Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation.In this work,Z-scheme semiconductors composed of WO3-x quantum dots supported on TiO2(WO3-xQDS/TiO2) were fabricated by solvoth...Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation.In this work,Z-scheme semiconductors composed of WO3-x quantum dots supported on TiO2(WO3-xQDS/TiO2) were fabricated by solvothermal and hydrogen-reduction methods.Characterization by transmission electron microscopy and X-ray diffraction indicated that the amount and size of the WO3-x QDs could be tuned by modulating the addition of the W precursor.Evidence from X-ray photoelectron spectroscopy and photoluminescence spectroscopy suggested that the hydrogen reduction of the composite induced the formation of oxygen vacancy(W^5+/Vo) defects in WO3.These defects led to ohmic contact between WO3-x and TiO2,which altered the charge-transfer pathway from type Ⅱ heterojunction to Z-scheme,and maintained the highly reductive and oxidative ability of TiO2 and WO3-x,respectively.Therefore,the Z-scheme sample showed 1.3-fold higher photoactivity than pure TiO2 in hydrogen generation.These results suggest that the formation of W^5+/Vo defects at the interface is highly beneficial for the fabrication of Z-scheme photocatalysts.展开更多
The surface of Titanium Hydride (TiH 2) is coated by Nano Titanium Dioxide (TiO 2) particles prepared in both of methods of hydrolysis reaction of Ti(OC 4H 9) 4 and base precipitation reaction of Ti(SO 4) 2. ...The surface of Titanium Hydride (TiH 2) is coated by Nano Titanium Dioxide (TiO 2) particles prepared in both of methods of hydrolysis reaction of Ti(OC 4H 9) 4 and base precipitation reaction of Ti(SO 4) 2. TiH 2 coated with nano TiO 2 particles, in which there is an oxidation film on its surface, shown in the experiments, will obviously achieve good effects on releasing hydrogen slowly in high temperature. There are different structures and properties of TiH 2 coated by nano TiO 2 particles prepared in different ways in high temperature, which can influence on releasing hydrogen.展开更多
Mg-based Mg-TiO2 composite powder was prepared by arc plasma evaporation of the Mg+5%TiO2 mixture followed by passivation in air. ICP, XRD and SEM techniques were used to characterize the composition, phase component...Mg-based Mg-TiO2 composite powder was prepared by arc plasma evaporation of the Mg+5%TiO2 mixture followed by passivation in air. ICP, XRD and SEM techniques were used to characterize the composition, phase components and microstructure of the composite powder. The hydrogen sorption properties of the composite powder were investigated by DSC and PCT techniques. According to the data from PCT measurements, the hydrogenation enthalpy and entropy changes of the composite powder are calculated to be-71.5 kJ/mol and-130.1 J/(K·mol), respectively. Besides, the hydrogenation activation energy is determined to be 77.2 kJ/ mol. The results indicate that TiO2 added into Mg by arc plasma method can act as a catalyst to improve the hydrogen sorption kinetic properties of Mg.展开更多
Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construc...Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H2 and H2O2 production. Both H2 and H2O2 are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^-1 h^–1 (first 1 h) for H2 and H2O2, respectively, which is much higher than that of a commercial Pt/TiO2(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H2O2, compared with the four-electron oxidation of water to O2.展开更多
TiO2@Ni(OH)2 core-shell microspheres were synthesized by a facile strategy to obtain a perfect 3D flower-like nanostructure with well-arranged Ni(OH)2 nanoflakes on the surfaces of TiO2 microspheres;this arrangement l...TiO2@Ni(OH)2 core-shell microspheres were synthesized by a facile strategy to obtain a perfect 3D flower-like nanostructure with well-arranged Ni(OH)2 nanoflakes on the surfaces of TiO2 microspheres;this arrangement led to a six-fold enhancement in photocatalytic hydrogen evolution. The unique p-n type heterostructure not only promotes the separation and transfer of photogenerated charge carriers significantly, but also offers more active sites for photocatalytic hydrogen production. A photocatalytic mechanism is proposed based on the results of electrochemical measurements and X-ray photoelectron spectroscopy.展开更多
