This article studies the role of electrochemical parameters in controlling the morphology of oxidized TiO_(2)nanotubes and the electrochemical performance of modified TiO_(2)nanotubes.Humidity is a key factor for fabr...This article studies the role of electrochemical parameters in controlling the morphology of oxidized TiO_(2)nanotubes and the electrochemical performance of modified TiO_(2)nanotubes.Humidity is a key factor for fabricating TiO_(2)nanotubes.When the relative humidity belows 70%,the TiO_(2)nanotubes can be successfully prepared.What's more,by changing the anodization voltage and time,the diameter and the length of TiO_(2)nanotubes can be adjusted.In addition,the TiO_(2)nanotubes are modified through electrochemical self-doping and loading Pt metal particles on the surface of the nanotubes,which promotes the performance of the supercapacitor.The sample anodized at 100 V for 3 h has a specific capacity of up to 2.576 mF/cm~2 at a scan rate of 100 mV/s after self-doping,and its capacity retention rate still remains at 89.55%after 5000 cycles,demonstrating excellent cycling stability.The Pt-modified sample has a specific capacity of up to 3.486 mF/cm~2 at the same scan rate,exhibiting more outstanding electrochemical performance.展开更多
TiO_(2)has demonstrated outstanding performance in electrochemical advanced oxidation processes(EAOPs)due to its structural stability and high oxygen overpotential.However,there is still much room for improving its el...TiO_(2)has demonstrated outstanding performance in electrochemical advanced oxidation processes(EAOPs)due to its structural stability and high oxygen overpotential.However,there is still much room for improving its electrochemical activity.Herein,narrow bandgap manganese oxide(MnO_(x))was composited with TiO_(2)nanotube arrays(TiO_(2)NTAs)that in-situ oxidized on porous Ti sponge,forming the MnO_(x)-TiO_(2)NTAs anode.XANES and XPS analysis further proved that the composition of MnO_(x)is Mn2O3.Electrochemical characterizations revealed that increasing the composited concentration of MnO_(x)can improve the conductivity and reduce oxygen evolution potential so as to improve the electrochemical activity of the composited MnO_(x)-TiO_(2)NTAs anode.Meanwhile,the optimal degradation rate of benzoic acid(BA)was achieved using MnO_(x)-TiO_(2)NTAs with a MnO_(x)concentration of 0.1 mmol L^(-1),and the role of MnO_(x)was proposed based on DFT calculation.Additionally,the required electrical energy(EE/O)to destroy BA was optimized by varying the composited concentration of MnO_(x)and the degradation voltage.These quantitative results are of great significance for the design and application of high-performance materials for EAOPs.展开更多
Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology r...Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.展开更多
Titanium dioxide(TiO_2) has been investigated broadly as a stable,safe,and cheap anode material for sodium-ion batteries in recent years.However,the poor electronic conductivity and inherent sluggish sodium ion diffus...Titanium dioxide(TiO_2) has been investigated broadly as a stable,safe,and cheap anode material for sodium-ion batteries in recent years.However,the poor electronic conductivity and inherent sluggish sodium ion diffusion hinder its practical applications.Herein,a self-template and in situ vulcanization strategy is developed to synthesize self-supported hybrid nanotube arrays composed of nitrogen/sulfur-codoped carbon coated sulfur-doped TiO_2 nanotubes(S-TiO_2@NS-C) starting from H_2 Ti_2 O_5-H_2 O nanoarrays.The S-TiO_2@NS-C composite with one-dimensional nano-sized subunits integrates several merits.Specifically,sulfur doping strongly improves the Na~+ storage ability of TiO_2@C-N nanotubes by narrowing the bandgap of original TiO_2.Originating from the nanoarrays structures built from hollow nanotubes,carbon layer and sulfur doping,the sluggish Na~+ insertion/extraction kinetics is effectively improved and the volume variation of the electrode material is significantly alleviated.As a result,the S-TiO_2@NS-C nanoarrays present efficient sodium storage properties.The greatly improved sodium storage performances of S-TiO_2@NS-C nanoarrays confirm the importance of rational engineering and synthesis of hollow array architectures with higher complexity.展开更多
