Hierarchical nanoporous HY zeolites were synthesized from acid-activated kaolin. The hierarchical factor (HF) was maximized by varying the aging and crystallization time. This was achieved by maximizing the external...Hierarchical nanoporous HY zeolites were synthesized from acid-activated kaolin. The hierarchical factor (HF) was maximized by varying the aging and crystallization time. This was achieved by maximizing the external surface area without greatly reducing the micropore volume. The resulting products were characterized using X-ray diffraction (XRD), X-ray fluorescence, N2 adsorption, and NH3 temperature-programmed desorption. The nanoporous HY zeolite with the highest HF was obtained by aging for 48 h and a crystallization time of 24 h. The acidiW and crystallinity varied depending on the operating parameters. Incorporation of an appropriate amount of NaCI was also vital in maximizing the HF, crystallinity, and acidity. The sample crystallinities were determined by comparing their XRD peak intensities with those of a conventional Y zeolite. The results show that optimizing this process could lead to a widely acceptable commercial route for FIY zeolite production.展开更多
The hierarchical mesoporous Zn/ZSM-5 zeolite catalyst was prepared by NaOH treatment and Zn impregnation, and its application in the conversion of methanol to gasoline (MTG) was studied. N2 adsorption-desorption res...The hierarchical mesoporous Zn/ZSM-5 zeolite catalyst was prepared by NaOH treatment and Zn impregnation, and its application in the conversion of methanol to gasoline (MTG) was studied. N2 adsorption-desorption results showed that the mesopores with sizes of 2-20 nm in HZ5/0.3AT was formed by 0.3 M NaOH alkali treatment. The zeolite samples after modification were also characterized by XRF, AAS, XRD, SEM and NH3-TPD methods. Zn impregnated catalyst Zn/HZ5/0.3AT exhibited dramatic improvements in catalytic lifetime and liquid hydrocarbons yield. The selectivity of aromatic hydrocarbons was also improved after Zn impregnation. It is suggested that the mesopores of Zn/HZ5/0.3AT enhanced the synergetic effect of Zn species and acid sites and the capability to coke tolerance, which were confirmed by the results of catalytic test and TGA analysis, respectively.展开更多
Novel cost-effective fuel cells have become more attractive due to the demands for rare and expensive platinum-group metal(PGM)catalysts for mitigating the sluggish kinetics of the oxygen reduction reaction(ORR).The h...Novel cost-effective fuel cells have become more attractive due to the demands for rare and expensive platinum-group metal(PGM)catalysts for mitigating the sluggish kinetics of the oxygen reduction reaction(ORR).The high-cost PGM catalyst in fuel cells can be replaced by earth-abundant transition-metalbased catalysts,that is,an Fe-N-C catalyst,which is considered one of the most promising alternatives.However,the performance of the Fe-N-C catalyst is hindered by the low catalytic activity and poor stability,which is caused by insufficient active sites and the lack of optimization of the triple-phase interface for mass transportation.Herein,a novel Fe–N–C catalyst consisting of mono-dispersed hierarchically mesoporous carbon sphere cores and single Fe atom-dispersed functional shells are presented.The synergistic effect between highly dispersed Fe-active sites and well-organized porous structures yields the combination of high ORR activity and high mass transfer performance.The half-wave potential of the catalyst in 0.1M H_(2)SO_(4) is 0.82 V versus reversible hydrogen electrode,and the peak power density is 812 mW·cm^(−2) in H_(2)–O_(2) fuel cells.Furthermore,it shows superior methanol tolerance,which is almost immune to methanol poisoning and generates up to 162 mW·cm^(−2) power density in direct methanol fuel cells.展开更多
A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization (in moderate conditions:200 °C, 12 h) of red liquor solids, a by-product of paper-making process. The prepared sulfonate...A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization (in moderate conditions:200 °C, 12 h) of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst (SC) had aromatic structure, composed of carbon enriched inner core, and oxygen-containing (SO3H, COOH, OH) groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts (strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five (HZSM-5), sulfated zir-conia) in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.展开更多
