The acidities of different Si O2/Al2O3 ratio ZSM-5 zeolites, CBV3024 E, CBV5524 G and CBV8014 were investigated with temperature-programmed desorption of ammonia and diffuse reflectance infrared Fourier transform spec...The acidities of different Si O2/Al2O3 ratio ZSM-5 zeolites, CBV3024 E, CBV5524 G and CBV8014 were investigated with temperature-programmed desorption of ammonia and diffuse reflectance infrared Fourier transform spectroscopy, and their catalytic performances were evaluated to screen the optimal CBV8014 catalyst for ethylene oligomerization. The mesoporosity development in CBV8014 zeolite was conducted by desilication in alkaline medium. The porous characteristics, structural properties and acidic properties of parent and alkali-treated CBV8014 zeolites were studied, and their catalytic performances were evaluated, indicating that CBV8014 treated by 0.2 mol/L NaO H solution has an appropriate mesoporosity development, well preservation of catalyst acidity and crystallinity, good catalytic activity and stability, and high liquid fuel yield for ethylene oligomerization. The effect of reaction pressure on ethylene oligomerization over 0.2HZ catalyst was also investigated, and JP-8 likely hydrocarbon jet fuel was obtained by using 0.2HZ catalyst at 0.344 75 MPa with a high catalyst stability and high liquid yield.展开更多
Mesoporous carbons have been widely utilized as the sulfur host for lithium-sulfur （Li-S） batteries. The ability to engineer the porosity, wall thickness, and graphitization degree of the carbon host is essential fo...Mesoporous carbons have been widely utilized as the sulfur host for lithium-sulfur （Li-S） batteries. The ability to engineer the porosity, wall thickness, and graphitization degree of the carbon host is essential for addressing issues that hamper commercialization of Li-S batteries, such as fast capacity decay and poor high-rate performance. In this work, highly ordered, ultrathin mesoporous graphitic-carbon frameworks （MGFs） having unique cage-like mesoporosity, derived from self-assembled Fe304 nanoparticle superlattices, are demonstrated to be an excellent host for encapsulating sulfur. The resulting S@MGFs exhibit high specific capacity （1,446 mAh.g-1 at 0.15 C）, good rate capability （430 mAh.g-1 at 6 C）, and exceptional cycling stability （-0.049% capacity decay per cycle at 1 C） when used as Li-S cathodes. The superior electrochemical performance of the S@MGFs is attributed to the many unique and advantageous structural features of MGFs. In addition to the interconnected, ultrathin graphitic-carbon framework that ensures rapid electron and lithium-ion transport, the microporous openings between adjacent mesopores efficiently suppress the diffusion of polysulfides, leading to improved capacity retention even at high current densities.展开更多
TiO_(2)-B/anatase nanotubes doped by vanadium have been synthesized through a facile one-step hydrothermal reaction.The material shows a mesoporous structure with a specific surface area of 179.1 m^(2)g^(-1).XPS data ...TiO_(2)-B/anatase nanotubes doped by vanadium have been synthesized through a facile one-step hydrothermal reaction.The material shows a mesoporous structure with a specific surface area of 179.1 m^(2)g^(-1).XPS data presume the presence of V^(3+),V^(4+),V^(5+),and Ti^(3+) in doped TiO2-B/anatase.As found by XRD and EIS investigations,the vanadium expands bronze titania crystal structure and enhances the conductivity of material by three orders of magnitude.When tested for lithium storage,the V-modified titania nanotubes show a specific capacity of 133 mA h g^(-1) after 100 charge/discharge cycles at the current density of 3000 mA g^(-1) with a Coulombic efficiency of around 98.9%,resulting in its good cycleability.The material still possesses a reversible capacity of 114 mA h g^(-1) at a very high current load of 6000 mA g^(-1),demonstrating superior rate characteristics for secondary lithium batteries.Furthermore,V-doped Ti O2-B/anatase mesoporous nanotubes show promise performance as anode material for sodium-ion batteries,delivering about 119 mA h g^(-1) and 101 m A h g^(-1) at the current loads of 10 and 1500 m A g^(-1),respectively.展开更多