TiO2 nanotube （TNT） arrays were fabricated by anodic oxidation of titanium foil in a fluoride- based solution, on which Cu20 particles were loaded via galvanostatic pulse electrodeposition in cupric acetate solution...TiO2 nanotube （TNT） arrays were fabricated by anodic oxidation of titanium foil in a fluoride- based solution, on which Cu20 particles were loaded via galvanostatic pulse electrodeposition in cupric acetate solutions in the absence of any other additives. The structure and optical properties of Cu2O-loaded TiO2 nanotube arrays （Cu2O-TNTs） were analyzed by scanning electron microscopy （SEM）, X-ray diffraction （XRD） and UV-Vis absorption, and the photoelectrochemical performance was measured using an electrochemical work station with a three-electrode configuration. The results show that the Cu2O particles distribute uniformly on the highly ordered anatase TiO2 nanotube arrays. The morphologies of Cu2O crystals change from branched, truncated octahedrons to dispersive single octahedrons with increasing deposition current densities. The Cu2O- TNTs exhibited remarkable visible light responses with obvious visible light absorption and greatly enhanced visible light photoelectrochemical performance. The I-V characteristics under visible light irradiation show a distinct plateau in the region between approximately -0.3 and 0 V, resulting in higher open-circuit voltages and larger short-circuit currents with increased Cu2O deposition.展开更多
The highly ordered TiO2 nanotubes (NTs) were fabricated by the anodic oxidation method. Their morphology, structure and crystalline phase were characterized by scanning electron microscopy (SEM) and X-ray diffractomet...The highly ordered TiO2 nanotubes (NTs) were fabricated by the anodic oxidation method. Their morphology, structure and crystalline phase were characterized by scanning electron microscopy (SEM) and X-ray diffractometer (XRD). The effects of morphology, specific surface area, pore structures and photo catalytic activity of the TiO2 NTs were investigated. UV-vis spectra analysis showed that its light absorption had been extended to the visible light range. The photocatalytic activity of the as-prepared samples was evaluated by photocatalytic oxidation of gaseous HCHO and MB aqueous solution. The samples had better adhesion strength in the dark and showed a higher photocatalytic activity than nanoparticles. Especially, with ultraviolet light pretreatment, the nanotubes exhibited more stable active for photocatalytic decomposition and the photodecomposition rate remained at high level after 3 cycles of the photocatalysis experiment. Thus, how the number of surface active group center dot OH increased and the mechanism for the great improvement for the photocatalytic activity are discussed. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great e...1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great efforts have been made to synthesize 1T-MoS_(2) and enhance its stability,it remains a big challenge to realize the phase control and stabilization of 1T-MoS_(2).Herein,based on crystal field theory analysis,we propose a new solution by designing an electrocatalyst of 1T-MoS_(2) nanosheets anchoring on black TiO2-xnanotube arrays in-situ grown on Ti plate(1T-MoS_(2)/TiO_(2-x)@Ti).The black TiO_(2-x)substrate is expected to play as electron donors to increase the charge in Mo 4 d orbits of 1T-MoS_(2) and thus weaken the asymmetric occupation of electrons in the Mo 4 d orbits.Experimental results demonstrate that black TiO_(2-x)nanotubes shift electrons to MoS_(2) and induce MoS_(2) to generate more 1 T phase due to stabilizing the 1T-MoS_(2) nanosheets compared with a Ti substrate.Thus 1T-MoS_(2/)TiO_(2-x)@Ti shows much improved HER performance with a small Tafel slope of 42 m V dec^(-1) and excellent catalytic stability with negligible degradation for 24 h.Theoretical calculations confirm that the black TiO_(2-x)substrate can effectively stabilize metastable 1T-MoS_(2) due to electrons transferring from black TiO_(2-x)to Mo 4 d orbits.This work sheds light on the instability of 1T-MoS_(2) and provides an essential method to stabilize and efficiently utilize 1T-MoS_(2) for HER.展开更多
