利用荧光能量转移设计高灵敏苦味酸光极膜

利用荧光能量转移设计高灵敏苦味酸光极膜王柯敏，曾恚恚，俞汝勤（湖南大学化学化工系，长沙，４１００８２）关键词荧光能量转移，光极，苦味酸基于稠环芳烃荧光熄灭的苦味酸光极膜［１ａ，２］在选择性方面优于传统苦味酸根离子电极，较适于实际应用，但在检测低浓度苦...

基于亲脂杯状芳烃Calix［6］arene的多巴胺选择性光极膜的研究

将亲脂杯状芳烃、氢离子敏感生色离子载体与阴离子定域体一同结合于增塑的ＰＶＣ膜中，发展了一种对多巴胺敏感的光极膜。

基于环糊精/卟啉包络物荧光猝灭的二氧化碳光学敏感膜的研究

全 -( 2 ,6-二 -O-异丁基 ) -β-环糊精 ( DOB-β-CD)对固定于增塑 PVC膜中的 meso-四 ( 4-甲氧基苯基 )卟啉( TMOPP)有明显的荧光增强效应 ,且该荧光可被溶液中的二氧化碳可逆猝灭 .本文据此研制了一种可用于测定水溶液中二氧化碳含量 ,即 [H2 CO3]浓度的荧光敏感膜 .研究了最佳膜的组成 .经过组成优化的敏感膜测定 [H2 CO3]浓度的范围为 4 .75× 1 0 - 7～ 3.9× 1 0 - 5 mol/L.该传感器响应迅速、重现性好 ,常见的离子无明显干扰 .

双硫腙修饰光极测定汞(Ⅱ)的研究(英文)

以双硫腙为探针构造了 PVC膜修饰光极 ,就该光极的识别机理 ,酸度、响应时间、选择性等对光度测定的影响和光极再生方法进行了探讨 ,建立了一种新型的 Hg2 + 离子选择性光极测定方法。结果表明 ,该修饰光极在 p H4 .5的缓冲溶液中对汞离子有灵敏的响应 ,测量范围 0～ 10 - 5 mol l- 1,检测限达 3.5× 10 - 7m ol l- 1,可应用于生活废水中汞离子的测定。

Photoelectrocatalytic reduction of CO_2 into formic acid using WO_(3-x)/TiO_2 film as novel photoanode

A novel WO3-x/TiO2 film as photoanode was synthesized for photoelectrocatalytic（PEC） reduction of CO2 into formic acid（HCOOH）. The films prepared by doctor blade method were characterized with X-ray diffractometer（XRD）, scanning electron microscope（SEM） and transmission electron microscope（TEM）. The existence of oxygen vacancies in the WO3-x was confirmed with an X-ray photoelectron spectroscopy（XPS）, and the accurate oxygen index was determined by a modified potentiometric titrimetry method. After 3h of photoelectrocatalytic reduction, the formic acid yield of the WO3-x/TiO2 film is 872 nmol/cm^2, which is 1.83 times that of the WO3/TiO2 film. The results of PEC performance demonstrate that the introduction of WO3-x nanoparticles can improve the charge transfer performance so as to enhance the performance of PEC reduction of CO2 into formic acid.

Preparation of TiO_2/ITO film by liquid phase deposition and its photoelectrocatalytic activity for degradation of 4-aminoantipyrine

A thin layer of TiO2 film was deposited on ITO surface via the liquid phase deposition （LPD） process. The photocurrent and electrochemical impedance spectroscopy （EIS） measurements indicated that the as-prepared LPD TiO2/ITO film had an excellent photoelectrochemical performance, which showed a sensitive and rapid response to the UV irradiation. The photogenerated electron-hole pairs could be effectively separated by applying an external bias to the TiO2 film electrode. The LPD TiO2/ITO film was employed to study the photoelectrocatalytic （PEC） degradation of 4-aminoantipyrine. Compared with other techniques, the PEC technique based on such a LPD film electrode had a synergetic effect for 4-aminoantipyrine degradation. When the applied bias potential was＋0.8 V and the supporting electrolyte concentration of Na2SO4 was 0.1 mol/L, the highest degradation efficiency within 120 min could reach 95%for 0.1 mmol/L 4-aminoantipyrine solution at pH 2.0.

Characterization and photoelectrochemical performance of Zn-doped TiO_2 films by sol-gel method

Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.