Developing carbon-based supercapacitors with high rate capability is of great importance to meet the emerging demands for devices that requires high energy density as well as high power density.However,it is hard to f...Developing carbon-based supercapacitors with high rate capability is of great importance to meet the emerging demands for devices that requires high energy density as well as high power density.However,it is hard to fabricate a nanocarbon with high electro-active surface area meanwhile maintaining superior conductivity to ensure the high rate capability since excellent conductivity is usually realized by high temperature graphitization,which would lead to the structural collapse and sintering resulting in low surface area.Herein,we reported a highly porous graphitic carbon nanosheet with an unprecedented rate capability of 98%of its initial capacitance from 0.5 to 50 A/g for ultrahigh-rate supercapacitive energy storage.These hierarchical mesoporous carbon nanosheets(HMCN)were fabricated by a template induced catalytic graphitization approach,in which sheet-like Mg(OH)_(2) was employed as catalytic template in situ catalytically polymerizing of catechol and formaldehyde and catalytically graphitizing of the formed carbon skeleton.Upon the co-effect of template(avoiding the sintering)and the deoxygenation(creating the pores)during the high temperature graphitization process,the obtained HMCN material possesses nanosheet morphology with highly porous graphitic microstructure rich in mesoporosity,large in surface area(2316 m^(2)/g),large in pore volume(3.58 cm^(3)/g)and excellent in conductivity(109.8 S/cm).In 1.0 M TEABF_(4)/AN,HMCN exhibits superior supercapacitive performance including large energy density of 52.2 Wh/kg at high power density of 118 k W/kg,long-cycling stability and excellent rate capability,making HMCN a promising electrode material for supercapacitor devices.展开更多
Hierarchical phases of the biomaterials can be used as template to transfer their intricate organization into biomimic inorganic solids. Herein, hierarchical mesoporous silica films with aligned pores have been templa...Hierarchical phases of the biomaterials can be used as template to transfer their intricate organization into biomimic inorganic solids. Herein, hierarchical mesoporous silica films with aligned pores have been templated by nanofibrillar alginic acid. An aqueous suspension of the alginic acid nanofibers was prepared by treating the brown seaweeds with sodium carbonate solution and subsequent precipitation in dilute hydrochloric acid. The alginic acid nanofibers of the organize into a hierarchical aligned phase in an acetic acid-sodium acetate buffer that was used to template silica-alginic acid composite films by evaporation induced self-assembly of alkoxysilane with nanofibrillar alginic acid. Calcination of the alginic acid template afforded hierarchical mesoporous silica glasses. Carbonization of the silica-alginic acid composites and subsequent etching the silica recovered mesoporous carbon supercapacitors.展开更多
Six carbon powders with varied surface areas and porosities were used to store and release acetaminophen (ACT). A 10 mg/mL solution of acetaminophen in phosphate buffer solution (pH = 7.0) at 25℃ with exposure to car...Six carbon powders with varied surface areas and porosities were used to store and release acetaminophen (ACT). A 10 mg/mL solution of acetaminophen in phosphate buffer solution (pH = 7.0) at 25℃ with exposure to carbon powder for 72 hours was used to drive the maximum loading of acetaminophen into the powders. Carboxen 1012 (BET surface area of1500 m2/g) powder exhibited the greatest maximum adsorption of ACT (up to 62% by mass). The maximum ACT adsorption was correlated with surface area and porosity. The most effective carbon powders for binding ACT were ones containing high mesopore volumes. Loaded carbon powder was separated from the ACT solution and then phosphate buffer solution (pH = 7.0) was combined with the loaded carbon powder and ACT absorbance readings at 243 nm were taken over time. The various carbon powders were able to release a portion of the ACT that they originally adsorbed. The Carboxen 1012 powder displayed the greatest ACT release with a rapid initial release followed by a steady but slightly declining release over a time period of 2 to 11 weeks. The results were supportive of mesoporous carbons such as Carboxen 1012 being suitable for drug loading and release.展开更多
