Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in i...Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in industrial processes.As the essential additives for preparing formed catalysts,binders are usually the catalytically inert components,but they would cover the surface and pore mouth of zeolite,thereby declining the accessibility of active sites.By recrystallizing the binder(silica)/Ti‐MWW extrudates with the assistance of dual organic structure‐directing agents,the silica binder was converted into MWW zeolite phase to form a structured binder‐free Ti‐MWW zeolite with Si‐rich shell,which enhanced the diffusion efficiency and maintained the mechanical strength.Meanwhile,due to the partial dissolution of Si in the Ti‐MWW matrix,abundant silanol nests formed and part of framework TiO4 species were transferred into open TiO_(6)ones,improving the accumulation and activation ability of H_(2)O_(2)inside the monolith.Successive piperidine treatment and fluoridation of the binder‐free Ti‐MWW further enhanced the H_(2)O_(2)activation and oxygen transfer ability of the active Ti sites,and stabilized the Ti‐OOH intermediate through hydrogen bond formed between the end H in Ti‐OOH and the adjacent Si‐F species,thus achieving a more efficient epoxidation process.Additionally,the side reaction of PO hydrolysis was inhibited because the modification effectively quenched numerous Si‐OH groups.The lifetime of the modified binder‐free Ti‐MWW catalyst was 2400 h with the H_(2)O_(2)conversion and PO selectivity both above 99.5%.展开更多
Rod-shaped mesoporous titanosilicate composites （RMTSs） with controllable aspect ratios （ARs） were fabricated using cetyltrimethylammonium bromide （CTAB） and ammonium hydroxide （NH4OH） at a continuous stirring...Rod-shaped mesoporous titanosilicate composites （RMTSs） with controllable aspect ratios （ARs） were fabricated using cetyltrimethylammonium bromide （CTAB） and ammonium hydroxide （NH4OH） at a continuous stirring rate, resulting in ARs ranging from 1 to 5. Slowing the stirring rate or increasing the concentration of CTAB mainly impacted the length growth, whereas NH4OH affected the width growth. Photocatalytic activity studies revealed that the length of RMTSs played a more significant role than the width at lower ARs in their photocatalytic activity.展开更多
A zeolitic titanosilicate with the composition of K_2TiSi_3O_9·H_2O, a structural analogue of natural mineral umbite K_2ZrSi_3O_9·H_2O, was hydrothermally synthesized in the SiO_2-TiO_2-K_2O-H_2O system and...A zeolitic titanosilicate with the composition of K_2TiSi_3O_9·H_2O, a structural analogue of natural mineral umbite K_2ZrSi_3O_9·H_2O, was hydrothermally synthesized in the SiO_2-TiO_2-K_2O-H_2O system and characterized by means of powder X-ray diffraction, SEM, IR and thermal analysis. The effects of TiO_2/SiO_2 and OH -/SiO_2 ratios on the crystallization of the umbite were discussed. The influence of the organic additives on the morphology of the crystal was also investigated and the crystals with different shapes were obtained.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 novel synthesis process for ETS-4 titanosilicate using commercial anatase as the titanium source in the absence of fluoride ions was studied. Fluoride ions and traced ETS-4 seeds have important roles in forming ETS-...A novel synthesis process for ETS-4 titanosilicate using commercial anatase as the titanium source in the absence of fluoride ions was studied. Fluoride ions and traced ETS-4 seeds have important roles in forming ETS-4 structures. However, the method using ETS-4 seeds instead of fluoride ions to improve product purity and productivity is environment-friendly. ETS-4, ETS-4（NS）, and ETS-4（NaF） were respectively synthesized using traced ETS-4 seeds, without seeds, and with fluoride ions. The as-synthesized samples were identified by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. Adsorption isotherms and adsorption heats of nitrogen and methane on the prepared ETS-4 were also measured. The results showed that ETS-4 samples could be prepared using anatase in the absence of fluoride ions, with good purity, comparable physicochemical properties, and excellent adsorption properties.展开更多