Hierarchically mesoporous titanosilicate Ti-SBA-1 was synthesized with organic mesomorphous complexes of polyelectrolyte(poly(acrylic acid)(PAA)) and cationic surfactant(hexadecyl pyridinium chloride(CPC)) a...Hierarchically mesoporous titanosilicate Ti-SBA-1 was synthesized with organic mesomorphous complexes of polyelectrolyte(poly(acrylic acid)(PAA)) and cationic surfactant(hexadecyl pyridinium chloride(CPC)) as template, tetraethylsiloxane as silica source and titanium ethoxide as titanium source.By adjusting the amount of titanium ethoxide in the synthesis, a series of Ti-SBA-1 particles with different Si/Ti ratio(79–180) were prepared. After incorporation of Ti into the silica framework the wellordered cubic Pm3n mesostructure remained, as well as the morphology, particle size. UV–vis DR spectra of the Ti-SBA-1 materials indicated that incorporated titanium species existed in a highly dispersed state and exhibited tetrahedral and octahedral coordination in the silica framework.展开更多
A series of hierarchical macro-/mesoporous silica supports (MMSs) were successfully synthesized using dual-templating technique employing polystyrene (PS) spheres and the Pluronic P123 surfactant. Pd was next load...A series of hierarchical macro-/mesoporous silica supports (MMSs) were successfully synthesized using dual-templating technique employing polystyrene (PS) spheres and the Pluronic P123 surfactant. Pd was next loaded on the hierarchical silica supports via colloids precipitation method. Physicochemical properties of the synthesized samples were characterized by various techniques and all catalysts were tested for the total oxidation of o-xylene. Among them, the Pd/MMS-b catalyst with tetraethoxysilane/polystyrene weight ratio of 1.0 exhibited superior catalytic activity, and under a higher gas hourly space velocity (GHSV) of 70000 h^-1, the 90% conversion of o-xylene has been obtained at around 200℃. The BET and SEM results indicated that Pd/MMS- b catalyst possesses high surface area and large pore volume, and well-ordered, interconnected macropores and 2D hexagonally mesopores hybrid network. This novel ordered hierarchical porous structure was highly beneficial to the dispersion of active sites Pd nanoparticles with less aggregation, and facilitates diffusion of reactants and products. Furthermore, the Pd/MMS-b catalyst possessed good stability and durability.展开更多
Trimodal hierarchical yolk-shell materials consisting of TS-1 core and mesoporous carbon shell (YS-TS- I@MC) was successfully synthesized by using TS-l@mesosilica as hard template, sucrose as carbon source and organ...Trimodal hierarchical yolk-shell materials consisting of TS-1 core and mesoporous carbon shell (YS-TS- I@MC) was successfully synthesized by using TS-l@mesosilica as hard template, sucrose as carbon source and organic base tetrapropylammonium hydroxide (TPAOH) as silica etching agent. The resultant YS-TS-I@MC contains the micropores (0.51 nm) in TS-1 core, the mesopores (2.9 rim) in carbon shell as well as a void or a stack pore between TS-1 fragements (TS-1 intercrystal mesopores, -18.4 nm). Under the rigorous etching conditions, the crystalline structure of TS-1 core was well retained. The YS-TS- I@MC served as a good support for palladium nano-particles (Pd NPs) or Rh(OH)x species, giving rise to efficient bifunctional catalysts for the tandem reactions including one-pot synthesis of propylene oxide or amides.展开更多
基金funded by Fundamental Research Grant Scheme,University of Malaya through the project number of FP031-2013A
文摘Hierarchical nanoporous HY zeolites were synthesized from acid-activated kaolin. The hierarchical factor (HF) was maximized by varying the aging and crystallization time. This was achieved by maximizing the external surface area without greatly reducing the micropore volume. The resulting products were characterized using X-ray diffraction (XRD), X-ray fluorescence, N2 adsorption, and NH3 temperature-programmed desorption. The nanoporous HY zeolite with the highest HF was obtained by aging for 48 h and a crystallization time of 24 h. The acidiW and crystallinity varied depending on the operating parameters. Incorporation of an appropriate amount of NaCI was also vital in maximizing the HF, crystallinity, and acidity. The sample crystallinities were determined by comparing their XRD peak intensities with those of a conventional Y zeolite. The results show that optimizing this process could lead to a widely acceptable commercial route for FIY zeolite production.