Both Ti foil and porous Ti were anodized in 0.5%HF and in ethylene glycol electrolyte containing 0.5%NH4F(mass fraction) separately. The results show that TiO2 nanotubes can be formed on Ti foil by both processes, whe...Both Ti foil and porous Ti were anodized in 0.5%HF and in ethylene glycol electrolyte containing 0.5%NH4F(mass fraction) separately. The results show that TiO2 nanotubes can be formed on Ti foil by both processes, whereas TiO2 nanotubes can be formed on porous Ti only in the second process. The overhigh current density led to the failure of the formation nanotubes on porous Ti in 0.5%HF electrolyte. TiO2 nanotubes were characterized by SEM and XRD. TiO2 nanotubes on porous Ti were thinner than those on Ti foil. Anatase was formed when TiO2 nanotubes were annealed at 400 °C and fully turned into rutile at 700 °C. To obtain good photodegradation, the optimal heat treatment temperature of TiO2 nanotubes was 450 °C. The porosity of the substrates influenced photodegradation properties. TiO2 nanotubes on porous Ti with 60% porosity had the best photodegradation.展开更多
基金National Natural Science Foundation of China(No.12004070)。
文摘This article studies the role of electrochemical parameters in controlling the morphology of oxidized TiO_(2)nanotubes and the electrochemical performance of modified TiO_(2)nanotubes.Humidity is a key factor for fabricating TiO_(2)nanotubes.When the relative humidity belows 70%,the TiO_(2)nanotubes can be successfully prepared.What's more,by changing the anodization voltage and time,the diameter and the length of TiO_(2)nanotubes can be adjusted.In addition,the TiO_(2)nanotubes are modified through electrochemical self-doping and loading Pt metal particles on the surface of the nanotubes,which promotes the performance of the supercapacitor.The sample anodized at 100 V for 3 h has a specific capacity of up to 2.576 mF/cm~2 at a scan rate of 100 mV/s after self-doping,and its capacity retention rate still remains at 89.55%after 5000 cycles,demonstrating excellent cycling stability.The Pt-modified sample has a specific capacity of up to 3.486 mF/cm~2 at the same scan rate,exhibiting more outstanding electrochemical performance.
基金the support from the Brook Byers Institute for Sustainable Systems,Hightower ChairGeorgia Research Alliance at the Georgia Institute of Technology。
文摘TiO_(2)has demonstrated outstanding performance in electrochemical advanced oxidation processes(EAOPs)due to its structural stability and high oxygen overpotential.However,there is still much room for improving its electrochemical activity.Herein,narrow bandgap manganese oxide(MnO_(x))was composited with TiO_(2)nanotube arrays(TiO_(2)NTAs)that in-situ oxidized on porous Ti sponge,forming the MnO_(x)-TiO_(2)NTAs anode.XANES and XPS analysis further proved that the composition of MnO_(x)is Mn2O3.Electrochemical characterizations revealed that increasing the composited concentration of MnO_(x)can improve the conductivity and reduce oxygen evolution potential so as to improve the electrochemical activity of the composited MnO_(x)-TiO_(2)NTAs anode.Meanwhile,the optimal degradation rate of benzoic acid(BA)was achieved using MnO_(x)-TiO_(2)NTAs with a MnO_(x)concentration of 0.1 mmol L^(-1),and the role of MnO_(x)was proposed based on DFT calculation.Additionally,the required electrical energy(EE/O)to destroy BA was optimized by varying the composited concentration of MnO_(x)and the degradation voltage.These quantitative results are of great significance for the design and application of high-performance materials for EAOPs.