Titanosilicates, with tetrahedrally coordinated Ti4＋ ions in highly crystalline zeolite frameworks, are a class of unique heterogeneous catalysts useful for the liquid-phase selective oxidation reactions. The great s...Titanosilicates, with tetrahedrally coordinated Ti4＋ ions in highly crystalline zeolite frameworks, are a class of unique heterogeneous catalysts useful for the liquid-phase selective oxidation reactions. The great success of green Ti-zeolites/H2O2 reaction system has aroused considerable scientific and industrial interests. The catalytic properties of titanosilicates relay on zeolite topologies, crystal morphology, the content and micro-environment of tetrahedral Ti4＋ ions. The ever-growing needs for the oxidation catalysts in processing bulky molecules in petrochemical and fine chemical industries have set off a new tide of developing novel titanosilicates with significantly improved cat- alytic performance than traditional ones. This mini review summarizes recent progresses in developing the titano- silicates with novel topology, morphology as well as chemically modified micro-environment.展开更多
Novel ammonia-treated titanosilicates have been prepared by heating the samples of Ti-MWW, TS-l and Ti-Beta under pure ammonia gas flow at 673 K for a period of time. The ammonia modification improved their catalytic ...Novel ammonia-treated titanosilicates have been prepared by heating the samples of Ti-MWW, TS-l and Ti-Beta under pure ammonia gas flow at 673 K for a period of time. The ammonia modification improved their catalytic performance in liquid-phase oxidations. Especially, the catalytic activities of ammonified Ti-MWW, N-Ti-MWW, were enhanced greatly in the epoxidation of 1-hexene with H2O2. The reason that the ammonia treat- ment played such an important role in post-modification of titanosilicate was investigated in details. In comparison to the parent Ti-MWW catalyst, N-Ti-MMW was more robust and produced less coke in oxidation reactions.展开更多
TS-2 microspheres,consisting of intergrown primary nanocrystals,was prepared by controlling the synthetic parameters.The effects of the amount of quaternary ammonium cations as structure-directing agent,H2O/Si ratio,t...TS-2 microspheres,consisting of intergrown primary nanocrystals,was prepared by controlling the synthetic parameters.The effects of the amount of quaternary ammonium cations as structure-directing agent,H2O/Si ratio,the presence of alcohol and the temperature were carefully investigated on the crystallization process.The high alkalinity was proved to be highly important for the preservation of the microsphere morphology initially formed,due to the unique intergrown stacking style.An alkali treatment with the aqueous solution of structure-directing agent,organic amine and ammonium salt and subsequent Na+ion-exchange were performed to enhance the catalytic activity of TS-2 microsphere in the cyclohexanone ammoximation reactions,with both the conversion and selectivity higher than 99%.In the continuous reaction,the TS-2 microspheres exhibited to be durable catalyst with potential application in industrial ammoximation processes.展开更多
Na_(2)TiSiO_(5)(NTSO)is a low-cost Li-ion battery anode with great application potential,such as the tetragonal NTSO(T-NTSO)with a high capacity and a low voltage.In addition to the tetragonal structure,NTSO has two o...Na_(2)TiSiO_(5)(NTSO)is a low-cost Li-ion battery anode with great application potential,such as the tetragonal NTSO(T-NTSO)with a high capacity and a low voltage.In addition to the tetragonal structure,NTSO has two other polymorphs.However,the basic understanding of the structure,ion insertion and transport mechanisms of these new materials is still lacking.Herein,we present a combined experimental and computational investigation of the tetragonal and orthorhombic NTSO to reveal the intrinsic mechanism leading to the superior electrochemical performance of T-NTSO.We determined that the insertion site with a flexible Ti^(4+)/Ti^(3+)redox pair is critical for Li+insertion stability.The large number of such flexible sites in the T-NTSO results in a higher capacity and higher ionic conductivity than those of orthorhombic polymorph.The understanding of intrinsic properties will accelerate the development and utilization of titanosilicates as the next generation low-voltage anode of Li-ion battery.展开更多