Precious metal-free electrocatalysts often require significantly more loadings to achieve similar performance as Pt does in fuel cells and metal air batteries.The high loadings cause substantial mass transportation re...Precious metal-free electrocatalysts often require significantly more loadings to achieve similar performance as Pt does in fuel cells and metal air batteries.The high loadings cause substantial mass transportation resistance.To address this challenge,we synthesized ordered mesoporous carbon nanofiber electrocatalyst that enables unimpeded mass transfer at mesoscale.The synthesis was based on electrospinning of supramolecular micelles,which were stretched under hydrodynamic forces and self-assembled as in oriented and ordered form.Ordered mesoporous carbon nanofibers(OMCNFs)were obtained after removing the micelle template.The aligned mesopores over electrode scale strongly accelerate diffusion kinetics.The OH−ion diffusion coefficient of OMCNF is 26 times larger than that of the nanofiber with non-ordered pores(NMCNF)and 206 times larger than that of Pt/C.As a result,the electrocatalytic performance of OMCNF was maintained at increased catalyst loadings,while performance deterioration was observed in NMCNF and Pt/C.The assembled zinc-air batteries using aqueous electrolyte and solid-state electrolyte delivered high power density and nice cycling performance.展开更多
A facile synthesis of hierarchical ZSM-5 with the three-dimensionally ordered mesoporosity(3DOm ZSM-5)was achieved by solid conversion(SC)of SiO_(2)colloidal crystals to high-crystalline ZSM-5.The products of 3DZ5_S/C...A facile synthesis of hierarchical ZSM-5 with the three-dimensionally ordered mesoporosity(3DOm ZSM-5)was achieved by solid conversion(SC)of SiO_(2)colloidal crystals to high-crystalline ZSM-5.The products of 3DZ5_S/C and 3DZ5_S,which were severally transformed from the carbon-padded SiO_(2)colloidal crystals and the initial SiO_(2)colloidal crystals,exhibited not only a similar ordered structure and acidity but also higher crystallinity and more balanced meso-/micropore combination in comparison with 3DZ5_C obtained by the conventional confined space crystallization approach.All three synthesized 3DZ5 catalysts showed improved methanol-to-propylene performance than the commercially microporous ZSM-5(CZ5),embodied in five times longer lifetime,higher propylene selectivity and S_(propylene)/S_(ethylene) ratio(P/E),and superior coke toleration with lower formation rate of coke(R_(coke)).Moreover,the 3DZ5_S catalyst in situ converted from SiO_(2)colloidal crystals presented the highest selectivities of propylene(42.51%)and light olefins(74.6%)among all three 3DZ5 catalysts.The high efficiency in synthesis and in situ utilization of SiO_(2)colloidal crystals demonstrate the proposed SC strategy to be more efficiently and eco-friendly for the high-yield production of not only 3DOm ZSM-5 but also other types of hierarchical zeolites.展开更多
Ultrafine mesoporous tungsten carbide （WC） was prepared from as-synthesized mesoporous WC using high-energy ball milling treatment. X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and nitrogen adsor...Ultrafine mesoporous tungsten carbide （WC） was prepared from as-synthesized mesoporous WC using high-energy ball milling treatment. X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and nitrogen adsorption-desorption techniques were used to characterize the samples. Brunauer-Emmett-Teller （BET） surface areas of WC samples increased with the increasing ball milling time and kept constant at 10-11 mZog 1 for over 9 h. The electrocatalytic properties of methanol electro-oxidation at WC powder microelectrodes were investigated by cyclic voltammetry, chronoamperometry, and quasi-steady-state polarization techniques. The results reveal that ball-milled WC exhibits higher activity for methanol electro-oxidation than as-synthesized mesoporous WC. The suitability of ball-milled WC for methanol electro-oxidation is better than platinum （Pt） micro-disk, although the current peak is not as high as the Pt micro-disk. Moreover, increasing the methanol concentration and reaction temperature promotes methanol electro-oxidation on ultrafine mesoporous WC.展开更多