基金financially supported by the National Natural Science Foundation of China (Nos.U2002212,52102058,52204414,52204413,and 52204412)the National Key R&D Program of China (Nos.2021YFC1910504,2019YFC1907101,2019YFC1907103,and 2017YFB0702304)+7 种基金the Key R&D Program of Ningxia Hui Autonomous Region,China (Nos.2021BEG01003 and2020BCE01001)the Xijiang Innovation and Entrepreneurship Team,China (No.2017A0109004)the Macao Young Scholars Program (No.AM2022024),Chinathe Beijing Natural Science Foundation (Nos.L212020 and 2214073),Chinathe Guangdong Basic and Applied Basic Research Foundation,China (Nos.2021A1515110998 and 2020A1515110408)the China Postdoctoral Science Foundation (No.2022M710349)the Fundamental Research Funds for the Central Universities,China (Nos.FRF-BD-20-24A,FRF-TP-20-031A1,FRF-IC-19-017Z,and 06500141)the Integration of Green Key Process Systems MIIT and Scientific and Technological Innovation Foundation of Foshan,China(Nos.BK22BE001 and BK21BE002)。
文摘Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.
基金financial supports provided by the National Natural Science Foundation of China (21871164)the Taishan Scholar Project Foundation of Shandong Province (ts20190908, ts201511004)the Natural Science Foundation of Shandong Province (ZR2019MB024)。
文摘Titanium dioxide(TiO_2) has been investigated broadly as a stable,safe,and cheap anode material for sodium-ion batteries in recent years.However,the poor electronic conductivity and inherent sluggish sodium ion diffusion hinder its practical applications.Herein,a self-template and in situ vulcanization strategy is developed to synthesize self-supported hybrid nanotube arrays composed of nitrogen/sulfur-codoped carbon coated sulfur-doped TiO_2 nanotubes(S-TiO_2@NS-C) starting from H_2 Ti_2 O_5-H_2 O nanoarrays.The S-TiO_2@NS-C composite with one-dimensional nano-sized subunits integrates several merits.Specifically,sulfur doping strongly improves the Na~+ storage ability of TiO_2@C-N nanotubes by narrowing the bandgap of original TiO_2.Originating from the nanoarrays structures built from hollow nanotubes,carbon layer and sulfur doping,the sluggish Na~+ insertion/extraction kinetics is effectively improved and the volume variation of the electrode material is significantly alleviated.As a result,the S-TiO_2@NS-C nanoarrays present efficient sodium storage properties.The greatly improved sodium storage performances of S-TiO_2@NS-C nanoarrays confirm the importance of rational engineering and synthesis of hollow array architectures with higher complexity.
基金Funded by the National Natural Science Foundation of China(No.51175363)the Youth Staff Fund of Taiyuan University of Technology(Nos.K201016,K201013)+1 种基金the Specialized Fund for Innovative of College Students of Taiyuan City(No.09122018)the Program for Changjiang Scholar and Innovative Research Team in University(No.IRT0972)
文摘TiO2 nanotube （TNT） arrays were fabricated by anodic oxidation of titanium foil in a fluoride- based solution, on which Cu20 particles were loaded via galvanostatic pulse electrodeposition in cupric acetate solutions in the absence of any other additives. The structure and optical properties of Cu2O-loaded TiO2 nanotube arrays （Cu2O-TNTs） were analyzed by scanning electron microscopy （SEM）, X-ray diffraction （XRD） and UV-Vis absorption, and the photoelectrochemical performance was measured using an electrochemical work station with a three-electrode configuration. The results show that the Cu2O particles distribute uniformly on the highly ordered anatase TiO2 nanotube arrays. The morphologies of Cu2O crystals change from branched, truncated octahedrons to dispersive single octahedrons with increasing deposition current densities. The Cu2O- TNTs exhibited remarkable visible light responses with obvious visible light absorption and greatly enhanced visible light photoelectrochemical performance. The I-V characteristics under visible light irradiation show a distinct plateau in the region between approximately -0.3 and 0 V, resulting in higher open-circuit voltages and larger short-circuit currents with increased Cu2O deposition.
