Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolu...Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.展开更多
The paper reports the fabrication of Zn-doped TiO_2 nanotubes(Zn-TONT)/ZnO nanoflakes heterostructure for the first time,which shows improved performance as a photoanode in dye-sensitized solar cell(DSSC).The layered ...The paper reports the fabrication of Zn-doped TiO_2 nanotubes(Zn-TONT)/ZnO nanoflakes heterostructure for the first time,which shows improved performance as a photoanode in dye-sensitized solar cell(DSSC).The layered structure of this novel nanoporous structure has been analyzed unambiguously by Rutherford backscattering spectroscopy,scanning electron microscopy,and X-ray diffractometer.The cell using the heterostructure as photoanode manifests an enhancement of about an order in the magnitude of the short circuit current and a seven-fold increase in efficiency,over pure TiO_2 photoanodes.Characterizations further reveal that the Zn-TONT is preferentially oriented in [001] direction and there is a Ti metal-depleted interface layer which leads to better band alignment in DSSC.展开更多
TiO2 nanotube arrays （TNTs） electrode loaded with Zn nanoparticles was prepared by anodization and the size of Zn nanoparticle loaded on TNTs electrode was controlled by chronoamperometry deposition time. Results of...TiO2 nanotube arrays （TNTs） electrode loaded with Zn nanoparticles was prepared by anodization and the size of Zn nanoparticle loaded on TNTs electrode was controlled by chronoamperometry deposition time. Results of SEM and XRD analysis show that Zn nanoparticles had a diameter of about 15-25 nm when the deposition time was 3-5 s. The UV-Vis diffuse reflectance spectra show the Zn loaded harvest light with 480-780 nm more effectively than the unloaded sample. The photocurrent response of Zn loaded TNTs electrodes were studied, the results showed that TNTs electrodes loaded with Zn nanoparti-cles has 50% increased photocurrent response under high-pressure mercury lamp irradiation compared with unloaded TNTs electrode.展开更多
Vertically orientated TiO2 nanotube array with diameters ranging from 60 up to 80 nm and length of 4 μm was grown on titanium by anodization.Crack initiation,propagation and saturation were studied using the substrat...Vertically orientated TiO2 nanotube array with diameters ranging from 60 up to 80 nm and length of 4 μm was grown on titanium by anodization.Crack initiation,propagation and saturation were studied using the substrate straining test.The results show that annealing obviously modifies the interfaces.With the increase of tensile strain,cracks in TiO2 nanotube films propagate rapidly and reach the saturation within a narrow strain gap.Interfacial shear strengths of TiO2 nanotube films without annealing,with 250 ℃ annealing and with 400 ℃ annealing can be estimated as 163.3,370.2 and 684.5 MPa,respectively.The critical energy release rates of TiO2 nanotube films are calculated as 49.6,102.6 and 392.7 J/m2,respectively.The fracture toughnesses of TiO2 nanotube films are estimated as 0.996,1.433 and 2.803 MPa-m1/2,respectively.The interfacial bonding mechanism of TiO2 nanotube film is chemical bonding.展开更多
Substrate straining test was carried out to study the buckling pattern of TiO2 nanotube film. The results show that the tensile strains of buckling occurrence of TiO2 nanotube films without annealing, with 250 ℃ anne...Substrate straining test was carried out to study the buckling pattern of TiO2 nanotube film. The results show that the tensile strains of buckling occurrence of TiO2 nanotube films without annealing, with 250 ℃ annealing and with 400 ℃ annealing are 2.5%, 8.9% and 7.8%, respectively, which indicates the modifying effects of temperature annealing. Through the SEM observation, the critical buckling stresses of TiO2 nanotube films without annealing, with 250 ℃ annealing and with 400 ℃ annealing can be estimated as 180.4, 410.2 and 619.5 MPa, respectively. The critical buckling stress of TiO2 nanotube films with 250 ℃ annealing from AFM observation is estimated as 470.2 MPa, which indicates good agreement with the critical buckling stress from SEM observation. The true stress and the critical energy release rate of TiO2 nanotube film with 250 ℃ annealing are given as 840.3 MPa and 77.2 J/m2, respectively. Excellent agreement of the critical energy release rate of TiO2 nanotube film with 250 ℃ annealing in terms of buckling perspective and crack perspective is obtained.展开更多
Curvature method was used to measure the residual stress and substrate straining tensile test was carried out to study the debonding behavior of TiO2 nanotube film. The results indicate that the internal residual stre...Curvature method was used to measure the residual stress and substrate straining tensile test was carried out to study the debonding behavior of TiO2 nanotube film. The results indicate that the internal residual stress is -54 MPa. The strains of debonding initiation of TiO2 nanotube films without annealing, with 250 °C annealing and with 400 °C annealing are 2.6%, 5.1% and 8.6%, respectively, and the average radii of the debonding patches with debonding initiation are 27.5, 17.1 and 19.4 μm, respectively. The true critical debonding stresses of TiO2 nanotube films without annealing, with 250 °C annealing and with 400 °C annealing can be estimated as 220.4, 394.5 and 627.9 MPa, respectively. Interfacial shear lag model is modified and polynomial fitting equation of the interfacial shear strength of TiO2 nanotube film is demonstrated under debonding conditions. The modification and polynomial fitting are reliable since good agreement of the interfacial shear strengths after fitting is obtained compared with those results from the crack density analysis.展开更多
