. It is found that hierarchical porosity markedly enhances the utility of zeolite and the se- lectivity towards xylenes via improved mass transport at higher Si/Al ratios. Under an optimized hierarchical ZSM-5 catalvst, xvlene selectivity reaches 34.9% at a Si/AI ratio of 180.
基金Project (No. 29976036) supported by the National Natural Science Foundation of China
文摘ZSM-5 zeolite was rapidly synthesized in system containing ethylenediamine from the initial gel: (5?8) Na2O: 44 EDA:Al2O3:100 SiO2:4000 H2O. The crystals were lath-shaped. The effect of pretreatment and alkalinity on crystallinity was investigated. The pretreatment of silicate source can cut down the crystallization time. Tuning the system alkalinity and controlling crystallization time can ensure forming of pure crystal.
基金financial support from the National Key Technology R&D Program (2012BAE05B01) of China
文摘The objective of this study is to explore the optimum composition of Y and ZSM-5 zeolites to develop novel catalysts for obtaining lower gasoline olefins content and higher propylene yield. Five composite zeolite catalysts with varying Y zeolite/ZSM-5 zeolite ratios have been prepared in this work to investigate the synergy between the Y zeolite and ZSM-5 zeolite on the selectivity to protolytic cracking, β-scission, oligomerization, and hydrogen transfer reactions using a FCC naphtha feedstock at 480 ℃ in a confined fluidized bed reactor. Experimental results showed that the composite catalyst with a Y zeolite/ZSM-5 zeolite ratio of 1:4 had the highest protolytic cracking and β-scission ability, which was even higher than that of pure ZSM-5 catalyst. On the other hand, the catalyst with a Y zeolite/ZSM-5 zeolite ratio of 3:2 exhibited the strongest hydrogen transfer functionality while the pure Y zeolite based catalyst had the highest oligomerization ability. For all the catalysts tested, increasing conversion enhanced the selectivity to protolytic cracking and hydrogen transfer reactions but reduced the selectivity to β-scission reaction. However, no clear trend was identified for the selectivity to oligomerization when an increased conversion was experienced.
基金the financial support of the National Key Technology R & D Program of China (NO.2012BAE05B01)
文摘The influence of operating parameters and type of zeolite catalysts on formation of ethylene and propylene during catalytic pyrolysis of methylcyclohexane (MCH) was studied in a laboratory fixed fluidized bed reactor. The results indicated that higher reaction temperature and lower WHSV tended to produce more ethylene and propylene, among which the reaction temperature was an important factor influencing the ethylene formation. Compared with the FAU and BEA type zeolites, the MFI structured zeolite catalyst, thanks to more acid sites and smaller pore diameter of the catalyst, was conducive to the formation of ethylene and propylene. The protonation occurred on different C—C bonds and C—H bonds in the carbon chain of MCH led to different product slates, and the protonation on C—C bonds located at naphthenic ring was favorable to the formation of ethylene and propylene.
文摘The development of highly active DFT catalysts for an electrocatalytic N_(2)reduction reaction(NRR)under mild conditions is a difficult challenge.In this study,a series of atom‐pair catalysts(APCs)for an NRR were fabricated using transition‐metal(TM)atoms(TM=Sc−Zn)doped into g‐CN monolayers.The electrochemical mechanism of APCs for an NRR has been reported by well‐defined density functional theory calculations.The calculated limiting potentials were−0.47 and−0.78 V for the Fe_(2)@CN and Co_(2)@CN catalysts,respectively.Owing to its high suppression of hydrogen evolution reactions,Co_(2)@CN is a superior electrocatalytic material for a N_(2)fixation.Stable Fe_(2)@CN may be a strongly attractive material for an NRR with a relatively low overpotential after an improvement in the selectivity.The two‐way charge transfer affirmed the donation‐acceptance procedure between N_(2)and Fe_(2)@CN or Co_(2)@CN,which play a crucial role in the activation of inert N≡N bonds.This study provides an in‐depth investigation into atom‐pair catalysts and will open up new avenues for highly efficient g‐CN‐based nanostructures for an NRR.
文摘Reactive distillation could be utilized to produce cyclohexanol through the cyclohexene hydration. By means of highly active zeolite catalyst HZSM-5, the kinetic-thermodynamic analysis of this reactive distillation has been carried out to get the characteristics of the reactive distillation. Results from kinetic and thermodynamic analysis indicate that the optimal pressure of this reactive distillation process should be set to higher pressure such as 0.3 or 0.4 MPa. To avoid the recovery of cyclohexanol at the top of the column, an unreactive section should be allocated at the upper column. In addition, the inert component benzene is more unfavorable to the reactive distillation process in comparison with the inert cyclohexane.