The conversion of CO_(2) to methanol with high activity and high selectivity remains challenging owing to the kinetic and thermodynamic limitations associated with the low chemical reactivity exhibited by CO_(2).Herei...The conversion of CO_(2) to methanol with high activity and high selectivity remains challenging owing to the kinetic and thermodynamic limitations associated with the low chemical reactivity exhibited by CO_(2).Herein,we report a novel Cd/TiO_(2) catalyst exhibiting a methanol selectivity of 81%,a CO_(2) conversion of 15.8%,and a CH_(4) selectivity below 0.7%.A combination of experimental and computational studies revealed that the unique electronic properties exhibited by the Cd clusters supported by the TiO_(2) matrix were responsible for the high selectivity of CO_(2) hydrogenation to methanol via the HCOO*pathway at the interfacial catalytic sites.展开更多
Noble metal palladium(Pd)is well‐known as excellent photocatalytic cocatalyst,but its strong adsorption to hydrogen causes its limited H2‐evolution activity.In this study,the transition metal Cu was successfully int...Noble metal palladium(Pd)is well‐known as excellent photocatalytic cocatalyst,but its strong adsorption to hydrogen causes its limited H2‐evolution activity.In this study,the transition metal Cu was successfully introduced into the metallic Pd to weaken its hydrogen‐adsorption strength to improve its interfacial H_(2)‐evolution rate via the Pd‐Cu alloying effect.Herein,the ultrasmall Pd_(100−x)Cu_(x) alloy nanodots(2−5 nm)as a novel H_(2)‐evolution cocatalyst were integrated with the TiO_(2) through a simple NaH_(2)PO_(2)‐mediated co‐deposition route.The resulting Pd_(100−x)Cu_(x)/TiO_(2) sample shows the significantly enhanced photocatalytic H_(2)‐generation performance(269.2μmol h^(−1)),which is much higher than the bare TiO2.Based on in situ irradiated X‐ray photoelectron spectroscopy(ISI‐XPS)and density functional theory(DFT)results,the as‐formed Pd_(100−x)Cu_(x) alloy nanodots can effectively promote the separation of photo‐generated charges and weak the adsorption strength for hydrogen to optimize the process of hydrogen‐desorption process on Pd_(75)Cu_(25) alloy,thus leading to high photocatalytic H_(2)‐evolution activity.Herein,the weakened H adsorption of Pd_(75)Cu_(25) cocatalyst can be ascribed to the formation of electron‐rich Pd after the introduction of weak electronegativity Cu.The present work about optimizing electronic structure for promoting interfacial reaction activity provides a new sight for the development of the highly efficient photocatalysts.展开更多
In this study,the Cr2O3/C@TiO2 composite was synthesized via the calcination of yolk–shell MIL-101@TiO2.The composite presented core–shell structure,where Cr-doped TiO2 and Cr2O3/C were the shell and core,respective...In this study,the Cr2O3/C@TiO2 composite was synthesized via the calcination of yolk–shell MIL-101@TiO2.The composite presented core–shell structure,where Cr-doped TiO2 and Cr2O3/C were the shell and core,respectively.The introduction of Cr^3+and Cr2O3/C,which were derived from the calcination of MIL-101,in the composite enhanced its visible light absorbing ability and lowered the recombination rate of the photogenerated electrons and holes.The large surface area of the Cr2O3/C@TiO2 composite provided numerous active sites for the photoreduction reaction.Consequently,the photocatalytic performance of the composite for the production of H2 was better than that of pure TiO2.Under the irradiation of a 300 W Xe arc lamp,the H2 production rate of the Cr2O3/C@TiO2 composite that was calcined at 500°C was 446μmol h−1 g−1,which was approximately four times higher than that of pristine TiO2 nanoparticles.Moreover,the composite exhibited the high H2 production rate of 25.5μmol h−1 g−1 under visible light irradiation(λ>420 nm).The high photocatalytic performance of Cr2O3/C@TiO2 could be attributed to its wide visible light photoresponse range and efficient separation of photogenerated electrons and holes.This paper offers some insights into the design of a novel efficient photocatalyst for water-splitting applications.展开更多
