We describe the new mineral species titanium, ideally Ti, found in the podiform chromitites of the Luobusha ophiolite in Tibet, People＇s Republic of China. The irregular crystals range from 0.1 to 0.6 mm in diameter ...We describe the new mineral species titanium, ideally Ti, found in the podiform chromitites of the Luobusha ophiolite in Tibet, People＇s Republic of China. The irregular crystals range from 0.1 to 0.6 mm in diameter and form an intergrowth with coesite and kyanite. Titanium is silver grey in colour, the luster is metallic, it is opaque, the streak is grayish black, and it is non-fluorescent. The mineral is malleable, has a rough to hackly fracture and has no apparent cleavage. The estimated Mohs hardness is 4, and the calculated density is 4.503 g/cm3. The composition is Ti 99.23-100.00 wt%. The mineral is hexagonal, space group P6flmmc. Unit-cell parameters are a 2.950 （2） ~, c 4.686 （1） A,V 35.32 （5） A3, Z = 2. The five strongest powder diffraction lines [d in A （hkl） （I/I0）] are： 2.569 （010） （32）, 2.254（011） （100）, 1.730 （012） （16）, 1.478 （110） （21）, and 0.9464 （121） （8）. The species and name were approved by the CNMNC （IMA 2010-044）.展开更多
Tailoring the Ti coordination states in titanosilicate zeolites to simultaneously improve feedstock conversion and maximize the target product selectivity remains a challenge in the pursuit of high-performance catalys...Tailoring the Ti coordination states in titanosilicate zeolites to simultaneously improve feedstock conversion and maximize the target product selectivity remains a challenge in the pursuit of high-performance catalysts for selective oxidation reactions.Herein,we provide a facile strategy to synthesize hierarchical anatase-free TS-1(MFI-type)zeolites with tetrahedrally coordinated(TiO_(4))and octahedrally coordinated Ti species(TiO_(6)).The TiO_(4)species provide high epoxide selectivity,while the TiO_(6)species afford improved alkene conversion.This strategy is achieved by synergistically using an L-lysine-assisted approach and a two-step crystallization;the two-step crystallization approach prevents the formation of anatase TiO_(2),while L-lysine stabilizes the TiO_(6)species and ensures efficient incorporation of TiO_(6)into the anatase-free TS-1 zeolites.Compared with their conventional counterparts,which only contain TiO_(4)species,the as-prepared TS-1 zeolites(Si/Ti=36.9)result in a higher 1-hexene conversion(33%),higher TON value(153),and comparable epoxide selectivity(95%).This synthetic strategy provides avenues to tailor the amount and distribution of Ti species in titanosilicate zeolites to achieve high catalytic performances in various processes.展开更多
A nanocomposite catalyst with a nonstoichiometric titanium oxide loaded on a special nanotubular alumina(γ‐Al2O3‐nt)was developed and used to reduce cinnamaldehyde to cinnamyl alcohol with sacrificial isopropanol,i...A nanocomposite catalyst with a nonstoichiometric titanium oxide loaded on a special nanotubular alumina(γ‐Al2O3‐nt)was developed and used to reduce cinnamaldehyde to cinnamyl alcohol with sacrificial isopropanol,i.e.,a Meerwein‐Ponndorf‐Verley type reaction.The deposition process produced a highly disperse layer of titanium oxide on the surface of aγ‐Al2O3‐nt support.After a reduction treatment,the as‐prepared TiOx/γ‐Al2O3‐nt was a highly efficient catalyst for the hydrogen transfer reaction between isopropanol and cinnamaldehyde.Selectivity for cinnamic alcohol was higher than99%and the conversion of cinnamaldehyde was higher than95%.The regular morphology of theγ‐Al2O3‐nt support with homogeneous surface sites and the uniformly dispersed titanium oxide featured a high concentration surface Ti(III)species.These factors contributed to the high performance of the TiOx/γ‐Al2O3‐nt catalyst.展开更多