A novel titanium dioxide （TiO2） film comprising both nanotubes and nanopaticles was fabricated by an anodization process of the modified titanium. The local electric field at the anodized surface was simulated and i...A novel titanium dioxide （TiO2） film comprising both nanotubes and nanopaticles was fabricated by an anodization process of the modified titanium. The local electric field at the anodized surface was simulated and its influence on the morphology of the TiO2 film was discussed. The results show that the electric field strength is enhanced by the covering. The growth rate of TiO2 increases with the assist of the local electric field. However, TiO2 dissolution is hindered since the local electric field prevents [TiF6]6- from diffusing. It means that the balance condition for the formation of nanotubes is broken, and TiO2 nanoparticles are formed. Moreover, the crystal structure of the TiO2 film was confirmed using X-ray diffraction and Raman analysis. The anatase is a main phase for the proposed film.展开更多
Two-dimensional (2D) ultrathin MoS2-modified black Ti^3+-TiO2 nanotubes were fabricated using an electrospinning-hydrothermal treatment-reduction method.Bare TiO2 nanotubes were fabricated via electrospinning.Then,2D ...Two-dimensional (2D) ultrathin MoS2-modified black Ti^3+-TiO2 nanotubes were fabricated using an electrospinning-hydrothermal treatment-reduction method.Bare TiO2 nanotubes were fabricated via electrospinning.Then,2D MoS2 lamellae were grown on the surface of the nanotubes and Ti^3+/Ov ions were introduced by reduction.The photocatalytic performance of the 2D MoS2/Ti^3+-TiO2 nanotubes was^15 times better than that of TiO2.The HER enhancement of the MoS2/Ti^3+-TiO2 nanotubes can be attributed to the Pt-like behavior of 2D MoS2 and the presence of Ti^3+-ions,which facilitated the quick diffusion of the photogenerated electrons to water,reducing the H2 activation barrier.The presence of Ov ions in the nanotubes and their hollow structure increased their solar utilization.展开更多
A PbO2/Sb-SnO2/TiO2 nanotube array composite electrode was successfully synthesized and its electrochemical oxidation properties were investigated.Field-emission scanning electron microscopy(FE-SEM)and X-ray diffracti...A PbO2/Sb-SnO2/TiO2 nanotube array composite electrode was successfully synthesized and its electrochemical oxidation properties were investigated.Field-emission scanning electron microscopy(FE-SEM)and X-ray diffraction(XRD)results showed that the PbO2 coating was composed of anα-PbO2 inner layer and aβ-PbO2 outer layer.Accelerated life measurement indicated that the composite electrode had a lifetime of 815 h.Rhodamine B(RhB)was employed as a model pollutant to analyze the electrocatalytic activity of the electrode.The effects of initial RhB concentration,current density,initial pH,temperature,and chloride ion concentration on the electrochemical oxidation were investigated in detail.Inductively coupled plasma atomic emission spectroscopy(ICP-AES)results suggested that the concentration of leached Pb^2+in the electrolyte during the electrocatalytic oxidation process can be neglected.Finally,the degradation mechanism during the electrocatalytic oxidation process was proposed based on the results of solid-phase micro-extraction-gas chromatography-mass spectrometry(SPME-GC-MS).The high electrocatalytic performance of the composite electrode makes it a promising anode for the treatment of organic pollutants in aqueous solution.展开更多
The process, that the polycrystalline TiO2 powders were converted into TiO2 nanotubes, was observed with transmission electron microscope. The results obtained indicated that in concentrated NaOH aqueous solution, an...The process, that the polycrystalline TiO2 powders were converted into TiO2 nanotubes, was observed with transmission electron microscope. The results obtained indicated that in concentrated NaOH aqueous solution, anisotropic swelling appears on the polycrystalline TiO2 granula at first, and then the nanotubes are formed.展开更多
TiO2 nanotube precursor was synthesized by the hydrothermal reaction of TiO2 powders with NaOH solution and the properties of the nanotube materials were tuned using different post-treatments. Transmission electron mi...TiO2 nanotube precursor was synthesized by the hydrothermal reaction of TiO2 powders with NaOH solution and the properties of the nanotube materials were tuned using different post-treatments. Transmission electron microscopic （TEM） observation revealed that the nanotube could be obtained by either a direct rinse with acid solution or rinse with distilled water followed by acid solution. The results of X-ray diffraction （XRD） and inductively coupled plasma （ICP） analysis indicated that the nanotube material was composed of H2Ti2O5·H2O. In addition, the photocatalytic activities of the resulting catalysts were found to be strongly dependent on the post-treatment. The results of the photocatalytic reaction showed that the degradation of Acid-red 3B dye fitted pseudo-zero-order kinetics and TiO2 nanotube prepared under direct rinse with acid solution exhibited a higher catalytic efficiency compared to other catalysts.展开更多