A simple and sensitive kinetic spectrophotometric method for the determination of trace amounts of titanium(IV),based upon the catalytic effect of Ti(IV) on the oxidation of acid chrome blue K (ACBK) by hydrogen perox...A simple and sensitive kinetic spectrophotometric method for the determination of trace amounts of titanium(IV),based upon the catalytic effect of Ti(IV) on the oxidation of acid chrome blue K (ACBK) by hydrogen peroxide in 0.002 mol/L sulfuric acid,is described. The reaction rate is monitored spectrophotometrically by measuring the decrease in absorbance of ACBK at 524 nm. The detection limit of the method is 1.01×10?9 g/mL,and the linear range is 0-0.048 mg/L. The influence of acidity,concentration of reactants,reaction time,reaction temperature and for-eign ions is also discussed. The optimum reaction conditions were established and some kinetic parameters determined. The apparent activation energy of the catalytic reaction is 5.32 kJ/mol. The relative standard deviation for the determi-nation of titanium(IV) at the concentration of 0.048 mg/L is calculated to be 1.31% (n = 11). In combination with sol-vent extraction separation,the method has been successfully applied to the determination of trace titanium(IV) in human hair,plant matter,tea and rock samples. The results are in good agreement with the certified values with the relative standard deviations (RSD) of 1.4%-3.5%.展开更多
Unveiling the active site of an electrocatalyst is fundamental for the development of efficient electrode material.For the two-electron water oxidation to produce H_(2)O_(2),competitive reactions,including four-and on...Unveiling the active site of an electrocatalyst is fundamental for the development of efficient electrode material.For the two-electron water oxidation to produce H_(2)O_(2),competitive reactions,including four-and one-electron water oxidation and surface reconstruction derived from the high-oxidative environment co-existed,leading to great challenges to identify the real active sites on the electrode.In this work,Ti/TiO_(2)-based electrodes calcined under air,nitrogen,or urea atmospheres were selected as electrocatalysts for two-electron water oxidation.Electrochemical analyses were applied to evaluate the catalytic activity and selectivity.The morphological and current change on the electrode surface were determined by scanning electrochemical microscopy,while the chemical and valence evolutions with depth distributions were tested by XPS combined with cluster argon ion sputtering.The results demonstrated that Ti/TiO_(2) nanotube arrays served as the support,while the functional groups of carbonyl groups and pyrrolic nitrogen derived from the co-pyrolysis with urea were the active sites for the H_(2)O_(2) production.This finding provided a new horizon to design efficient catalysts for H_(2)O_(2) production.展开更多
基金supported by the National Natural Science Foundation of China (21506156, 21676193)the Tianjin Municipal Natural Science Foundation (15JCZDJC37300, 16JCQNJC05200)~~
文摘Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation.In this work,Z-scheme semiconductors composed of WO3-x quantum dots supported on TiO2(WO3-xQDS/TiO2) were fabricated by solvothermal and hydrogen-reduction methods.Characterization by transmission electron microscopy and X-ray diffraction indicated that the amount and size of the WO3-x QDs could be tuned by modulating the addition of the W precursor.Evidence from X-ray photoelectron spectroscopy and photoluminescence spectroscopy suggested that the hydrogen reduction of the composite induced the formation of oxygen vacancy(W^5+/Vo) defects in WO3.These defects led to ohmic contact between WO3-x and TiO2,which altered the charge-transfer pathway from type Ⅱ heterojunction to Z-scheme,and maintained the highly reductive and oxidative ability of TiO2 and WO3-x,respectively.Therefore,the Z-scheme sample showed 1.3-fold higher photoactivity than pure TiO2 in hydrogen generation.These results suggest that the formation of W^5+/Vo defects at the interface is highly beneficial for the fabrication of Z-scheme photocatalysts.
文摘The surface of Titanium Hydride (TiH 2) is coated by Nano Titanium Dioxide (TiO 2) particles prepared in both of methods of hydrolysis reaction of Ti(OC 4H 9) 4 and base precipitation reaction of Ti(SO 4) 2. TiH 2 coated with nano TiO 2 particles, in which there is an oxidation film on its surface, shown in the experiments, will obviously achieve good effects on releasing hydrogen slowly in high temperature. There are different structures and properties of TiH 2 coated by nano TiO 2 particles prepared in different ways in high temperature, which can influence on releasing hydrogen.