基金supported by the Fundamental Research Funds for the Central Universities, HUST (No. Z2009008)the National Natural Science Foundation of China (No. 20973068)
文摘The hierarchical mesoporous Zn/ZSM-5 zeolite catalyst was prepared by NaOH treatment and Zn impregnation, and its application in the conversion of methanol to gasoline (MTG) was studied. N2 adsorption-desorption results showed that the mesopores with sizes of 2-20 nm in HZ5/0.3AT was formed by 0.3 M NaOH alkali treatment. The zeolite samples after modification were also characterized by XRF, AAS, XRD, SEM and NH3-TPD methods. Zn impregnated catalyst Zn/HZ5/0.3AT exhibited dramatic improvements in catalytic lifetime and liquid hydrocarbons yield. The selectivity of aromatic hydrocarbons was also improved after Zn impregnation. It is suggested that the mesopores of Zn/HZ5/0.3AT enhanced the synergetic effect of Zn species and acid sites and the capability to coke tolerance, which were confirmed by the results of catalytic test and TGA analysis, respectively.
基金We gratefully acknowledge support from the National Natural Science Foundation of China(Grant Nos.21905220,51772240,21503158,51425301,U1601214,21703184)the China Postdoctoral Science Foundation(2020M673408)+5 种基金the Key Research and Development Plan of Shaanxi Province,China(Grant No.2018ZDXM-GY-135)the Fundamental Research Funds for“Young Talent Support Plan”of Xi'an Jiaotong University(HG6J003)the“1000‐Plan program”of Shaanxi Province,the Promotion Program for Young and Middle-Aged Teacher in Science and Technology Research of Huaqiao University(ZQN-PY506)the Scientific Research Funds of Huaqiao University(17BS405)the State Key Laboratory for Mechanical Behavior of Materials(20192101)the Natural Science Foundation Committee of Jiangsu Province(BK20201190).
文摘Novel cost-effective fuel cells have become more attractive due to the demands for rare and expensive platinum-group metal(PGM)catalysts for mitigating the sluggish kinetics of the oxygen reduction reaction(ORR).The high-cost PGM catalyst in fuel cells can be replaced by earth-abundant transition-metalbased catalysts,that is,an Fe-N-C catalyst,which is considered one of the most promising alternatives.However,the performance of the Fe-N-C catalyst is hindered by the low catalytic activity and poor stability,which is caused by insufficient active sites and the lack of optimization of the triple-phase interface for mass transportation.Herein,a novel Fe–N–C catalyst consisting of mono-dispersed hierarchically mesoporous carbon sphere cores and single Fe atom-dispersed functional shells are presented.The synergistic effect between highly dispersed Fe-active sites and well-organized porous structures yields the combination of high ORR activity and high mass transfer performance.The half-wave potential of the catalyst in 0.1M H_(2)SO_(4) is 0.82 V versus reversible hydrogen electrode,and the peak power density is 812 mW·cm^(−2) in H_(2)–O_(2) fuel cells.Furthermore,it shows superior methanol tolerance,which is almost immune to methanol poisoning and generates up to 162 mW·cm^(−2) power density in direct methanol fuel cells.