Interaction of hydrogen with TiO2 plays a vital role in TiO2-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species...Interaction of hydrogen with TiO2 plays a vital role in TiO2-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species on a rutile TiO2（110） surface formed by atomic H exposure at 320 and 115 K by means of thermal desorption spectroscopy, X-ray photoelectron spectroscopy and low energy electron diffraction. Atomic H interaction with rutile TiO2（110） at 115 K forms surface TiààH hydride, surface hydroxyl group, and chemisorbed water. Upon heating, surface TiààH hydride reacts to produce H2 while surface hydroxyl groups react to form both water and H2. Atomic H interaction with rutile TiO2（110） at 320 K strongly reduces TiO2 due to the continuous formation and desorption of water and forms surface hydroxyl groups and likely subsurface/bulk hydrogen species. Upon heating, hydrogen forms as the only gas-phase product and its desorption activation energy decreases with the subsurface/bulk reduction extent of rutile TiO2（110）. Surface Ti-H hydride exhibits photo-induced reactivity while both surface TiààH hydride and surface hydroxyl group exhibit electro-induced reactivity. These results have important implications for understanding the hydrogen-involved thermal and photo reactions on TiO2-based catalysts.展开更多
The exploration of high-efficient catalysts based on hierarchical Ti-containing zeolites with optimized active titanium species distribution is of great value in enhancing the epoxidation of bulky olefins. Herein, hie...The exploration of high-efficient catalysts based on hierarchical Ti-containing zeolites with optimized active titanium species distribution is of great value in enhancing the epoxidation of bulky olefins. Herein, hierarchical TS-1(MFI) zeolite with an extra-large external surface area(210 m2/g) and highly active octahedral- coordinated Ti species was prepared via organic base-assisted sequential post-treatment. Such a catalyst afforded a high turnover number value(TON, 114) in 1-octene epoxidation reaction, which was over twice than that(53) of the untreated conventional microporous TS-1 parent. According to the detailed characterization results, we revealed the hierarchical porosity construction effect of tetrapropylamonium hydroxide(TPAOH) treatment(first step) and the octahedral-coordinated Ti species fabrication effect of ethylamine(EA) treatment(second step) under hydrothermal condition. Such a facile post-treatment strategy reported in this work may provide guidance for the rational synthesis of TS-1 zeolite with enhanced catalytic activity.展开更多
Low-cost nickels can be used as cocatalyst to improve the performance of photocatalysts,which may be promising materials applied in the field of photocatalytic water splitting.In this study,different nickel species Ni...Low-cost nickels can be used as cocatalyst to improve the performance of photocatalysts,which may be promising materials applied in the field of photocatalytic water splitting.In this study,different nickel species Ni,Ni(OH)2,NiO,NiOx,and NiS are used to modified titanium dioxide(P25)to investigate their roles on the photocatalytic hydrogen evolution activities.UV-visible,X-ray diffraction(XRD),Brunner-Emmet-Teller(BET)measurements,transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS)analysis etc.are employed to characterize the physical and chemical properties of catalysts.The results indicate that all the nickel species can improve the photocatalytic hydrogen production activity of P25.The P25 modified with NiOx and NiS has more superior photocatalytic hydrogen evolution activities than those modified with other nickel species.The reason for this is that NiOx and NiS can form p-n junctions with P25 respectively.In addition,NiOx can be selectively deposited on the active sites of P25 via in situ the photodeposition method and NiS is beneficial for H+reacting with photo-excited electrons.展开更多