A layer of graphene(GR)particles was successfully deposited at the interface between Co(OH)2 nanoparticles and TiO2 nanotubes,aiming to improve the photoelectrochemical performance of the large-bandgap semiconductor T...A layer of graphene(GR)particles was successfully deposited at the interface between Co(OH)2 nanoparticles and TiO2 nanotubes,aiming to improve the photoelectrochemical performance of the large-bandgap semiconductor TiO2.The obtained Co(OH)2/GR/TiO2 was extensively characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV–vis absorption spectra and photoluminescence(PL)emission spectra.Electrochemical impedance spectra,photogenerated potential-time(E-t),photocurrent density-time(i-t)and i-E curves and open circuit potential(OCP)curves were measured to investigate the photoelectrochemical activities and photogenerated cathodic protection properties.The results revealed that Co(OH)2/GR/TiO2 exhibits excellent photoelectrochemical and photogenerated cathodic performance due to synergistic effect between Co(OH)2 and graphene.Co(OH)2 and graphene co-modified TiO2 photoanode could provide an effective protection for 304 stainless steel(304 SS)in 3.5 wt%Na Cl solution for 12 h,which would be promising for future practical applications in the field of marine corrosion protection.展开更多
We report the development of a novel visible response BiVO_4/TiO_2(N_2) nanotubes photoanode for photoelectrocatalytic applications. The nitrogen-treated TiO_2 nanotube shows a high carrier concentration rate, thus re...We report the development of a novel visible response BiVO_4/TiO_2(N_2) nanotubes photoanode for photoelectrocatalytic applications. The nitrogen-treated TiO_2 nanotube shows a high carrier concentration rate, thus resulting in a high efficient charge transportation and low electron–hole recombination in the TiO_2–BiVO_4. Therefore, the BiVO_4/TiO_2(N_2) NTs photoanode enabled with a significantly enhanced photocurrent of 2.73 mA cm^(-2)(at 1 V vs. Ag/Ag Cl) and a degradation efficiency in the oxidation of dyes under visible light. Field emission scanning electron microscopy, X-ray diffractometry, energy-dispersive X-ray spectrometer, and UV–Vis absorption spectrum were conducted to characterize the photoanode and demonstrated the presence of both metal oxides as a junction composite.展开更多
Due to increasingly serious environmental problems,many researchers are investigating green cleanenergy to solve the world’s energy supply issues.So the strategy that Au nanoparticles(Au NPs)and bismuth sulfide(Bi2S3...Due to increasingly serious environmental problems,many researchers are investigating green cleanenergy to solve the world’s energy supply issues.So the strategy that Au nanoparticles(Au NPs)and bismuth sulfide(Bi2S3)NPs are used to evenly decorate TiO2 nanotube arrays(TiO2 NTAs)was carried out.Composite materials demonstrated enhanced solar light absorption ability and excellent photoelectrochemical performance.This was attributed to the presence of Bi2S3 NPs with a narrow band gap and the decoration with noble metallic Au NPs which resulted in local surface plasmon resonance(LSPR)effects.The Au/Bi2S3@TiO2 NTAs composites exhibit improved photocatalytic activity for the degradation of methylene blue(MB)under irradiation of UV and visible light.Moreover,the Au/Bi2S3@TiO2 NTAs exhibits high fluorescence emission at 822 nm.Due to the better binding affinity between Bi2S3,TiO2 and Fe3+ions,the synthesized nanocomposites exhibit high selectivity to Fe3+ions.The number of binding sites for Au/Bi2S3@TiO2 NTAs was estimated to be 1.41 according to the double logarithmic regression method.The calculated value of"K"was 1862 M-1.Fluorescence emission intensity decreases with increasing concentration(30μM–5000μM).The detection limit of the synthesized sensor is 0.221μM.展开更多
Well crystallized niobium-doped TiO; nanotube arrays （TiNbO-NT） were successfully synthesized via the anodization of titanium/niobium alloy sheets, followed with a heat treatment at 550 ℃ for 2 h. Morphology analys...Well crystallized niobium-doped TiO; nanotube arrays （TiNbO-NT） were successfully synthesized via the anodization of titanium/niobium alloy sheets, followed with a heat treatment at 550 ℃ for 2 h. Morphology analysis results demonstrated that both the titanium/niobium alloy microstructure and the dissolution strength of electrolyte played major roles in the formation of nanotube structure. A single-phase microstructure was more favorable to the formation of uniform nanotube arrays, while modulating the dissolution strength of electrolyte was required to obtain nanotube arrays from the alloys with multi-phase microstructures. X-ray diffraction （XRD） and X-ray photoelectron （XPS） analysis results clearly demonstrated that niobium dopants （Nb^5＋） were successfully doped into TiO2 anatase lattice by substituting Ti^4＋ in this approach.展开更多
TiO2 nanotube arrays were prepared by means of an electrochemical anodization technique in an organic electrolyte solution doped with polyvinyl pyrrolidone (PVP) and were subsequently modified with phosphomolybdic aci...TiO2 nanotube arrays were prepared by means of an electrochemical anodization technique in an organic electrolyte solution doped with polyvinyl pyrrolidone (PVP) and were subsequently modified with phosphomolybdic acid (PMoA) to obtain PMoA/TiO2 nanotube arrays. The microstructure and photochromic properties were investigated via X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-vis), and X-ray photoelectron spectroscopy (XPS). The results indicated that the Keggin structure of PMoA and the nanotube structure of TiO2 were not destroyed, and there was a strong degree of interaction between PMoA and TiO2 at the biphasic interface with lattice interlacing during the compositing process. The XPS results further indicated that there was a change in the chemical microenvironment during the formation process of the composite, and a new charge transfer bridge was formed through the Mo-O-Ti bond. Under visible light irradiation, the colorless PMoA/TiO2 nanotube array quickly turned blue and exhibited a photochromic response together with reversible photochromism in the presence of H2O2. After visible light irradiation for 60s, the appearance of Mo^5+ species in the XPS spectra indicated a photoreduction process in accordance with a photoinduced electron transfer mechanism.展开更多