Efficiency analysis of a-SiC:H thin film light emitting diodes

The hole injection,the radiative recombination and the device luminescent efficiencies of amorphous silicon carbide thin film p-i-n junction light emitting diodes are quantitatively calculated,and the effect of the carrier(especially the hole) injection and recombination processes on the device luminescent characteristics are revealed.Without considering the device junction temperature,it is found that the device luminescent efficiency mainly depends on the hole injection efficiency at low field and the hole radiative recombination efficiency at high field respectively.The theoretical analyses are in well agreement with the experimental results.

One-step fabrication of TiO2/graphene hybrid mesoporous film with enhanced photocatalytic activity and photovoltaic performance

We synthesized a mesoporous film based on TiO2-reduced graphene oxide(RGO)hybrids using a one-step vapor-thermal method without the need for an additional annealing process.The vapor-thermally prepared TiO2-graphene hybrid(VTH)features unique structures with an ultra-large specific surface area of^260 m^2 g^-1 and low aggregation,giving rise to enhanced light harvesting and increased charge generation and separation efficiency.It was observed that a mesoporous film with uniform pore distribution is simultaneously obtained during the VTH growth process.When a 5.0 wt%RGO VTH film was used as the active layer in photocatalysis,the highest photocatalytic activity for degradation of methyl orange was achieved.For another,when a 0.75 wt%RGO VTH film was used as the photoanode in a dye-sensitized solar cell,the power conversion efficiency reached 7.58%,which represents an increase of 73.1%compared to a solar cell using an a photoanode of pure TiO2 synthesized by a traditional solvothermal method.It is expected that this facile method for the synthesis of TiO2/graphene hybrid mesoporous films will be useful in practical applications for preparing other metal oxide/graphene hybrids with ultra-high photocatalytic activity and photovoltaic performance.

TiO2 Nanoparticles Produced by Electric-Discharge-Nanofluid-Process as Photoelectrode of DSSC

Self-made TiO2 nanoparticles were used as photoelectrode material of dye sensitized solar cell. The TiO2 thin film coats through spreading nanoparticles evenly onto the ITO glass via self-made spin-heat platform, and then TiO2 thin film is soaked in the dye N-719 more than 12 h to prepare the photoelectrode device. The TiO2 nanoparticles produced by electric-discharge-nanofluid-process have premium anatase crystal property, and its diameter can be controlled within a range of 20-50 nm. The surface energy zeta potential of nanofluid is from -22 mV to -28.8 mV, it is a stable particle suspension in the deionized water. A trace of surfactant Triton X-100 put upon the surface of ITO glass can produce a uniform and dense TiO2 thin film and heating up the spin platform to 200 oC is able to eliminate mixed surfac-tant. Self-made TiO2 film presents excellent dye absorption performance and even doesn＇t need heat treatment procedure to enhance essential property. Results of energy analysis show the thicker film structure will increase the short-circuit current density that causes higher conversion efficiency. But, as the film structure is large and thick, both the open-circuit voltage and fill factor will decline gradually to lead bad efficiency of dye-sensitized solar cell.

Photo-Corrosion of CdSe Film Electrode by Electrochemical Modulation Reflectance Spectrum

The photo-corrosion of electrodeposited polycrystalline CdSe electrode was inhibited effectively by coating a thin layer of the conductive polyaniline （PAN） film. The relation between the performance and internal band structure of such film-covered PAN/CdSe electrode was studied by the electrochemical modulation reflectance spectrum （EMRS）. EMRS of both CdSe and PAN/CdSe electrodes in K4Fe（CN）6/K3Fe（CN）6 solution exhibited typical France-Keidysh oscillations, by which the values of the energy gap and flat band potential were determined. The EMRS results indicated that the energy band structure of CdSe electrode was not changed after coated with PAN film, so that the photoelectrochemical characteristic of PAN/CdSe electrode was rather similar to that of CdSe electrode.

Analysis and simulation of lateral PIN photodiode gated by transparent electrode fabricated on fully-depleted SOI film

A novel device, lateral PIN photodiode gated by transparent electrode （LPIN PD-GTE） fabricated on fully-depleted SOI film was proposed. ITO film was adopted in the device as gate electrode to reduce the light absorption. Thin Si film was fully depleted under gate voltage to achieve low dark current and high photo4o-dark current ratio. The model of gate voltage was obtained and the numerical simulations were presented by ATLAS. Current-voltage characteristics of LPIN PD-GTE obtained in dark （dark current） and under 570 nm illumination （photo current） were studied to achieve the greatest photo-to-dark current ratio for active channel length from 2 to 12 /am. The results show that the photo-to-dark current ratio is 2.0×10^7, with dark current of around 5×10^-4 pA under VGK=0.6 V, PrN=5 mW/cm2, for a total area of 10μm×10μm in fully depleted SOI technology. Thus, the LPIN PD-GTE can be suitable for high-grade photoelectric systems such as blue DVD.