TiO2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve its photocatalytic activity, the Ti-coating Mg Al hydrotalcite（Ti–Mg Al–LDH） was...TiO2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve its photocatalytic activity, the Ti-coating Mg Al hydrotalcite（Ti–Mg Al–LDH） was prepared by chemical vapor deposition（CVD） method.Response surface method（RSM） was employed to evaluate the effect of Ti species coating parameters on the photocatalytic activity, which was found to be affected by the furnace temperature, N2 flow rate and influx time of precursor gas. Application of RSM successfully increased the photocatalytic efficiency of the Ti–Mg Al–LDH in methylene blue photodegradation under UV irradiation, leading to improved economy of the process.According to the results from X-ray diffraction, scanning electron microscopy, Brunner–Emmet–Teller and Barrett–Joyner–Hallender, thermogravimetric and differential thermal analysis, UV–vis diffuse reflectance spectra analyses, the Ti species（TiO2or/and Ti^（4＋）） were successfully coated on the Mg Al–LDH matrix. The Ti species on the surface of the Ti–Mg Al–LDH lead to a higher photocatalytic performance than commercial TiO2-P25. The results suggested that CVD method provided a new approach for the industrial preparation of Ti-coating Mg Al–LDH material with good photocatalytic performances.展开更多
The catalytic performances over propylene epoxidation with H_(2)and O_(2)(HOPO process)are significantly affected by the properties(e.g.,surface properties,Ti coordination,morphology)of titanosilicate zeolite.Introduc...The catalytic performances over propylene epoxidation with H_(2)and O_(2)(HOPO process)are significantly affected by the properties(e.g.,surface properties,Ti coordination,morphology)of titanosilicate zeolite.Introducing urea into zeolite synthesis is a simple and convenient method to modify these properties of titanosilicate zeolite.Uncalcined pore-blocked titanium silicalite-1(TS-1,i.e.,TS-1-B)with the lower urea dosage possesses more defective structure and unsaturated coordinated Ti sites verified by 29Si nuclear magnetic resonance(NMR)and X-ray photoelectron spectroscopy(XPS)analysis,which results in a high initial activity and hydrogen efficiency;while the high surface acidity generated by these Ti species leads to a continuous decrease in the activity and the propylene oxide(PO)selectivity during the reaction.As the amount of urea gradually increases,the TS-1-B samples present the reduced surface defects and defective and unsaturated Ti species.Specially,TS-1-B-0.30U presents the weaker PO adsorption on PO-diffusion reflectance infrared Fourier transform spectra(DRIFTS),thus results in the high stable PO formation rate and selectivity over its Au catalyst.Furthermore,a flat-plate-like shape with a shorter thickness of 100 nm along the b-axis direction is observed on the urea-modified TS-1.Compared with the conventional ellipsoidal TS-1 with crystal sizes of 200 and 500 nm,the flat-plate-like TS-1-0.30U displays the less surface defects,unsaturated Ti species,the weaker Lewis acid,which is favorable for the desorption and intracrystalline diffusion of PO,thus reduces the occurrence of side reactions for the improved selectivity and stability.This work may provide a reference for developing titanium-containing materials with high activity and stability over HOPO reaction.展开更多
TiO2 supports doped with different amounts of Si were prepared by a sol-gel method, and 1 wt% vanadia （V2O5） loaded on Si-doped TiO2 was obtained by an impregnation method. The mole ratio of Si/Ti was 0.2, NOx conve...TiO2 supports doped with different amounts of Si were prepared by a sol-gel method, and 1 wt% vanadia （V2O5） loaded on Si-doped TiO2 was obtained by an impregnation method. The mole ratio of Si/Ti was 0.2, NOx conversion exceeds 94% at 300℃ and GHSV of 41,324 hr-1 , which is about 20% higher than pure V2O5/TiO2 . The catalysts were characterized by XRD, BET, TEM, FT-IR, NH3-TPD, XPS, H2-TPR, Raman and in situ DRIFTS. The results of FT-IR and XPS indicated that Si was doped into the TiO2 lattice successfully and a solid solution was obtained. V2O5 active component could be dispersed well on the support with the increasing of surface area of the catalyst, which was confirmed by Raman and XRD results. Above all, the numbers of acid sites （especially the Br nsted-acid） and oxidation properties were enhanced for Si-doped V2O5/TiO2 catalysts, which improved the deNOx catalytic activity.展开更多
