TiO_2纳米粉的制备及其表征

用UV -vis,XRD和TEM法对用不同方法制备的 3种纳米TiO2 进行了表征 .紫外可见吸收光谱表明TiO2 (C -Q) ,TiO2 (S -Q)和TiO2 (S -dar) 3种样品吸收阈值分别为 35 0 ,36 0和 380nm .对应的禁带宽度分别为 3 .5 ,3 .44和 3 .2eV .XRD结果表明 ,所制得的 3种样品均为锐钛矿型 .

Photoelectrocatalysis for high‐value‐added chemicals production

Photoelectrocatalysis(PEC)is a promising approach that can convert renewable solar energy into chemical energy,while most concern is concentrated on PEC water splitting to obtain high‐value‐added fuel—hydrogen.In practice,more economic benefits can be produced based on PEC technique,such as H_(2)O oxidative H_(2)O_(2) synthesis,organic selective oxidation,organic pollutants degradation and CO_(2) reduction.Although there are plenty of excellent reviews focusing on the PEC water splitting system,the production of various high‐value‐added chemicals in PEC systems has not been discussed synthetically.This Account will focus on the production process of various high‐value‐added chemicals through PEC technology.The photoelectrode design,reaction environment and working mechanisms of PEC systems are also discussed in detail.We believe that this comprehensive Account of the expanded application of photoelectrocatalysis can add an inestimable impetus to the follow‐up development of this technology.

NiFe layered double-hydroxide nanoparticles for efficiently enhancing performance of BiVO_4 photoanode in photoelectrochemical water splitting

A bismuth vanadate(BiVO4)photoanode with a cocatalyst consisting of NiFe layered double‐hydroxide(NiFe‐LDH)nanoparticles was fabricated for photoelectrochemical(PEC)water splitting.NiFe‐LDH nanoparticles,which can improve light‐absorption capacities and facilitate efficient hole transfer to the surface,were deposited on the surface of the BiVO4 photoanode by a hydrothermal method.All the samples were characterized using X‐ray diffraction,scanning electron microscopy,and diffuse‐reflectance spectroscopy.Linear sweep voltammetry and current‐time plots were used to investigate the PEC activity.The photocurrent response of NiFe‐LDH/BiVO4 at 1.23 V vs the reversible hydrogen electrode was higher than those of Ni(OH)2/BiVO4,Fe(OH)2/BiVO4 and pure BiVO4 electrodes under visible‐light illumination.NiFe‐LDH/BiVO4 also gave a superior PEC hydrogen evolution performance.Furthermore,the stability of the NiFe‐LDH/BiVO4 photoanode was excellent compared with that of the bare BiVO4 photoanode,and offers a novel method for solar‐assisted water splitting.

Effects of Metal Oxide Modifications on Photoelectrochemical Properties of Mesoporous TiO2 Nanoparticles Electrodes for Dye-Sensitized Solar Cells

Mesoporous TiO2 （m-TiO2） nanoparticles were used to prepare the porous film electrodes for dye-sensitized solar cells, and a second metal oxide （MgO, ZnO, A1203, or NiO） modifi- cation was carried out by dipping the m-TiO2 electrode into their respective nitrate solution followed by annealing at 500 ℃. Experimental results indicated that the above second metal oxide modifications on m-TiO2 electrode are shown in all cases to act as barrier layer for the interracial charge transfer processes, but film electron transport and interfacial charge recombination characteristics under applied bias voltage were dependent significantly on the existing states and kinds of these second metal oxides. Those changes based on sec- ond metal oxide modifications showed good correlation with the current-voltage analyses of dye-sensitized solar cell, and all modifications were found to increase the open-circuit photo- voltage in various degrees, while the MgO, ZnO, and NiO modifications result in 23%, 13%, and 6% improvement in cell conversion efficiency, respectively. The above observations indi- cate that controlling the charge transport and recombination is very important to improve the photovoltaic performance of TiO2-based solar cell.

Dye-sensitized photoanode decorated with pyridine additives for efficient solar water oxidation

Splitting water into hydrogen and oxygen by dye-sensitized photoelectrochemical cell(DSPEC)is a promising approach to solar fuels production.In this study,a series of pyridine derivatives as surface additives were modified on a molecular chromophore and water oxidation catalyst co-loaded TiO_(2)photoanode,TiO_(2)|RuP,1(RuP=Ru(4,4′-(PO3H2)2-2,2′-bipyridine)(2,2′-bipyridine)2,1=Ru(bda)(L)2,(bda=2,2′-bipyridine-6,6′-dicarboxylate,L=10-(pyridin-4-yloxy)decyl)phosphonic acid).The addition of pyridine additives was found to result in up to 42%increase in photocurrent.Under simulated sun-light irradiation,TiO_(2)|RuP,1,P1(P1=4-Hydroxypyridine)produced a photocurrent density of 1 mA/cm2 at a bias of 0.4 V vs.NHE in acetate buffer.Moreover,the observed photocurrents are correlated with the electron-donating ability of the substituent groups on pyridine ring.Transient absorption measurements and electrochemical impedance spectroscopy revealed that surface-bound pyridine can effectively retard the back-electron transfer from the TiO_(2)conduction band to the oxidized dye,which is a major process responsible for energy loss in DSPECs.