Electrodeposition and Characterization of ZnO Thin Films

Thin films of ZnO were electrodeposited from an aqueous solution of Zn（NO3 ）2 on indium tin oxide（ITO）-covered glass substrate. The analysis of X-ray diffraction（XRD） and scanning electron micrograph （SEM） indicated that the obtained ZnO films had a compact hexagonal wurtzite type structure with preferable （002） growth direction. A sharp near-UV emission peak located at 380 nm and a strong orange-red emission peak located at 593 nm were observed in the photoluminescence, when excited with 325 nm wavelength at room temperature. Then the prepared ZnO films were introduced as anode phosphors into the field emission test. It was found that orange-red cathode-luminescence was observed and the luminescent brightness was enhanced by annealing. When annealing temperature increased about 600 ℃, the photoluminescence with peak of 531 nm and the green cathode-luminescence were observed. The tests showed that the brightness of about 2 × 102 cd/m^2 was obtained at electric field of 2 V/μm for annealed sample. The results revealed that the film could be a good kind of low-voltage drived cathode-luminescence phosphor.

Suppression of charge recombination by application of CueZnSnS4-graphene counter electrode to thin dye-sensitized solar cells

This paper proposes a new mechanism to explain the performance of thin dye-sensitized solar cells （DSSC）. Near-stoichiometric flower-like Cu2ZnSnS4 （CZTS） microspheres with a high specific surface area was fabri- cated for use as the photocathode in a DSSC. To improve the extraction and transfer of electrons, graphene was added to the CZTS. A DSSC with a 10-gin TiO2 pho- toanode layer exhibited a slightly degraded efficiency with a CZTS-graphene photocathode, relative to a Pt counter electrode （CE）. Nevertheless, when the thickness of the TiO2 photoanode was reduced to 2 lam, the efficiency of a DSSC with a CZTS-graphene photocathode was greater than that of a Pt-DSSC. It is speculated that, unlike the Pt CE, a CZTS-graphene photocathode not only collects electrons from an external circuit and catalyzes the reduction of the triiodide ions in the electrolyte, but also utilizes unabsorbed photons to produce photo-excited electrons and suppresses charge recombination, thus enhancing the performance of the cell. The use of narrowband gap p-type semiconductors as photocathodes offers a new means of fabricating thin dye-sensitized solar cells and effectively improving the cell performance.

Near vacuum-ultraviolet aperiodic oscillation emission of Al N films

An accurate measurement of the refractive index is necessary for the optical design of both deep ultraviolet laser diodes and light-emitting diodes. Generally, the refractive indices along different crystallographic axes of anisotropic thin films are measured using variable angle spectroscopic ellipsometry.However, there are still some limitations concerning this method. Here we proposed a potential method to measure the band edge refractive index of wide bandgap semiconductor. An aperiodic oscillation emission phenomenon due to the Fabry-Perot effect was observed in the fluorescence spectrum of an AlN film with a thickness of 1500 nm. Based on the characteristics of the fluorescence spectrum and the definition of Fabry-Perot effect, we obtained the ordinary refractive index of the AlN thin film near the band edge directly. This refractive index measurement method is a supplement to the variable angle ellipsometry,and it is a more direct and effective method for transferred film and thinner samples to measure the fluorescence spectrum.

Rational design of perfectly oriented thermally activated delayed fluorescence emitter for efficient red electroluminescence

How to control the dipole orientation of organic emitters is a challenge in the field of organic light-emitting diodes(OLEDs).Herein,a linear thermally activated delayed fluorescence(TADF)molecule,PhNAI-PMSBA,bearing a 1,8-naphthalimide-acridine framework was designed by a doublesite long-axis extension strategy to actively control the dipole orientation.The horizontal ratio of emitting dipole orientation of PhNAI-PMSBA reaches 95%,substantially higher than that of isotropic emitters(67%).This unique feature is associated with the intrinsically horizontal molecular orientation of PhNAI-PMSBA and the good agreement between its transition dipole moment direction and molecular long axis.The PhNAI-PMSBA-based OLED achieves an ultrahigh optical outcoupling efficiency of 43.2%and thus affords one of the highest red electroluminescence with an external quantum efficiency of 22.3%and the Commission International de l’Eclairage 1931 coordinates at around(0.60,0.40).