基金supported by the National Natural Science Foundation of China (40472025, 40620120098,40872043)
文摘We describe the new mineral species titanium, ideally Ti, found in the podiform chromitites of the Luobusha ophiolite in Tibet, People＇s Republic of China. The irregular crystals range from 0.1 to 0.6 mm in diameter and form an intergrowth with coesite and kyanite. Titanium is silver grey in colour, the luster is metallic, it is opaque, the streak is grayish black, and it is non-fluorescent. The mineral is malleable, has a rough to hackly fracture and has no apparent cleavage. The estimated Mohs hardness is 4, and the calculated density is 4.503 g/cm3. The composition is Ti 99.23-100.00 wt%. The mineral is hexagonal, space group P6flmmc. Unit-cell parameters are a 2.950 （2） ~, c 4.686 （1） A,V 35.32 （5） A3, Z = 2. The five strongest powder diffraction lines [d in A （hkl） （I/I0）] are： 2.569 （010） （32）, 2.254（011） （100）, 1.730 （012） （16）, 1.478 （110） （21）, and 0.9464 （121） （8）. The species and name were approved by the CNMNC （IMA 2010-044）.
文摘Tailoring the Ti coordination states in titanosilicate zeolites to simultaneously improve feedstock conversion and maximize the target product selectivity remains a challenge in the pursuit of high-performance catalysts for selective oxidation reactions.Herein,we provide a facile strategy to synthesize hierarchical anatase-free TS-1(MFI-type)zeolites with tetrahedrally coordinated(TiO_(4))and octahedrally coordinated Ti species(TiO_(6)).The TiO_(4)species provide high epoxide selectivity,while the TiO_(6)species afford improved alkene conversion.This strategy is achieved by synergistically using an L-lysine-assisted approach and a two-step crystallization;the two-step crystallization approach prevents the formation of anatase TiO_(2),while L-lysine stabilizes the TiO_(6)species and ensures efficient incorporation of TiO_(6)into the anatase-free TS-1 zeolites.Compared with their conventional counterparts,which only contain TiO_(4)species,the as-prepared TS-1 zeolites(Si/Ti=36.9)result in a higher 1-hexene conversion(33%),higher TON value(153),and comparable epoxide selectivity(95%).This synthetic strategy provides avenues to tailor the amount and distribution of Ti species in titanosilicate zeolites to achieve high catalytic performances in various processes.
基金supported by the National Natural Science Foundation of China (91434101)the National Key R&D Plan (2017YFB0702800)~~
文摘A nanocomposite catalyst with a nonstoichiometric titanium oxide loaded on a special nanotubular alumina(γ‐Al2O3‐nt)was developed and used to reduce cinnamaldehyde to cinnamyl alcohol with sacrificial isopropanol,i.e.,a Meerwein‐Ponndorf‐Verley type reaction.The deposition process produced a highly disperse layer of titanium oxide on the surface of aγ‐Al2O3‐nt support.After a reduction treatment,the as‐prepared TiOx/γ‐Al2O3‐nt was a highly efficient catalyst for the hydrogen transfer reaction between isopropanol and cinnamaldehyde.Selectivity for cinnamic alcohol was higher than99%and the conversion of cinnamaldehyde was higher than95%.The regular morphology of theγ‐Al2O3‐nt support with homogeneous surface sites and the uniformly dispersed titanium oxide featured a high concentration surface Ti(III)species.These factors contributed to the high performance of the TiOx/γ‐Al2O3‐nt catalyst.