Silicoaluminophosphates （SAPOs） with different pore structures were synthesized through the implementation of polyethylene glycol （PEG） as a mesopores impregnation agent. Using PEGs with different molecular weigh...Silicoaluminophosphates （SAPOs） with different pore structures were synthesized through the implementation of polyethylene glycol （PEG） as a mesopores impregnation agent. Using PEGs with different molecular weights （MWs） and concentrations in the synthesis precursor, several samples were synthesized and characterized. Applying a PEG capping agent to the precursors led to the formation of tuned mesopores within the microporous matrix of the SAPO. The effects of the PEG molecular weight and PEG/Al molar ratio were investigated to maximize the efficiency of the catalyst in the methanol-to-olefin （MTO） process. Using PEG with a MW of 6000 resulted in the formation of both Zeolite Rho and chabazite structural frameworks （i.e., DNL-6 and SAPO-34）. Pure SAPO-34 samples were successfully prepared using PEG with a MW of 4000. Our results showed that the PEG concentrations affect the porosity and acidity of the synthesized materials. Furthermore, the SAPO-34 sample synthesized with PEG （MW of 4000） and a PEG/Al molar ratio of 0.0125 showed a superior catalytic stability in the MTO reaction owing to the tuned bi-modal porosity and tailored acidity pattern. Finally, through reactivation experiments, it was found that the catalyst is stable even after several regeneration cycles.展开更多
High catalytic activity and substrate specificity make enzymes a rich source of inspiration for catalyst development.Co-opting the advantages of natural materials while tuning them to a modified form and purpose,howev...High catalytic activity and substrate specificity make enzymes a rich source of inspiration for catalyst development.Co-opting the advantages of natural materials while tuning them to a modified form and purpose,however,is not a straightforward synthetic task.Polymerization of L-3,4-dihydroxyphenylalanine(L-DOPA)results in amorphous polymer nanoparticles that are similar in many ways to natural eumelanin.Herein,the authors introduce mesoporosity and iron ion chelation to synthesize a variant of the L-DOPA polymer with high peroxidase-like activity.Our results indicate catalytic reaction with peroxide under mildly acidic conditions(pH 5.4 and 6)with a greater maximum reaction velocity(Vmax)than horseradish peroxidase(HRP)at optimal pH 3.5–4.5.Comparison between Fe(Ⅲ)and Fe(Ⅱ)loading indicates that either can be used as a starting point to trigger reactivity,though Fe(Ⅱ)loading leads to materials with twice the Vmax of the Fe(Ⅲ)-loaded sample.The lack of catalyst degradation despite the redox changes and presence of radical species is consistent with the robust nature and redox versatility of polydopamine-based materials and demonstrates strong potential as a versatile redox-catalysis platform.展开更多
文摘The acidities of different Si O2/Al2O3 ratio ZSM-5 zeolites, CBV3024 E, CBV5524 G and CBV8014 were investigated with temperature-programmed desorption of ammonia and diffuse reflectance infrared Fourier transform spectroscopy, and their catalytic performances were evaluated to screen the optimal CBV8014 catalyst for ethylene oligomerization. The mesoporosity development in CBV8014 zeolite was conducted by desilication in alkaline medium. The porous characteristics, structural properties and acidic properties of parent and alkali-treated CBV8014 zeolites were studied, and their catalytic performances were evaluated, indicating that CBV8014 treated by 0.2 mol/L NaO H solution has an appropriate mesoporosity development, well preservation of catalyst acidity and crystallinity, good catalytic activity and stability, and high liquid fuel yield for ethylene oligomerization. The effect of reaction pressure on ethylene oligomerization over 0.2HZ catalyst was also investigated, and JP-8 likely hydrocarbon jet fuel was obtained by using 0.2HZ catalyst at 0.344 75 MPa with a high catalyst stability and high liquid yield.
基金A. G. D. acknowledges the financial support from the National Basic Research Program of China （No. 2014CB845602）, Natural National Science Foundation of China （No. 21373052）, and Shanghai International Science and Technology Cooperation Project （No. 15520720100）. D. Y. is grateful for financial support from Natural National Science Foundation of China （Nos. 51373035, 51373040, 51573030, and 51573028）, and International Science and Technology Cooperation Program of China （No. 2014DFE40130）.