基金Project(11ZR1417600)supported by Shanghai Natural Science Foundation from Science and Technology Committee of Shanghai,ChinaProject(11PJ1406000)supported by‘Pujiang’Project from the Science and Technology Committee of Shanghai+1 种基金Project(12ZZ017)supported by Shanghai Education Commission,ChinaProject(20100073120007)supported by China Education Commission
文摘Mg-based Mg-TiO2 composite powder was prepared by arc plasma evaporation of the Mg+5%TiO2 mixture followed by passivation in air. ICP, XRD and SEM techniques were used to characterize the composition, phase components and microstructure of the composite powder. The hydrogen sorption properties of the composite powder were investigated by DSC and PCT techniques. According to the data from PCT measurements, the hydrogenation enthalpy and entropy changes of the composite powder are calculated to be-71.5 kJ/mol and-130.1 J/(K·mol), respectively. Besides, the hydrogenation activation energy is determined to be 77.2 kJ/ mol. The results indicate that TiO2 added into Mg by arc plasma method can act as a catalyst to improve the hydrogen sorption kinetic properties of Mg.
基金supported by the National Natural Science Foundation of China(21703046)the National Key R&D of China(2016YFF0203803 and 2016YFA0200902)~~
文摘Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H2 and H2O2 production. Both H2 and H2O2 are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^-1 h^–1 (first 1 h) for H2 and H2O2, respectively, which is much higher than that of a commercial Pt/TiO2(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H2O2, compared with the four-electron oxidation of water to O2.
基金supported by the National Natural Science Foundation of China(21773031)the Natural Science Foundation of Fujian Province(2018J01686)the State Key Laboratory of Photocatalysis on Energy and Environment(SKLPEE-2017A01 and SKLPEE-2017B02)~~
文摘TiO2@Ni(OH)2 core-shell microspheres were synthesized by a facile strategy to obtain a perfect 3D flower-like nanostructure with well-arranged Ni(OH)2 nanoflakes on the surfaces of TiO2 microspheres;this arrangement led to a six-fold enhancement in photocatalytic hydrogen evolution. The unique p-n type heterostructure not only promotes the separation and transfer of photogenerated charge carriers significantly, but also offers more active sites for photocatalytic hydrogen production. A photocatalytic mechanism is proposed based on the results of electrochemical measurements and X-ray photoelectron spectroscopy.
文摘The conversion of CO_(2) to methanol with high activity and high selectivity remains challenging owing to the kinetic and thermodynamic limitations associated with the low chemical reactivity exhibited by CO_(2).Herein,we report a novel Cd/TiO_(2) catalyst exhibiting a methanol selectivity of 81%,a CO_(2) conversion of 15.8%,and a CH_(4) selectivity below 0.7%.A combination of experimental and computational studies revealed that the unique electronic properties exhibited by the Cd clusters supported by the TiO_(2) matrix were responsible for the high selectivity of CO_(2) hydrogenation to methanol via the HCOO*pathway at the interfacial catalytic sites.
文摘Noble metal palladium(Pd)is well‐known as excellent photocatalytic cocatalyst,but its strong adsorption to hydrogen causes its limited H2‐evolution activity.In this study,the transition metal Cu was successfully introduced into the metallic Pd to weaken its hydrogen‐adsorption strength to improve its interfacial H_(2)‐evolution rate via the Pd‐Cu alloying effect.Herein,the ultrasmall Pd_(100−x)Cu_(x) alloy nanodots(2−5 nm)as a novel H_(2)‐evolution cocatalyst were integrated with the TiO_(2) through a simple NaH_(2)PO_(2)‐mediated co‐deposition route.The resulting Pd_(100−x)Cu_(x)/TiO_(2) sample shows the significantly enhanced photocatalytic H_(2)‐generation performance(269.2μmol h^(−1)),which is much higher than the bare TiO2.Based on in situ irradiated X‐ray photoelectron spectroscopy(ISI‐XPS)and density functional theory(DFT)results,the as‐formed Pd_(100−x)Cu_(x) alloy nanodots can effectively promote the separation of photo‐generated charges and weak the adsorption strength for hydrogen to optimize the process of hydrogen‐desorption process on Pd_(75)Cu_(25) alloy,thus leading to high photocatalytic H_(2)‐evolution activity.Herein,the weakened H adsorption of Pd_(75)Cu_(25) cocatalyst can be ascribed to the formation of electron‐rich Pd after the introduction of weak electronegativity Cu.The present work about optimizing electronic structure for promoting interfacial reaction activity provides a new sight for the development of the highly efficient photocatalysts.