基金financially supported by the National Natural Science Foundation of China (Nos. 21525313, 21761132005)Chinese Academy of Sciences (No. KJZD-EW-M03)+1 种基金MOE Fundamental Research Funds for the Central Universities (No. WK2060030017)Collaborative Innovation Center of Suzhou Nano Science and Technology
文摘Interaction of hydrogen with TiO2 plays a vital role in TiO2-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species on a rutile TiO2（110） surface formed by atomic H exposure at 320 and 115 K by means of thermal desorption spectroscopy, X-ray photoelectron spectroscopy and low energy electron diffraction. Atomic H interaction with rutile TiO2（110） at 115 K forms surface TiààH hydride, surface hydroxyl group, and chemisorbed water. Upon heating, surface TiààH hydride reacts to produce H2 while surface hydroxyl groups react to form both water and H2. Atomic H interaction with rutile TiO2（110） at 320 K strongly reduces TiO2 due to the continuous formation and desorption of water and forms surface hydroxyl groups and likely subsurface/bulk hydrogen species. Upon heating, hydrogen forms as the only gas-phase product and its desorption activation energy decreases with the subsurface/bulk reduction extent of rutile TiO2（110）. Surface Ti-H hydride exhibits photo-induced reactivity while both surface TiààH hydride and surface hydroxyl group exhibit electro-induced reactivity. These results have important implications for understanding the hydrogen-involved thermal and photo reactions on TiO2-based catalysts.
基金This work was supported by the National Natural Science Foundation of China (Nos.21835002,21621001,22001090)the "111" Project of China(No.B17020)the China Postdoctoral Science Foundation(No.2021T140259).
文摘The exploration of high-efficient catalysts based on hierarchical Ti-containing zeolites with optimized active titanium species distribution is of great value in enhancing the epoxidation of bulky olefins. Herein, hierarchical TS-1(MFI) zeolite with an extra-large external surface area(210 m2/g) and highly active octahedral- coordinated Ti species was prepared via organic base-assisted sequential post-treatment. Such a catalyst afforded a high turnover number value(TON, 114) in 1-octene epoxidation reaction, which was over twice than that(53) of the untreated conventional microporous TS-1 parent. According to the detailed characterization results, we revealed the hierarchical porosity construction effect of tetrapropylamonium hydroxide(TPAOH) treatment(first step) and the octahedral-coordinated Ti species fabrication effect of ethylamine(EA) treatment(second step) under hydrothermal condition. Such a facile post-treatment strategy reported in this work may provide guidance for the rational synthesis of TS-1 zeolite with enhanced catalytic activity.
基金the National Natural Science Foundation of China(Grant Nos.21773153 and 31700311)the Collaborative Innovation Project of Jiangxi Academy of Sciences(2017-XTPH1-05)the Post-Doctoral Project of Jiangxi Academy of Sciences.
文摘Low-cost nickels can be used as cocatalyst to improve the performance of photocatalysts,which may be promising materials applied in the field of photocatalytic water splitting.In this study,different nickel species Ni,Ni(OH)2,NiO,NiOx,and NiS are used to modified titanium dioxide(P25)to investigate their roles on the photocatalytic hydrogen evolution activities.UV-visible,X-ray diffraction(XRD),Brunner-Emmet-Teller(BET)measurements,transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS)analysis etc.are employed to characterize the physical and chemical properties of catalysts.The results indicate that all the nickel species can improve the photocatalytic hydrogen production activity of P25.The P25 modified with NiOx and NiS has more superior photocatalytic hydrogen evolution activities than those modified with other nickel species.The reason for this is that NiOx and NiS can form p-n junctions with P25 respectively.In addition,NiOx can be selectively deposited on the active sites of P25 via in situ the photodeposition method and NiS is beneficial for H+reacting with photo-excited electrons.