文摘Mesoporous carbons have been widely utilized as the sulfur host for lithium-sulfur （Li-S） batteries. The ability to engineer the porosity, wall thickness, and graphitization degree of the carbon host is essential for addressing issues that hamper commercialization of Li-S batteries, such as fast capacity decay and poor high-rate performance. In this work, highly ordered, ultrathin mesoporous graphitic-carbon frameworks （MGFs） having unique cage-like mesoporosity, derived from self-assembled Fe304 nanoparticle superlattices, are demonstrated to be an excellent host for encapsulating sulfur. The resulting S@MGFs exhibit high specific capacity （1,446 mAh.g-1 at 0.15 C）, good rate capability （430 mAh.g-1 at 6 C）, and exceptional cycling stability （-0.049% capacity decay per cycle at 1 C） when used as Li-S cathodes. The superior electrochemical performance of the S@MGFs is attributed to the many unique and advantageous structural features of MGFs. In addition to the interconnected, ultrathin graphitic-carbon framework that ensures rapid electron and lithium-ion transport, the microporous openings between adjacent mesopores efficiently suppress the diffusion of polysulfides, leading to improved capacity retention even at high current densities.
文摘TiO_(2)-B/anatase nanotubes doped by vanadium have been synthesized through a facile one-step hydrothermal reaction.The material shows a mesoporous structure with a specific surface area of 179.1 m^(2)g^(-1).XPS data presume the presence of V^(3+),V^(4+),V^(5+),and Ti^(3+) in doped TiO2-B/anatase.As found by XRD and EIS investigations,the vanadium expands bronze titania crystal structure and enhances the conductivity of material by three orders of magnitude.When tested for lithium storage,the V-modified titania nanotubes show a specific capacity of 133 mA h g^(-1) after 100 charge/discharge cycles at the current density of 3000 mA g^(-1) with a Coulombic efficiency of around 98.9%,resulting in its good cycleability.The material still possesses a reversible capacity of 114 mA h g^(-1) at a very high current load of 6000 mA g^(-1),demonstrating superior rate characteristics for secondary lithium batteries.Furthermore,V-doped Ti O2-B/anatase mesoporous nanotubes show promise performance as anode material for sodium-ion batteries,delivering about 119 mA h g^(-1) and 101 m A h g^(-1) at the current loads of 10 and 1500 m A g^(-1),respectively.
基金financially supported by the National Science Foundation of China(22172073 and 21773112)the Fundamental Research Funds for the Central Universitiesthe Science and Technology Innovation Team Plan for the youths in universities of Hubei province(T2020021)。
文摘Developing carbon-based supercapacitors with high rate capability is of great importance to meet the emerging demands for devices that requires high energy density as well as high power density.However,it is hard to fabricate a nanocarbon with high electro-active surface area meanwhile maintaining superior conductivity to ensure the high rate capability since excellent conductivity is usually realized by high temperature graphitization,which would lead to the structural collapse and sintering resulting in low surface area.Herein,we reported a highly porous graphitic carbon nanosheet with an unprecedented rate capability of 98%of its initial capacitance from 0.5 to 50 A/g for ultrahigh-rate supercapacitive energy storage.These hierarchical mesoporous carbon nanosheets(HMCN)were fabricated by a template induced catalytic graphitization approach,in which sheet-like Mg(OH)_(2) was employed as catalytic template in situ catalytically polymerizing of catechol and formaldehyde and catalytically graphitizing of the formed carbon skeleton.Upon the co-effect of template(avoiding the sintering)and the deoxygenation(creating the pores)during the high temperature graphitization process,the obtained HMCN material possesses nanosheet morphology with highly porous graphitic microstructure rich in mesoporosity,large in surface area(2316 m^(2)/g),large in pore volume(3.58 cm^(3)/g)and excellent in conductivity(109.8 S/cm).In 1.0 M TEABF_(4)/AN,HMCN exhibits superior supercapacitive performance including large energy density of 52.2 Wh/kg at high power density of 118 k W/kg,long-cycling stability and excellent rate capability,making HMCN a promising electrode material for supercapacitor devices.
文摘Hierarchical phases of the biomaterials can be used as template to transfer their intricate organization into biomimic inorganic solids. Herein, hierarchical mesoporous silica films with aligned pores have been templated by nanofibrillar alginic acid. An aqueous suspension of the alginic acid nanofibers was prepared by treating the brown seaweeds with sodium carbonate solution and subsequent precipitation in dilute hydrochloric acid. The alginic acid nanofibers of the organize into a hierarchical aligned phase in an acetic acid-sodium acetate buffer that was used to template silica-alginic acid composite films by evaporation induced self-assembly of alkoxysilane with nanofibrillar alginic acid. Calcination of the alginic acid template afforded hierarchical mesoporous silica glasses. Carbonization of the silica-alginic acid composites and subsequent etching the silica recovered mesoporous carbon supercapacitors.