A TAPO-11 molecular sieve with the space group lcm2 was synthesized successfully. The samples with different space group were controlled simply only by adjusting the crystallization temperature （CT） in the hydrother...A TAPO-11 molecular sieve with the space group lcm2 was synthesized successfully. The samples with different space group were controlled simply only by adjusting the crystallization temperature （CT） in the hydrothermal system. In the system of gel with a molar composition of 0.7R- xTiO2： P2O5： Al2O3： 30H2O, where x is 0.01-0.10 and the R is a mixture of di-n-propylamine and diisopropylamine as templates. When CT was between 150-160℃, the calcined sample showed the space group of Icm^2, while it showed Pna21 at CT larger than 190℃. The characterizations of UV-Vis and FT-IR confirmed that Ti was incorporated into the AEL framework successfully.展开更多
A titanosilicate Ti-ECNU-8 with a FER type sub-zeolite structure was developed by pots-synthesis and applied to the epoxdiation of alkenes with hydrogen peroxide.A controlled acid treatment on the pure silica layered ...A titanosilicate Ti-ECNU-8 with a FER type sub-zeolite structure was developed by pots-synthesis and applied to the epoxdiation of alkenes with hydrogen peroxide.A controlled acid treatment on the pure silica layered precursor PLS-3 of FER topology gave rise to a sub-zeolite ECNU-8.Composed of a collection of FER sheets without an ordered stacking manner along layer related[100]direction,the structure of ECNU-8 was constructed by a reorientation of interlayer hydrogen bond moieties caused by partial removal of interlayer organic structure directing agent.ECNU-8 possessed an external surface area enlarged by ca.30% in comparison to corresponding three-dimensional FER zeolite.Through a solid-gas reaction with TiCl4 vapor,tetrahedral Ti active sites were introduced into the framework.The resultant Ti-ECNU-8 retained the structural properties of ECNU-8,and exhibited an excellent catalytic performance for the epoxidation of cycloalkenes owing to the accessible Ti sites located in open reaction space.展开更多
Epoxidation of propylene to propylene oxide(PO)with hydrogen peroxide(HPPO)is an environmentally friendly and cost-efficient process in which titanosilicates are used as catalysts.Ti-MWW is a potential industrial cata...Epoxidation of propylene to propylene oxide(PO)with hydrogen peroxide(HPPO)is an environmentally friendly and cost-efficient process in which titanosilicates are used as catalysts.Ti-MWW is a potential industrial catalyst for this process,which involves the addition of HPPO to PO.The silanol groups generated during secondary crystallization unavoidably result in ring-opening of PO and inefficient decomposition of HPPO,which diminish the PO selectivity and the lifespan of Ti-MWW.To address this issue,we conducted post-treatment modifications of the structured Bf-Ti-MWW catalyst with potassium fluoride aqueous solutions.By quenching the silanol groups with potassium fluoride and implanting electron-withdrawing fluoride groups into the Ti-MWW framework,both the catalytic activity and HPPO utilization efficiency were increased.Moreover,the ring opening reaction of PO was prohibited.In a continuous fixed-bed liquid-phase propylene epoxidation reaction,the KF-treated structured Ti-MWW catalyst displayed an exceptionally long lifespan of 2700 h,with a PO yield of 590 g·kg^(-1)·h^(-1).展开更多
文摘Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in industrial processes.As the essential additives for preparing formed catalysts,binders are usually the catalytically inert components,but they would cover the surface and pore mouth of zeolite,thereby declining the accessibility of active sites.By recrystallizing the binder(silica)/Ti‐MWW extrudates with the assistance of dual organic structure‐directing agents,the silica binder was converted into MWW zeolite phase to form a structured binder‐free Ti‐MWW zeolite with Si‐rich shell,which enhanced the diffusion efficiency and maintained the mechanical strength.Meanwhile,due to the partial dissolution of Si in the Ti‐MWW matrix,abundant silanol nests formed and part of framework TiO4 species were transferred into open TiO_(6)ones,improving the accumulation and activation ability of H_(2)O_(2)inside the monolith.Successive piperidine treatment and fluoridation of the binder‐free Ti‐MWW further enhanced the H_(2)O_(2)activation and oxygen transfer ability of the active Ti sites,and stabilized the Ti‐OOH intermediate through hydrogen bond formed between the end H in Ti‐OOH and the adjacent Si‐F species,thus achieving a more efficient epoxidation process.Additionally,the side reaction of PO hydrolysis was inhibited because the modification effectively quenched numerous Si‐OH groups.The lifetime of the modified binder‐free Ti‐MWW catalyst was 2400 h with the H_(2)O_(2)conversion and PO selectivity both above 99.5%.