Copper and titanium remain relatively plentiful in earth crust.Therefore,using them in solar energy conversion technologies are of significant interest.In this work,cuprous oxide（Cu2O）-modified short TiO2 nanotube a...Copper and titanium remain relatively plentiful in earth crust.Therefore,using them in solar energy conversion technologies are of significant interest.In this work,cuprous oxide（Cu2O）-modified short TiO2 nanotube array electrode was prepared based on the following two design ideas:first,the short titania nanotubes obtained from sonoelectrochemical anodization possess excellent charge separation and transportation properties as well as desirable mechanical stability;second,the sonoelectrochemical deposition technique favours the improvement in the combination between Cu2O and TiO2 nanotubes,and favours the dispersion of Cu2O particles.UV-Vis absorption and photo-electronchemical measurements proved that the Cu2O coating extended the visible spectrum absorption and the solar spectrum-induced photocurrent response.Under AM1.5 irradiation,the photocurrent density of the composite electrode（i.e.sonoelectrochemical deposition for 5 min） was more than 4.75 times as high as the pure nanotube electrode.Comparing the photoactivity of the Cu2O/TiO2 electrode obtained using sonoelectrochemical deposition with others that synthesized using plain electrochemical deposition,the photocurrent density of the former electrode was 2.2 times higher than that of the latter when biased at 1.0 V（vs.Ag/AgCl）.The reproducible photocurrent response under intermittent illumination demonstrated the excellent stability of the composite electrode.Such kind of composite electrode material will have many potential applications in solar cell and other fields.展开更多
IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and character...IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and characterized by means of structural,surface analytical and electrochemical techniques.Nb doping of titania significantly increased the surface area of the support from 145(TNTs)to 260 m2g-1(Nb-TNTs),which was significantly higher than those of the Nb-doped titania supports previously reported in the literature.The surface analytical techniques showed good dispersion of the catalysts onto the supports.The X-ray photoelectron spectroscopy analyses showed that Nb was mainly in the form of Nb(IV)species,the suitable form to behave as a donor introducing free electrons to the conduction band of titania.The redox transitions of the cyclic voltammograms,in agreement with the XPS results,were found to be reversible.Despite the supported materials presented bigger crystallite sizes than the unsupported ones,the total number of active sites of the former was also higher due to their better catalyst dispersion.Considering the outer and the total charges of the cyclic voltammograms in the range 0.1–1.4 V,stability and electrode potentials at given current densities,the preferred catalyst was Ir O2 supported on the Nb-TNTs.The electrode potentials corresponding to given current densities were between the smallest ones given in the literature despite the small oxide loading used in this work and its Nb doping,thus making the Nb-TNTs-supported IrO2 catalyst a promising candidate for the OER.The good dispersion of IrO2,high specific surface area of the Nb-doped supports,accessibility of the electroactive centers,increased stability due to Nb doping and electron donor properties of the Nb(IV)oxide species were considered the main reasons for its good performance.展开更多
Polyaniline （PANI） composite nanotubes （90-130 nm in diameter） containing titanium dioxide （TiO2） nanoparticles （about 10 nm in diameter） were synthesized through a self-assembly process in the presence of a-n...Polyaniline （PANI） composite nanotubes （90-130 nm in diameter） containing titanium dioxide （TiO2） nanoparticles （about 10 nm in diameter） were synthesized through a self-assembly process in the presence of a-naphthalenesulfonic acid （a-NSA） as the dopant. It was found that PANI-TiO2 composites and PANI nanotubes both behaved with significant photocatalytic activities towards AZO dyes, during 2 h photocatalytic processes under natural light, the degradation ratio was 94.2% and 97.2% respectively （methyl orange and orange II）. The morphology of such products was characterized by SEM. The specific surface area of such composite nanotubes was 14.7 m2/g compared to normal polyaniline which was 0.27 m2/g. IR and X-ray diffraction characterizations showed that the chemical chain of the composite nanotubes was identical to that of the doped PANI. It may provide a new way for photodegradation of organic contaminants by using conjugated polymer with dimensional structure.展开更多
基金support from the European Union Horizon 2020 program(project HERMES,nr.952184)the Ministry of Education,Youth and Sports of the Czech Republic for supporting CEMNAT(LM2023037)+1 种基金Czech-NanoLab(LM2023051)infrastructures for providing ALD,SEM,EDX,XPS,TEM,and XRDCzech Science Foundation(project 23-08019X,EXPRO).