文摘Six carbon powders with varied surface areas and porosities were used to store and release acetaminophen (ACT). A 10 mg/mL solution of acetaminophen in phosphate buffer solution (pH = 7.0) at 25℃ with exposure to carbon powder for 72 hours was used to drive the maximum loading of acetaminophen into the powders. Carboxen 1012 (BET surface area of1500 m2/g) powder exhibited the greatest maximum adsorption of ACT (up to 62% by mass). The maximum ACT adsorption was correlated with surface area and porosity. The most effective carbon powders for binding ACT were ones containing high mesopore volumes. Loaded carbon powder was separated from the ACT solution and then phosphate buffer solution (pH = 7.0) was combined with the loaded carbon powder and ACT absorbance readings at 243 nm were taken over time. The various carbon powders were able to release a portion of the ACT that they originally adsorbed. The Carboxen 1012 powder displayed the greatest ACT release with a rapid initial release followed by a steady but slightly declining release over a time period of 2 to 11 weeks. The results were supportive of mesoporous carbons such as Carboxen 1012 being suitable for drug loading and release.
基金supported by National Natural Science Foundation of China(Grant 52225204,52173233,and 52402231)the Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-03-E00109)+3 种基金the Program for Professor of Special Appointment(Eastern Scholar)at the Shanghai Institutions of Higher Learning,the Natural Science Foundation of Shanghai(23ZR1479200)“Shuguang Program”supported by the Shanghai Education Development Foundation and Shanghai Municipal Education Commission(20SG33)the Fundamental Research Funds for the Central Universities(2232024Y-01)DHU Distinguished Young Professor Program(LZA2022001).
文摘Precious metal-free electrocatalysts often require significantly more loadings to achieve similar performance as Pt does in fuel cells and metal air batteries.The high loadings cause substantial mass transportation resistance.To address this challenge,we synthesized ordered mesoporous carbon nanofiber electrocatalyst that enables unimpeded mass transfer at mesoscale.The synthesis was based on electrospinning of supramolecular micelles,which were stretched under hydrodynamic forces and self-assembled as in oriented and ordered form.Ordered mesoporous carbon nanofibers(OMCNFs)were obtained after removing the micelle template.The aligned mesopores over electrode scale strongly accelerate diffusion kinetics.The OH−ion diffusion coefficient of OMCNF is 26 times larger than that of the nanofiber with non-ordered pores(NMCNF)and 206 times larger than that of Pt/C.As a result,the electrocatalytic performance of OMCNF was maintained at increased catalyst loadings,while performance deterioration was observed in NMCNF and Pt/C.The assembled zinc-air batteries using aqueous electrolyte and solid-state electrolyte delivered high power density and nice cycling performance.
基金supported by the National Natural Science Foundation of China(Grant No.21978238)the Natural Science Foundation of Shaanxi Provincial Department of Education(Grant No.21JY041)the Key R&D Program of Shaanxi Province(Grant No.2024GX-YBXM-426)。
文摘A facile synthesis of hierarchical ZSM-5 with the three-dimensionally ordered mesoporosity(3DOm ZSM-5)was achieved by solid conversion(SC)of SiO_(2)colloidal crystals to high-crystalline ZSM-5.The products of 3DZ5_S/C and 3DZ5_S,which were severally transformed from the carbon-padded SiO_(2)colloidal crystals and the initial SiO_(2)colloidal crystals,exhibited not only a similar ordered structure and acidity but also higher crystallinity and more balanced meso-/micropore combination in comparison with 3DZ5_C obtained by the conventional confined space crystallization approach.All three synthesized 3DZ5 catalysts showed improved methanol-to-propylene performance than the commercially microporous ZSM-5(CZ5),embodied in five times longer lifetime,higher propylene selectivity and S_(propylene)/S_(ethylene) ratio(P/E),and superior coke toleration with lower formation rate of coke(R_(coke)).Moreover,the 3DZ5_S catalyst in situ converted from SiO_(2)colloidal crystals presented the highest selectivities of propylene(42.51%)and light olefins(74.6%)among all three 3DZ5 catalysts.The high efficiency in synthesis and in situ utilization of SiO_(2)colloidal crystals demonstrate the proposed SC strategy to be more efficiently and eco-friendly for the high-yield production of not only 3DOm ZSM-5 but also other types of hierarchical zeolites.