基金supported by the National Natural Science Foundation of China(Nos.20976100,51372124)the Natural Science Foundation of Shandong Province(Nos.ZR2010BM013, ZR2011BQ009)+1 种基金the Program for Scientific Research Innovation Team in Colleges and Universities of Shandong Province(No. 201207)Key Laboratory of Colloid and Surface Chemistry, Ministry of Education(Shandong University,No.201205)
文摘Rod-shaped mesoporous titanosilicate composites （RMTSs） with controllable aspect ratios （ARs） were fabricated using cetyltrimethylammonium bromide （CTAB） and ammonium hydroxide （NH4OH） at a continuous stirring rate, resulting in ARs ranging from 1 to 5. Slowing the stirring rate or increasing the concentration of CTAB mainly impacted the length growth, whereas NH4OH affected the width growth. Photocatalytic activity studies revealed that the length of RMTSs played a more significant role than the width at lower ARs in their photocatalytic activity.
基金Supported by the National Natural Science Foundation of China and the state key laboratory of Inorganic Synthesi
文摘A zeolitic titanosilicate with the composition of K_2TiSi_3O_9·H_2O, a structural analogue of natural mineral umbite K_2ZrSi_3O_9·H_2O, was hydrothermally synthesized in the SiO_2-TiO_2-K_2O-H_2O system and characterized by means of powder X-ray diffraction, SEM, IR and thermal analysis. The effects of TiO_2/SiO_2 and OH -/SiO_2 ratios on the crystallization of the umbite were discussed. The influence of the organic additives on the morphology of the crystal was also investigated and the crystals with different shapes were obtained.
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supported by the National Natural Science Foundation of China (No. 51074205)
文摘A novel synthesis process for ETS-4 titanosilicate using commercial anatase as the titanium source in the absence of fluoride ions was studied. Fluoride ions and traced ETS-4 seeds have important roles in forming ETS-4 structures. However, the method using ETS-4 seeds instead of fluoride ions to improve product purity and productivity is environment-friendly. ETS-4, ETS-4（NS）, and ETS-4（NaF） were respectively synthesized using traced ETS-4 seeds, without seeds, and with fluoride ions. The as-synthesized samples were identified by X-ray diffraction, scanning electron microscopy, and thermogravimetric analysis. Adsorption isotherms and adsorption heats of nitrogen and methane on the prepared ETS-4 were also measured. The results showed that ETS-4 samples could be prepared using anatase in the absence of fluoride ions, with good purity, comparable physicochemical properties, and excellent adsorption properties.
文摘Titanosilicates, with tetrahedrally coordinated Ti4＋ ions in highly crystalline zeolite frameworks, are a class of unique heterogeneous catalysts useful for the liquid-phase selective oxidation reactions. The great success of green Ti-zeolites/H2O2 reaction system has aroused considerable scientific and industrial interests. The catalytic properties of titanosilicates relay on zeolite topologies, crystal morphology, the content and micro-environment of tetrahedral Ti4＋ ions. The ever-growing needs for the oxidation catalysts in processing bulky molecules in petrochemical and fine chemical industries have set off a new tide of developing novel titanosilicates with significantly improved cat- alytic performance than traditional ones. This mini review summarizes recent progresses in developing the titano- silicates with novel topology, morphology as well as chemically modified micro-environment.
文摘Novel ammonia-treated titanosilicates have been prepared by heating the samples of Ti-MWW, TS-l and Ti-Beta under pure ammonia gas flow at 673 K for a period of time. The ammonia modification improved their catalytic performance in liquid-phase oxidations. Especially, the catalytic activities of ammonified Ti-MWW, N-Ti-MWW, were enhanced greatly in the epoxidation of 1-hexene with H2O2. The reason that the ammonia treat- ment played such an important role in post-modification of titanosilicate was investigated in details. In comparison to the parent Ti-MWW catalyst, N-Ti-MMW was more robust and produced less coke in oxidation reactions.
文摘TS-2 microspheres,consisting of intergrown primary nanocrystals,was prepared by controlling the synthetic parameters.The effects of the amount of quaternary ammonium cations as structure-directing agent,H2O/Si ratio,the presence of alcohol and the temperature were carefully investigated on the crystallization process.The high alkalinity was proved to be highly important for the preservation of the microsphere morphology initially formed,due to the unique intergrown stacking style.An alkali treatment with the aqueous solution of structure-directing agent,organic amine and ammonium salt and subsequent Na+ion-exchange were performed to enhance the catalytic activity of TS-2 microsphere in the cyclohexanone ammoximation reactions,with both the conversion and selectivity higher than 99%.In the continuous reaction,the TS-2 microspheres exhibited to be durable catalyst with potential application in industrial ammoximation processes.