文摘Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.
基金UGC-DAE CSR,Indore,for funding through a collaborative project and SAIF IIT Bombay for the help with SEMsupported by the Michigan Space Grant Consortium+1 种基金by Hope CollegeDAE-BRNS for funding the preliminary works
文摘The paper reports the fabrication of Zn-doped TiO_2 nanotubes(Zn-TONT)/ZnO nanoflakes heterostructure for the first time,which shows improved performance as a photoanode in dye-sensitized solar cell(DSSC).The layered structure of this novel nanoporous structure has been analyzed unambiguously by Rutherford backscattering spectroscopy,scanning electron microscopy,and X-ray diffractometer.The cell using the heterostructure as photoanode manifests an enhancement of about an order in the magnitude of the short circuit current and a seven-fold increase in efficiency,over pure TiO_2 photoanodes.Characterizations further reveal that the Zn-TONT is preferentially oriented in [001] direction and there is a Ti metal-depleted interface layer which leads to better band alignment in DSSC.
基金ACKNOWLEDGMENTS This work was supported by the Science Foundation of Chongqing Science and Technology Committee （No.CSTS2009BB4047）, and Innovative Talent Training Project, the Third Stage of ＂211 Project＂ of Chongqing University （No.S-09109）.
文摘TiO2 nanotube arrays （TNTs） electrode loaded with Zn nanoparticles was prepared by anodization and the size of Zn nanoparticle loaded on TNTs electrode was controlled by chronoamperometry deposition time. Results of SEM and XRD analysis show that Zn nanoparticles had a diameter of about 15-25 nm when the deposition time was 3-5 s. The UV-Vis diffuse reflectance spectra show the Zn loaded harvest light with 480-780 nm more effectively than the unloaded sample. The photocurrent response of Zn loaded TNTs electrodes were studied, the results showed that TNTs electrodes loaded with Zn nanoparti-cles has 50% increased photocurrent response under high-pressure mercury lamp irradiation compared with unloaded TNTs electrode.
基金Project(50604017) supported by the National Natural Science Foundation of ChinaProject(20110946Z) supported by the State Key Laboratory of Powder Metallurgy,China
文摘Vertically orientated TiO2 nanotube array with diameters ranging from 60 up to 80 nm and length of 4 μm was grown on titanium by anodization.Crack initiation,propagation and saturation were studied using the substrate straining test.The results show that annealing obviously modifies the interfaces.With the increase of tensile strain,cracks in TiO2 nanotube films propagate rapidly and reach the saturation within a narrow strain gap.Interfacial shear strengths of TiO2 nanotube films without annealing,with 250 ℃ annealing and with 400 ℃ annealing can be estimated as 163.3,370.2 and 684.5 MPa,respectively.The critical energy release rates of TiO2 nanotube films are calculated as 49.6,102.6 and 392.7 J/m2,respectively.The fracture toughnesses of TiO2 nanotube films are estimated as 0.996,1.433 and 2.803 MPa-m1/2,respectively.The interfacial bonding mechanism of TiO2 nanotube film is chemical bonding.
基金Project (51274248) supported by the National Natural Science Foundation of ChinaProject (20110946Z) supported by State Key Laboratory of Powder Metallurgy, China
文摘Substrate straining test was carried out to study the buckling pattern of TiO2 nanotube film. The results show that the tensile strains of buckling occurrence of TiO2 nanotube films without annealing, with 250 ℃ annealing and with 400 ℃ annealing are 2.5%, 8.9% and 7.8%, respectively, which indicates the modifying effects of temperature annealing. Through the SEM observation, the critical buckling stresses of TiO2 nanotube films without annealing, with 250 ℃ annealing and with 400 ℃ annealing can be estimated as 180.4, 410.2 and 619.5 MPa, respectively. The critical buckling stress of TiO2 nanotube films with 250 ℃ annealing from AFM observation is estimated as 470.2 MPa, which indicates good agreement with the critical buckling stress from SEM observation. The true stress and the critical energy release rate of TiO2 nanotube film with 250 ℃ annealing are given as 840.3 MPa and 77.2 J/m2, respectively. Excellent agreement of the critical energy release rate of TiO2 nanotube film with 250 ℃ annealing in terms of buckling perspective and crack perspective is obtained.