基金Project supported by Science and Technology Major Project in International Cooperation of Zhejiang Province （No. 2008C14040）, Key Project of Natural Science Foundation of Zhejiang Province （No. Z4100790） and International Science ＆ Technology Cooperation Program of China （No. 2010DFB63680）.
文摘Ultrafine mesoporous tungsten carbide （WC） was prepared from as-synthesized mesoporous WC using high-energy ball milling treatment. X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and nitrogen adsorption-desorption techniques were used to characterize the samples. Brunauer-Emmett-Teller （BET） surface areas of WC samples increased with the increasing ball milling time and kept constant at 10-11 mZog 1 for over 9 h. The electrocatalytic properties of methanol electro-oxidation at WC powder microelectrodes were investigated by cyclic voltammetry, chronoamperometry, and quasi-steady-state polarization techniques. The results reveal that ball-milled WC exhibits higher activity for methanol electro-oxidation than as-synthesized mesoporous WC. The suitability of ball-milled WC for methanol electro-oxidation is better than platinum （Pt） micro-disk, although the current peak is not as high as the Pt micro-disk. Moreover, increasing the methanol concentration and reaction temperature promotes methanol electro-oxidation on ultrafine mesoporous WC.
文摘Silicoaluminophosphates （SAPOs） with different pore structures were synthesized through the implementation of polyethylene glycol （PEG） as a mesopores impregnation agent. Using PEGs with different molecular weights （MWs） and concentrations in the synthesis precursor, several samples were synthesized and characterized. Applying a PEG capping agent to the precursors led to the formation of tuned mesopores within the microporous matrix of the SAPO. The effects of the PEG molecular weight and PEG/Al molar ratio were investigated to maximize the efficiency of the catalyst in the methanol-to-olefin （MTO） process. Using PEG with a MW of 6000 resulted in the formation of both Zeolite Rho and chabazite structural frameworks （i.e., DNL-6 and SAPO-34）. Pure SAPO-34 samples were successfully prepared using PEG with a MW of 4000. Our results showed that the PEG concentrations affect the porosity and acidity of the synthesized materials. Furthermore, the SAPO-34 sample synthesized with PEG （MW of 4000） and a PEG/Al molar ratio of 0.0125 showed a superior catalytic stability in the MTO reaction owing to the tuned bi-modal porosity and tailored acidity pattern. Finally, through reactivation experiments, it was found that the catalyst is stable even after several regeneration cycles.
基金support from the Air Force of Scientific Research MURI(grant no.FA9550-18-1-0142)supported by the National Science Foundation(grant no.ECCS-1542148)M.K.is supported by the Department of Defense(DoD)through the National Defense Science and Engineering Graduate(NDSEG)Fellowship Program.
文摘High catalytic activity and substrate specificity make enzymes a rich source of inspiration for catalyst development.Co-opting the advantages of natural materials while tuning them to a modified form and purpose,however,is not a straightforward synthetic task.Polymerization of L-3,4-dihydroxyphenylalanine(L-DOPA)results in amorphous polymer nanoparticles that are similar in many ways to natural eumelanin.Herein,the authors introduce mesoporosity and iron ion chelation to synthesize a variant of the L-DOPA polymer with high peroxidase-like activity.Our results indicate catalytic reaction with peroxide under mildly acidic conditions(pH 5.4 and 6)with a greater maximum reaction velocity(Vmax)than horseradish peroxidase(HRP)at optimal pH 3.5–4.5.Comparison between Fe(Ⅲ)and Fe(Ⅱ)loading indicates that either can be used as a starting point to trigger reactivity,though Fe(Ⅱ)loading leads to materials with twice the Vmax of the Fe(Ⅲ)-loaded sample.The lack of catalyst degradation despite the redox changes and presence of radical species is consistent with the robust nature and redox versatility of polydopamine-based materials and demonstrates strong potential as a versatile redox-catalysis platform.