基金Supported by the National Natural Science Foundation of China(21276076)the Fundamental Research Funds for the Central Universities of China(WA1014003)State Key Laboratory of Chemical Engineering(SKL-ChE-10C06)
文摘A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization (in moderate conditions:200 °C, 12 h) of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst (SC) had aromatic structure, composed of carbon enriched inner core, and oxygen-containing (SO3H, COOH, OH) groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts (strong-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five (HZSM-5), sulfated zir-conia) in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.
基金supported by National Science Foundation of China (Nos. 21373116 and 21421001)Tianjin Natural Science Research Fund (No. 13JCYBJC18300)+3 种基金RFDP (No. 20120031110005)the Technology Planning Project of Hunan Province (No. 2014SK2019)National Science Foundation for Post-doctoral Scientists of China (No. 2014T70774)the Scientific Research Fund of Hunan Provincial Education Department (No. 14C0343)
文摘Hierarchically mesoporous titanosilicate Ti-SBA-1 was synthesized with organic mesomorphous complexes of polyelectrolyte(poly(acrylic acid)(PAA)) and cationic surfactant(hexadecyl pyridinium chloride(CPC)) as template, tetraethylsiloxane as silica source and titanium ethoxide as titanium source.By adjusting the amount of titanium ethoxide in the synthesis, a series of Ti-SBA-1 particles with different Si/Ti ratio(79–180) were prepared. After incorporation of Ti into the silica framework the wellordered cubic Pm3n mesostructure remained, as well as the morphology, particle size. UV–vis DR spectra of the Ti-SBA-1 materials indicated that incorporated titanium species existed in a highly dispersed state and exhibited tetrahedral and octahedral coordination in the silica framework.
基金This work was financially supported by the National Natural Science Foundation (Grant Nos. 21337003 and 21477149), and the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB05050200).
文摘A series of hierarchical macro-/mesoporous silica supports (MMSs) were successfully synthesized using dual-templating technique employing polystyrene (PS) spheres and the Pluronic P123 surfactant. Pd was next loaded on the hierarchical silica supports via colloids precipitation method. Physicochemical properties of the synthesized samples were characterized by various techniques and all catalysts were tested for the total oxidation of o-xylene. Among them, the Pd/MMS-b catalyst with tetraethoxysilane/polystyrene weight ratio of 1.0 exhibited superior catalytic activity, and under a higher gas hourly space velocity (GHSV) of 70000 h^-1, the 90% conversion of o-xylene has been obtained at around 200℃. The BET and SEM results indicated that Pd/MMS- b catalyst possesses high surface area and large pore volume, and well-ordered, interconnected macropores and 2D hexagonally mesopores hybrid network. This novel ordered hierarchical porous structure was highly beneficial to the dispersion of active sites Pd nanoparticles with less aggregation, and facilitates diffusion of reactants and products. Furthermore, the Pd/MMS-b catalyst possessed good stability and durability.
基金the National Natural Science Foundation of China(No.21273076,U1162102)the National Key Technology R&D Program(No.2012BAE05B02)+1 种基金Ph.D Programs Foundation of Ministry of Education(No.2012007613000)the Shanghai Leading Academic Discipline Project(B409)
文摘Trimodal hierarchical yolk-shell materials consisting of TS-1 core and mesoporous carbon shell (YS-TS- I@MC) was successfully synthesized by using TS-l@mesosilica as hard template, sucrose as carbon source and organic base tetrapropylammonium hydroxide (TPAOH) as silica etching agent. The resultant YS-TS-I@MC contains the micropores (0.51 nm) in TS-1 core, the mesopores (2.9 rim) in carbon shell as well as a void or a stack pore between TS-1 fragements (TS-1 intercrystal mesopores, -18.4 nm). Under the rigorous etching conditions, the crystalline structure of TS-1 core was well retained. The YS-TS- I@MC served as a good support for palladium nano-particles (Pd NPs) or Rh(OH)x species, giving rise to efficient bifunctional catalysts for the tandem reactions including one-pot synthesis of propylene oxide or amides.