基金supported by the Hunan 2011 Collaborative Innovation Center of Chemical Engineering & Technology with Environmental Benignity and Effective Resource Utilization
文摘TiO2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve its photocatalytic activity, the Ti-coating Mg Al hydrotalcite（Ti–Mg Al–LDH） was prepared by chemical vapor deposition（CVD） method.Response surface method（RSM） was employed to evaluate the effect of Ti species coating parameters on the photocatalytic activity, which was found to be affected by the furnace temperature, N2 flow rate and influx time of precursor gas. Application of RSM successfully increased the photocatalytic efficiency of the Ti–Mg Al–LDH in methylene blue photodegradation under UV irradiation, leading to improved economy of the process.According to the results from X-ray diffraction, scanning electron microscopy, Brunner–Emmet–Teller and Barrett–Joyner–Hallender, thermogravimetric and differential thermal analysis, UV–vis diffuse reflectance spectra analyses, the Ti species（TiO2or/and Ti^（4＋）） were successfully coated on the Mg Al–LDH matrix. The Ti species on the surface of the Ti–Mg Al–LDH lead to a higher photocatalytic performance than commercial TiO2-P25. The results suggested that CVD method provided a new approach for the industrial preparation of Ti-coating Mg Al–LDH material with good photocatalytic performances.
基金the funds from the Research Fund for National Key Research and Development Program of China(No.2021YFA1501403)the National Natural Science Foundation of China(Nos.21922803 and 22038003)+1 种基金Shanghai Rising-Star Program(No.17QA1401200)the Innovation Program of the Shanghai Municipal Education Commission(No.17ZR1407300).
文摘The catalytic performances over propylene epoxidation with H_(2)and O_(2)(HOPO process)are significantly affected by the properties(e.g.,surface properties,Ti coordination,morphology)of titanosilicate zeolite.Introducing urea into zeolite synthesis is a simple and convenient method to modify these properties of titanosilicate zeolite.Uncalcined pore-blocked titanium silicalite-1(TS-1,i.e.,TS-1-B)with the lower urea dosage possesses more defective structure and unsaturated coordinated Ti sites verified by 29Si nuclear magnetic resonance(NMR)and X-ray photoelectron spectroscopy(XPS)analysis,which results in a high initial activity and hydrogen efficiency;while the high surface acidity generated by these Ti species leads to a continuous decrease in the activity and the propylene oxide(PO)selectivity during the reaction.As the amount of urea gradually increases,the TS-1-B samples present the reduced surface defects and defective and unsaturated Ti species.Specially,TS-1-B-0.30U presents the weaker PO adsorption on PO-diffusion reflectance infrared Fourier transform spectra(DRIFTS),thus results in the high stable PO formation rate and selectivity over its Au catalyst.Furthermore,a flat-plate-like shape with a shorter thickness of 100 nm along the b-axis direction is observed on the urea-modified TS-1.Compared with the conventional ellipsoidal TS-1 with crystal sizes of 200 and 500 nm,the flat-plate-like TS-1-0.30U displays the less surface defects,unsaturated Ti species,the weaker Lewis acid,which is favorable for the desorption and intracrystalline diffusion of PO,thus reduces the occurrence of side reactions for the improved selectivity and stability.This work may provide a reference for developing titanium-containing materials with high activity and stability over HOPO reaction.
基金supported by the National Natural Science Foundation of China (No. 51078185, U1162119)the research fund of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province (No. AE201001)the research fund for the Doctoral Program of Higher Education of China (No.20113219110009)
文摘TiO2 supports doped with different amounts of Si were prepared by a sol-gel method, and 1 wt% vanadia （V2O5） loaded on Si-doped TiO2 was obtained by an impregnation method. The mole ratio of Si/Ti was 0.2, NOx conversion exceeds 94% at 300℃ and GHSV of 41,324 hr-1 , which is about 20% higher than pure V2O5/TiO2 . The catalysts were characterized by XRD, BET, TEM, FT-IR, NH3-TPD, XPS, H2-TPR, Raman and in situ DRIFTS. The results of FT-IR and XPS indicated that Si was doped into the TiO2 lattice successfully and a solid solution was obtained. V2O5 active component could be dispersed well on the support with the increasing of surface area of the catalyst, which was confirmed by Raman and XRD results. Above all, the numbers of acid sites （especially the Br nsted-acid） and oxidation properties were enhanced for Si-doped V2O5/TiO2 catalysts, which improved the deNOx catalytic activity.