文摘In this study,the Cr2O3/C@TiO2 composite was synthesized via the calcination of yolk–shell MIL-101@TiO2.The composite presented core–shell structure,where Cr-doped TiO2 and Cr2O3/C were the shell and core,respectively.The introduction of Cr^3+and Cr2O3/C,which were derived from the calcination of MIL-101,in the composite enhanced its visible light absorbing ability and lowered the recombination rate of the photogenerated electrons and holes.The large surface area of the Cr2O3/C@TiO2 composite provided numerous active sites for the photoreduction reaction.Consequently,the photocatalytic performance of the composite for the production of H2 was better than that of pure TiO2.Under the irradiation of a 300 W Xe arc lamp,the H2 production rate of the Cr2O3/C@TiO2 composite that was calcined at 500°C was 446μmol h−1 g−1,which was approximately four times higher than that of pristine TiO2 nanoparticles.Moreover,the composite exhibited the high H2 production rate of 25.5μmol h−1 g−1 under visible light irradiation(λ>420 nm).The high photocatalytic performance of Cr2O3/C@TiO2 could be attributed to its wide visible light photoresponse range and efficient separation of photogenerated electrons and holes.This paper offers some insights into the design of a novel efficient photocatalyst for water-splitting applications.
基金Project 0520002 supported by the Natural Science Foundation of Jiangxi Province
文摘A simple and sensitive kinetic spectrophotometric method for the determination of trace amounts of titanium(IV),based upon the catalytic effect of Ti(IV) on the oxidation of acid chrome blue K (ACBK) by hydrogen peroxide in 0.002 mol/L sulfuric acid,is described. The reaction rate is monitored spectrophotometrically by measuring the decrease in absorbance of ACBK at 524 nm. The detection limit of the method is 1.01×10?9 g/mL,and the linear range is 0-0.048 mg/L. The influence of acidity,concentration of reactants,reaction time,reaction temperature and for-eign ions is also discussed. The optimum reaction conditions were established and some kinetic parameters determined. The apparent activation energy of the catalytic reaction is 5.32 kJ/mol. The relative standard deviation for the determi-nation of titanium(IV) at the concentration of 0.048 mg/L is calculated to be 1.31% (n = 11). In combination with sol-vent extraction separation,the method has been successfully applied to the determination of trace titanium(IV) in human hair,plant matter,tea and rock samples. The results are in good agreement with the certified values with the relative standard deviations (RSD) of 1.4%-3.5%.
基金Project(2021JJ30792) supported by the Natural Science Foundation of Hunan Province,ChinaProject(52170031) supported by the National Natural Science Foundation of ChinaProject supported by the Fundamental Research Funds for the Central Universities,China。
文摘Unveiling the active site of an electrocatalyst is fundamental for the development of efficient electrode material.For the two-electron water oxidation to produce H_(2)O_(2),competitive reactions,including four-and one-electron water oxidation and surface reconstruction derived from the high-oxidative environment co-existed,leading to great challenges to identify the real active sites on the electrode.In this work,Ti/TiO_(2)-based electrodes calcined under air,nitrogen,or urea atmospheres were selected as electrocatalysts for two-electron water oxidation.Electrochemical analyses were applied to evaluate the catalytic activity and selectivity.The morphological and current change on the electrode surface were determined by scanning electrochemical microscopy,while the chemical and valence evolutions with depth distributions were tested by XPS combined with cluster argon ion sputtering.The results demonstrated that Ti/TiO_(2) nanotube arrays served as the support,while the functional groups of carbonyl groups and pyrrolic nitrogen derived from the co-pyrolysis with urea were the active sites for the H_(2)O_(2) production.This finding provided a new horizon to design efficient catalysts for H_(2)O_(2) production.