基金Project (51274248) supported by the National Natural Science Foundation of ChinaProject (20110946Z) supported by the State Key Laboratory of Powder Metallurgy, China
文摘Curvature method was used to measure the residual stress and substrate straining tensile test was carried out to study the debonding behavior of TiO2 nanotube film. The results indicate that the internal residual stress is -54 MPa. The strains of debonding initiation of TiO2 nanotube films without annealing, with 250 °C annealing and with 400 °C annealing are 2.6%, 5.1% and 8.6%, respectively, and the average radii of the debonding patches with debonding initiation are 27.5, 17.1 and 19.4 μm, respectively. The true critical debonding stresses of TiO2 nanotube films without annealing, with 250 °C annealing and with 400 °C annealing can be estimated as 220.4, 394.5 and 627.9 MPa, respectively. Interfacial shear lag model is modified and polynomial fitting equation of the interfacial shear strength of TiO2 nanotube film is demonstrated under debonding conditions. The modification and polynomial fitting are reliable since good agreement of the interfacial shear strengths after fitting is obtained compared with those results from the crack density analysis.
文摘A novel titanium dioxide （TiO2） film comprising both nanotubes and nanopaticles was fabricated by an anodization process of the modified titanium. The local electric field at the anodized surface was simulated and its influence on the morphology of the TiO2 film was discussed. The results show that the electric field strength is enhanced by the covering. The growth rate of TiO2 increases with the assist of the local electric field. However, TiO2 dissolution is hindered since the local electric field prevents [TiF6]6- from diffusing. It means that the balance condition for the formation of nanotubes is broken, and TiO2 nanoparticles are formed. Moreover, the crystal structure of the TiO2 film was confirmed using X-ray diffraction and Raman analysis. The anatase is a main phase for the proposed film.
基金supported by the National Natural Science Foundation of China(Grant Nos.51672249,51802282,and 11804301)the Zhejiang Provincial Natural Science Foundation of China(Grant Nos.LQ17F040004 and LY17E020001)Fundamental Research Funds of Zhejiang Sci-Tech University(No.2019Q062)。
文摘Two-dimensional (2D) ultrathin MoS2-modified black Ti^3+-TiO2 nanotubes were fabricated using an electrospinning-hydrothermal treatment-reduction method.Bare TiO2 nanotubes were fabricated via electrospinning.Then,2D MoS2 lamellae were grown on the surface of the nanotubes and Ti^3+/Ov ions were introduced by reduction.The photocatalytic performance of the 2D MoS2/Ti^3+-TiO2 nanotubes was^15 times better than that of TiO2.The HER enhancement of the MoS2/Ti^3+-TiO2 nanotubes can be attributed to the Pt-like behavior of 2D MoS2 and the presence of Ti^3+-ions,which facilitated the quick diffusion of the photogenerated electrons to water,reducing the H2 activation barrier.The presence of Ov ions in the nanotubes and their hollow structure increased their solar utilization.
基金supported by the National Natural Science Foundation of China(21507104)Natural Science Basic Research Plan in Shaanxi Province of China(2017JM2015)~~
文摘A PbO2/Sb-SnO2/TiO2 nanotube array composite electrode was successfully synthesized and its electrochemical oxidation properties were investigated.Field-emission scanning electron microscopy(FE-SEM)and X-ray diffraction(XRD)results showed that the PbO2 coating was composed of anα-PbO2 inner layer and aβ-PbO2 outer layer.Accelerated life measurement indicated that the composite electrode had a lifetime of 815 h.Rhodamine B(RhB)was employed as a model pollutant to analyze the electrocatalytic activity of the electrode.The effects of initial RhB concentration,current density,initial pH,temperature,and chloride ion concentration on the electrochemical oxidation were investigated in detail.Inductively coupled plasma atomic emission spectroscopy(ICP-AES)results suggested that the concentration of leached Pb^2+in the electrolyte during the electrocatalytic oxidation process can be neglected.Finally,the degradation mechanism during the electrocatalytic oxidation process was proposed based on the results of solid-phase micro-extraction-gas chromatography-mass spectrometry(SPME-GC-MS).The high electrocatalytic performance of the composite electrode makes it a promising anode for the treatment of organic pollutants in aqueous solution.
基金This project was supported by the National Natural Science Foundation of China (20071010).
文摘The process, that the polycrystalline TiO2 powders were converted into TiO2 nanotubes, was observed with transmission electron microscope. The results obtained indicated that in concentrated NaOH aqueous solution, anisotropic swelling appears on the polycrystalline TiO2 granula at first, and then the nanotubes are formed.
文摘TiO2 nanotube precursor was synthesized by the hydrothermal reaction of TiO2 powders with NaOH solution and the properties of the nanotube materials were tuned using different post-treatments. Transmission electron microscopic （TEM） observation revealed that the nanotube could be obtained by either a direct rinse with acid solution or rinse with distilled water followed by acid solution. The results of X-ray diffraction （XRD） and inductively coupled plasma （ICP） analysis indicated that the nanotube material was composed of H2Ti2O5·H2O. In addition, the photocatalytic activities of the resulting catalysts were found to be strongly dependent on the post-treatment. The results of the photocatalytic reaction showed that the degradation of Acid-red 3B dye fitted pseudo-zero-order kinetics and TiO2 nanotube prepared under direct rinse with acid solution exhibited a higher catalytic efficiency compared to other catalysts.