基金financial support from Tianjin Science and Technology Support Plan Key Projects(NO.12ZCZDJC35600)
文摘The highly ordered TiO2 nanotubes (NTs) were fabricated by the anodic oxidation method. Their morphology, structure and crystalline phase were characterized by scanning electron microscopy (SEM) and X-ray diffractometer (XRD). The effects of morphology, specific surface area, pore structures and photo catalytic activity of the TiO2 NTs were investigated. UV-vis spectra analysis showed that its light absorption had been extended to the visible light range. The photocatalytic activity of the as-prepared samples was evaluated by photocatalytic oxidation of gaseous HCHO and MB aqueous solution. The samples had better adhesion strength in the dark and showed a higher photocatalytic activity than nanoparticles. Especially, with ultraviolet light pretreatment, the nanotubes exhibited more stable active for photocatalytic decomposition and the photodecomposition rate remained at high level after 3 cycles of the photocatalysis experiment. Thus, how the number of surface active group center dot OH increased and the mechanism for the great improvement for the photocatalytic activity are discussed. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
基金supported by the New Zealand China Doctoral Research Scholarship (Grant no. 201706080124)support from the China Scholarships Council (CSC) for his study at the University of Auckland
文摘1T phase MoS_(2)(1T-MoS_(2)) is a promising substitute of platinum electrocatalyst for hydrogen evolution reaction(HER)due to its high intrinsic activity but suffering from thermodynamical instability.Although great efforts have been made to synthesize 1T-MoS_(2) and enhance its stability,it remains a big challenge to realize the phase control and stabilization of 1T-MoS_(2).Herein,based on crystal field theory analysis,we propose a new solution by designing an electrocatalyst of 1T-MoS_(2) nanosheets anchoring on black TiO2-xnanotube arrays in-situ grown on Ti plate(1T-MoS_(2)/TiO_(2-x)@Ti).The black TiO_(2-x)substrate is expected to play as electron donors to increase the charge in Mo 4 d orbits of 1T-MoS_(2) and thus weaken the asymmetric occupation of electrons in the Mo 4 d orbits.Experimental results demonstrate that black TiO_(2-x)nanotubes shift electrons to MoS_(2) and induce MoS_(2) to generate more 1 T phase due to stabilizing the 1T-MoS_(2) nanosheets compared with a Ti substrate.Thus 1T-MoS_(2/)TiO_(2-x)@Ti shows much improved HER performance with a small Tafel slope of 42 m V dec^(-1) and excellent catalytic stability with negligible degradation for 24 h.Theoretical calculations confirm that the black TiO_(2-x)substrate can effectively stabilize metastable 1T-MoS_(2) due to electrons transferring from black TiO_(2-x)to Mo 4 d orbits.This work sheds light on the instability of 1T-MoS_(2) and provides an essential method to stabilize and efficiently utilize 1T-MoS_(2) for HER.
基金Project(1254G024)supported by the Young Core Instructor Foundation from Heilongjiang Educational Committee,ChinaProject(2012RFQXS113)supported by Scientific and Technological Innovation Talents of Harbin,China
文摘Both Ti foil and porous Ti were anodized in 0.5%HF and in ethylene glycol electrolyte containing 0.5%NH4F(mass fraction) separately. The results show that TiO2 nanotubes can be formed on Ti foil by both processes, whereas TiO2 nanotubes can be formed on porous Ti only in the second process. The overhigh current density led to the failure of the formation nanotubes on porous Ti in 0.5%HF electrolyte. TiO2 nanotubes were characterized by SEM and XRD. TiO2 nanotubes on porous Ti were thinner than those on Ti foil. Anatase was formed when TiO2 nanotubes were annealed at 400 °C and fully turned into rutile at 700 °C. To obtain good photodegradation, the optimal heat treatment temperature of TiO2 nanotubes was 450 °C. The porosity of the substrates influenced photodegradation properties. TiO2 nanotubes on porous Ti with 60% porosity had the best photodegradation.