Preparation of TiO_2/ITO film electrode by AP-MOCVD for photoelectrocatalytic application

Titanium dioxide （TiO2） thin films were grown onto Indium tin oxide （ITO） glass under atmospheric pressure by chemical va- por deposition （AP-MOCVD） using titanium tetraisopropoxide astitanium precursor. The as-prepared TiOe/ITO films were characterized using X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS） and photoelectrochemical measurements. Their photocatalytic （PC） and photoelec- trocatalytic （PEC） activities were evaluated based on the results of methyl orange dye （MO） degradation experiments in aque- ous solution. The difference between the front side （EE, electrolyte/electrode interface） and the back side （SE, sub- strate/electrode interface） illumination was evaluated in both photocurrent and MO degradation experiments. The effect of the film thickness on degradation rate by PEC under the two illumination directions was also studied. Stability of TiO2/ITO film electrode was investigated in repetitive degradation experiments. Overall, the TiO2/ITO film with thickness ranging from 321 to1440 nm deposited by MOCVD method is an effective photoelectrode for MO degradation under SE illumination in PEC reaction system.

SnO_2 nanosheet as a photoanode interfacial layer for dyesensitized solar cells

SnO2 nanosheet films about 200 nm in thickness are successfully fabricated on fluorine-doped tin oxide （FTO） glass by a facile solution-grown approach. The prepared SnO2 nanosheet film is appfied as an interfacial layer between the nanocrystalline TiO2 film and the FTO substrate in dye-sensitized solar cells （DSCs）. Experimental results show that the introduction of a SnO2 nanosheet film not only suppresses the electron back-transport reaction at the electrolyte/FTO interface but also provides an efficient electron transition channel along the SnO2 nanosheets, and as a result, increasing the open circuit voltage and short current density, and finally improving the conversion efficiency for the DSCs from 3.89% to 4.62%.

Hybrid photoanode films based on sparse ZnO rod array-TiO_2 nanoparticles in dye-sensitized solar cells

ZnO-TiO2 hybrid photoanodes were fabricated via the doctor-blade method by integrating vertically-grown sparse ZnO arrays with hydrothermal TiO2 nanoparticles. A special surface-coating technique was developed to deposit a thin TiO2 layer on the surface of ZnO rods. Microstructure, optical and photoelectrochemical performance of the hybrid photoanodes were investigated. The denser ZnO array exhibited bad filling behavior of nanoparticles in the interspace of ZnO rods, strong scattering and low conversion efficiency (0.27%). The sparser array showed a much better integrated microstructure, improved transmittance and high conversion efficiency (2.68%). The surface modification of ZnO rods by the TiO2 thin layer was found useful in improving the interfacial microstructure between the ZnO rod and the TiO2 bulk film, and the total conversion efficiency of 3.01% was achieved, higher than that of the pure TiO2 nanoparticle cell (2.93%). The increased scattering effects on the incident light, the enhanced electron transportation at TiO2/dye/electrolyte interface, and the inhabited recombination were responsible for this improvement.

A n-Si/CoOx/Ni:CoOOH photoanode producing 600 mV photovoltage for efficient photoelectrochemical water splitting

n-Si,believed as a promising photoanode candidate,has suffered from sluggish oxygen evolution reaction(OER)kinetics and poor chemical stability when exposed to aqueous electrolyte.Herein,CoO_(x)/Ni:CoOOH bilayers were successfully deposited on n-Si substrate by atomic layer-deposition(ALD)and photoassisted electrochemical deposition(PED)for stabilizing and catalyzing photoelectrochemical(PEC)water oxidation.In comparison to the n-Si/CoO_(x)photoanode as reference,the prepared n-Si/CoO_(x)/Ni:CoOOH photoanode upon the optimized PED process presents a much improved PEC performance for water splitting,with the onset potential cathodically shifted to~1.03 V vs.reversible hydrogen electrode(RHE)and the photocurrent density much increased to 20 mA cm^(−2)at 1.23 V vs.RHE.It is revealed that the introduction of Ni dopants increases the work functions of the deposited Ni:CoOOH overlayers,which gives rise to the upward band bending weakened at the n-Si/CoO_(x)/Ni:CoOOH cascading interface while strengthened at the Ni:CoOOH/electrolyte interface(with the band bending shifted from downward to upward),contributing to the decreased and the increased driving forces for charge transfer at the interfaces,respectively.Then,the balanced driving forces at the interfaces would endow the n-Si/CoO_(x)/Ni:CoOOH photoanode with the best PEC performance.Moreover,PED has been evidenced superior to ED to dope Ni into CoOOH with the formed overlayer effectively catalyzing and stabilizing PEC water splitting.