基金supported financially by the National Natural Science Foundation of China(Nos.51622106 and 51871049)the Fundamental Research Funds for the Central Universities(No.160708001).
文摘A layer of graphene(GR)particles was successfully deposited at the interface between Co(OH)2 nanoparticles and TiO2 nanotubes,aiming to improve the photoelectrochemical performance of the large-bandgap semiconductor TiO2.The obtained Co(OH)2/GR/TiO2 was extensively characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),UV–vis absorption spectra and photoluminescence(PL)emission spectra.Electrochemical impedance spectra,photogenerated potential-time(E-t),photocurrent density-time(i-t)and i-E curves and open circuit potential(OCP)curves were measured to investigate the photoelectrochemical activities and photogenerated cathodic protection properties.The results revealed that Co(OH)2/GR/TiO2 exhibits excellent photoelectrochemical and photogenerated cathodic performance due to synergistic effect between Co(OH)2 and graphene.Co(OH)2 and graphene co-modified TiO2 photoanode could provide an effective protection for 304 stainless steel(304 SS)in 3.5 wt%Na Cl solution for 12 h,which would be promising for future practical applications in the field of marine corrosion protection.
基金the National Nature Science Foundation of China(21507085,21576162)Shanghai Sailing Program of China(14YF1401500)for financial support
文摘We report the development of a novel visible response BiVO_4/TiO_2(N_2) nanotubes photoanode for photoelectrocatalytic applications. The nitrogen-treated TiO_2 nanotube shows a high carrier concentration rate, thus resulting in a high efficient charge transportation and low electron–hole recombination in the TiO_2–BiVO_4. Therefore, the BiVO_4/TiO_2(N_2) NTs photoanode enabled with a significantly enhanced photocurrent of 2.73 mA cm^(-2)(at 1 V vs. Ag/Ag Cl) and a degradation efficiency in the oxidation of dyes under visible light. Field emission scanning electron microscopy, X-ray diffractometry, energy-dispersive X-ray spectrometer, and UV–Vis absorption spectrum were conducted to characterize the photoanode and demonstrated the presence of both metal oxides as a junction composite.
基金supported by the National Natural Science Foundation of China(Nos.51972063 and 21501127)the 111 Project(No.D17005)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Due to increasingly serious environmental problems,many researchers are investigating green cleanenergy to solve the world’s energy supply issues.So the strategy that Au nanoparticles(Au NPs)and bismuth sulfide(Bi2S3)NPs are used to evenly decorate TiO2 nanotube arrays(TiO2 NTAs)was carried out.Composite materials demonstrated enhanced solar light absorption ability and excellent photoelectrochemical performance.This was attributed to the presence of Bi2S3 NPs with a narrow band gap and the decoration with noble metallic Au NPs which resulted in local surface plasmon resonance(LSPR)effects.The Au/Bi2S3@TiO2 NTAs composites exhibit improved photocatalytic activity for the degradation of methylene blue(MB)under irradiation of UV and visible light.Moreover,the Au/Bi2S3@TiO2 NTAs exhibits high fluorescence emission at 822 nm.Due to the better binding affinity between Bi2S3,TiO2 and Fe3+ions,the synthesized nanocomposites exhibit high selectivity to Fe3+ions.The number of binding sites for Au/Bi2S3@TiO2 NTAs was estimated to be 1.41 according to the double logarithmic regression method.The calculated value of"K"was 1862 M-1.Fluorescence emission intensity decreases with increasing concentration(30μM–5000μM).The detection limit of the synthesized sensor is 0.221μM.
基金supported by the National Natural Science Foundation of China (Grant No. 51102246)the Knowledge Innovation Program of Institute of Metal Research, Chinese Academy of Sciences (Grant No.Y0N5A111A1)the Youth Innovation Promotion Association, Chinese Academy of Sciences (Grant No.Y2N5711171)
文摘Well crystallized niobium-doped TiO; nanotube arrays （TiNbO-NT） were successfully synthesized via the anodization of titanium/niobium alloy sheets, followed with a heat treatment at 550 ℃ for 2 h. Morphology analysis results demonstrated that both the titanium/niobium alloy microstructure and the dissolution strength of electrolyte played major roles in the formation of nanotube structure. A single-phase microstructure was more favorable to the formation of uniform nanotube arrays, while modulating the dissolution strength of electrolyte was required to obtain nanotube arrays from the alloys with multi-phase microstructures. X-ray diffraction （XRD） and X-ray photoelectron （XPS） analysis results clearly demonstrated that niobium dopants （Nb^5＋） were successfully doped into TiO2 anatase lattice by substituting Ti^4＋ in this approach.