基金financially supported by Beijing Youth Scholar Program(No.PXM2021_014204_000023)Beijing Natural Science Foundation(No.JQ19003)the National Natural Science Foundation of China(Nos.22002004 and 22075007)。
文摘Na_(2)TiSiO_(5)(NTSO)is a low-cost Li-ion battery anode with great application potential,such as the tetragonal NTSO(T-NTSO)with a high capacity and a low voltage.In addition to the tetragonal structure,NTSO has two other polymorphs.However,the basic understanding of the structure,ion insertion and transport mechanisms of these new materials is still lacking.Herein,we present a combined experimental and computational investigation of the tetragonal and orthorhombic NTSO to reveal the intrinsic mechanism leading to the superior electrochemical performance of T-NTSO.We determined that the insertion site with a flexible Ti^(4+)/Ti^(3+)redox pair is critical for Li+insertion stability.The large number of such flexible sites in the T-NTSO results in a higher capacity and higher ionic conductivity than those of orthorhombic polymorph.The understanding of intrinsic properties will accelerate the development and utilization of titanosilicates as the next generation low-voltage anode of Li-ion battery.
基金This work was supported by the National Natural Science Foundation of China （No. 20473027） Science and Technology Commission of Shanghai Municipality （No. 05dz22306）Pujiang project （No. 05PJ14041）.
文摘A TAPO-11 molecular sieve with the space group lcm2 was synthesized successfully. The samples with different space group were controlled simply only by adjusting the crystallization temperature （CT） in the hydrothermal system. In the system of gel with a molar composition of 0.7R- xTiO2： P2O5： Al2O3： 30H2O, where x is 0.01-0.10 and the R is a mixture of di-n-propylamine and diisopropylamine as templates. When CT was between 150-160℃, the calcined sample showed the space group of Icm^2, while it showed Pna21 at CT larger than 190℃. The characterizations of UV-Vis and FT-IR confirmed that Ti was incorporated into the AEL framework successfully.
基金the National Natural Science Foundation of China(Nos.21373089,U1162102)PhD Programs Foundation of Ministry of Education(No.2012007613000)+1 种基金the National Key Technology R&D Program(No.2012BAE05B02)the Shanghai Leading Academic Discipline Project(No.B409)
文摘A titanosilicate Ti-ECNU-8 with a FER type sub-zeolite structure was developed by pots-synthesis and applied to the epoxdiation of alkenes with hydrogen peroxide.A controlled acid treatment on the pure silica layered precursor PLS-3 of FER topology gave rise to a sub-zeolite ECNU-8.Composed of a collection of FER sheets without an ordered stacking manner along layer related[100]direction,the structure of ECNU-8 was constructed by a reorientation of interlayer hydrogen bond moieties caused by partial removal of interlayer organic structure directing agent.ECNU-8 possessed an external surface area enlarged by ca.30% in comparison to corresponding three-dimensional FER zeolite.Through a solid-gas reaction with TiCl4 vapor,tetrahedral Ti active sites were introduced into the framework.The resultant Ti-ECNU-8 retained the structural properties of ECNU-8,and exhibited an excellent catalytic performance for the epoxidation of cycloalkenes owing to the accessible Ti sites located in open reaction space.
基金support from the National Key R&D Program of China(Grant Nos.2021YFA1501401 and 2023YFB3810602)the National Natural Science Foundation of China(Grant No.22222201)。
文摘Epoxidation of propylene to propylene oxide(PO)with hydrogen peroxide(HPPO)is an environmentally friendly and cost-efficient process in which titanosilicates are used as catalysts.Ti-MWW is a potential industrial catalyst for this process,which involves the addition of HPPO to PO.The silanol groups generated during secondary crystallization unavoidably result in ring-opening of PO and inefficient decomposition of HPPO,which diminish the PO selectivity and the lifespan of Ti-MWW.To address this issue,we conducted post-treatment modifications of the structured Bf-Ti-MWW catalyst with potassium fluoride aqueous solutions.By quenching the silanol groups with potassium fluoride and implanting electron-withdrawing fluoride groups into the Ti-MWW framework,both the catalytic activity and HPPO utilization efficiency were increased.Moreover,the ring opening reaction of PO was prohibited.In a continuous fixed-bed liquid-phase propylene epoxidation reaction,the KF-treated structured Ti-MWW catalyst displayed an exceptionally long lifespan of 2700 h,with a PO yield of 590 g·kg^(-1)·h^(-1).