基金supported by the National Natural Science Foundation of China (No.61774073)Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University (No. 2016-25)Science and Technology Development Program of Jilin province (No. 20170101086JC)
文摘TiO2 nanotube arrays were prepared by means of an electrochemical anodization technique in an organic electrolyte solution doped with polyvinyl pyrrolidone (PVP) and were subsequently modified with phosphomolybdic acid (PMoA) to obtain PMoA/TiO2 nanotube arrays. The microstructure and photochromic properties were investigated via X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-vis), and X-ray photoelectron spectroscopy (XPS). The results indicated that the Keggin structure of PMoA and the nanotube structure of TiO2 were not destroyed, and there was a strong degree of interaction between PMoA and TiO2 at the biphasic interface with lattice interlacing during the compositing process. The XPS results further indicated that there was a change in the chemical microenvironment during the formation process of the composite, and a new charge transfer bridge was formed through the Mo-O-Ti bond. Under visible light irradiation, the colorless PMoA/TiO2 nanotube array quickly turned blue and exhibited a photochromic response together with reversible photochromism in the presence of H2O2. After visible light irradiation for 60s, the appearance of Mo^5+ species in the XPS spectra indicated a photoreduction process in accordance with a photoinduced electron transfer mechanism.
基金the State Key Development Program for Basic Research of China (Grant No.2009CB220004)the Shanghai Basic Research Key Project (08JC1411300,0952nm01800)+1 种基金the National High Technology Research and Development Program of China (Grant No.2009 AA063003)Shanghai Tongji Gao Tingyao Environmental Science and Technology Development Foundation for financial support
文摘Copper and titanium remain relatively plentiful in earth crust.Therefore,using them in solar energy conversion technologies are of significant interest.In this work,cuprous oxide（Cu2O）-modified short TiO2 nanotube array electrode was prepared based on the following two design ideas:first,the short titania nanotubes obtained from sonoelectrochemical anodization possess excellent charge separation and transportation properties as well as desirable mechanical stability;second,the sonoelectrochemical deposition technique favours the improvement in the combination between Cu2O and TiO2 nanotubes,and favours the dispersion of Cu2O particles.UV-Vis absorption and photo-electronchemical measurements proved that the Cu2O coating extended the visible spectrum absorption and the solar spectrum-induced photocurrent response.Under AM1.5 irradiation,the photocurrent density of the composite electrode（i.e.sonoelectrochemical deposition for 5 min） was more than 4.75 times as high as the pure nanotube electrode.Comparing the photoactivity of the Cu2O/TiO2 electrode obtained using sonoelectrochemical deposition with others that synthesized using plain electrochemical deposition,the photocurrent density of the former electrode was 2.2 times higher than that of the latter when biased at 1.0 V（vs.Ag/AgCl）.The reproducible photocurrent response under intermittent illumination demonstrated the excellent stability of the composite electrode.Such kind of composite electrode material will have many potential applications in solar cell and other fields.
文摘IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and characterized by means of structural,surface analytical and electrochemical techniques.Nb doping of titania significantly increased the surface area of the support from 145(TNTs)to 260 m2g-1(Nb-TNTs),which was significantly higher than those of the Nb-doped titania supports previously reported in the literature.The surface analytical techniques showed good dispersion of the catalysts onto the supports.The X-ray photoelectron spectroscopy analyses showed that Nb was mainly in the form of Nb(IV)species,the suitable form to behave as a donor introducing free electrons to the conduction band of titania.The redox transitions of the cyclic voltammograms,in agreement with the XPS results,were found to be reversible.Despite the supported materials presented bigger crystallite sizes than the unsupported ones,the total number of active sites of the former was also higher due to their better catalyst dispersion.Considering the outer and the total charges of the cyclic voltammograms in the range 0.1–1.4 V,stability and electrode potentials at given current densities,the preferred catalyst was Ir O2 supported on the Nb-TNTs.The electrode potentials corresponding to given current densities were between the smallest ones given in the literature despite the small oxide loading used in this work and its Nb doping,thus making the Nb-TNTs-supported IrO2 catalyst a promising candidate for the OER.The good dispersion of IrO2,high specific surface area of the Nb-doped supports,accessibility of the electroactive centers,increased stability due to Nb doping and electron donor properties of the Nb(IV)oxide species were considered the main reasons for its good performance.
基金Funded in Part by the Research Fund of Hubei Provincial Department of Education,China(No.Q20121102)
文摘Polyaniline （PANI） composite nanotubes （90-130 nm in diameter） containing titanium dioxide （TiO2） nanoparticles （about 10 nm in diameter） were synthesized through a self-assembly process in the presence of a-naphthalenesulfonic acid （a-NSA） as the dopant. It was found that PANI-TiO2 composites and PANI nanotubes both behaved with significant photocatalytic activities towards AZO dyes, during 2 h photocatalytic processes under natural light, the degradation ratio was 94.2% and 97.2% respectively （methyl orange and orange II）. The morphology of such products was characterized by SEM. The specific surface area of such composite nanotubes was 14.7 m2/g compared to normal polyaniline which was 0.27 m2/g. IR and X-ray diffraction characterizations showed that the chemical chain of the composite nanotubes was identical to that of the doped PANI. It may provide a new way for photodegradation of organic contaminants by using conjugated polymer with dimensional structure.