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.

Highly-ordered dye-sensitized TiO_2 nanotube arrays film used for improving photoelectrochemical electrodes

Thin titanium oxide nanotube arrays (TNAs) films were synthesized by anodization of titanium foil in an aqueous dimethyl sulfoxide solution using a platinum foil counter electrode.TNAs up to 6.8 μm in length,120 nm in inner pore diameter,and 20 nm in wall thickness were obtained by 40 V potentials anodization for 24 h.Their microstructures and surface morphologies were characterized by XRD,TEM,SAED and UV-vis spectroscopy.The photoelectrochemical properties of as-prepared unsensitized and dye-sensitized TNAs electrodes were examined under simulated solar light (AM 1.5,100 mW/cm2) illumination.The results showed that the photocurrent of the dye-sensitized TNAs electrodes reached 6.9 mA/cm2,which was 6 times more than that of the dye-sensitized TiO2 nanoparticles (TNPs) electrodes.It implied that the electron transport process and the charge recombination suppression within TNAs electrodes were much more favorable in comparison with that in the TNPs electrodes.Electrodes applying such kind of titania nanotubes will have a potential to further enhance the efficiencies of TNAs-based dye-sensitized solar cells.

Flexible thermocells for utilization of body heat

Plastic thermo-electrochemical ceils （thermocells） involving aqueous potassium ferricyanide/ferrocyanide electrolyte have been investigated as an alternative to conventional thermoelectrics for thermal energy harvesting. Plastic thermocells that consist of all pliable materials such as polyethylene terephthalate （PET）, fabrics, and wires are flexible enough to be wearable on the human body and to be wrapped around cylindrical shapes. The performance of the thermocells is enhanced by incorporating carbon nanotubes into activated carbon textiles, due to improved charge transfer at the interface. In cold weather conditions （a surrounding temperature of 5 ℃）, the thermocell generates a short-circuit current density of 0.39 A/m2 and maximum power density of 0.46 mW/m2 from body heat （temperature of 36℃）. For practical use, we have shown that the thermocell charges up a capacitor when worn on a T-shirt by a person. We also have demonstrated that the electrical energy generated from waste pipe heat using a serial array of the thermocells and voltage converters can power a typical commercial light emitting diode （LED）.

Ultrasensitive polarized-light photodetectors based on 2D hybrid perovskite ferroelectric crystals with a low detection limit

Polarized-light photodetectors are the indispensable elements for practical optical and optoelectronic device applications.Two-dimensional(2D)hybrid perovskite ferroelectrics,in which the coupling of spontaneous polarization(P_(s))and light favors the dissociation of photo-induced carriers,have taken a booming position within this portfolio.However,polarized-light photodetectors with a low detectionlimit remain unexplored in this 2D ferroelectric family.In this work,the high-quality individual crystals of a 2D perovskite ferroelectric,BA_(2)CsPb_(2)Br_(7)(1,where BA^(+)is n-butylammonium),were used to fabricate ultrasensitive polarized-light detectors.Its unique bilayered structural motif results in quite strong electric and optical anisotropy with a large absorption ratio of a_(c)/α_(a)≈3.2(λ=405 nm).Besides,the presence of ferroelectric Psalso endows high built-in electric field along the polar c-axis that favors photoelectric activities.Under an extremely low detectable limit of 40 n W/cm^(2),the detector of 1 exhibits a notable dichroism ratio(I_(ph)^(c)/I_(ph)^(a)≈1.5),a large responsivity of~39.5 m A/W and a specific detectivity of~1.2×10^(12)Jones.Moreover,crystal-based devices of 1 also exhibit a fast response speed(~300μs)and excellent anti-fatigue merits.This work highlights great potentials of hybrid perovskite ferroelectrics toward polarized-light photodetection.

3D interconnected nanoporous TaN films for photoelectrochemical water splitting: thickness-controlled synthesis and insights into stability

Solar-driven photoelectrochemical(PEC) water splitting is a promising technology for sustainable hydrogen production, which relies on the development of efficient and stable photoanodes for water oxidation reaction. The thickness and microstructure of semiconductor films are generally crucial to their PEC properties. Herein, three-dimensional(3D) interconnected nanoporous Ta3N5 film photoanodes with controlled thickness were successfully fabricated via galvanostatic anodization and NH3 nitridation. The porous Ta3N5 nanoarchitectures(NAs) of 900 nm in thickness showed the highest PEC performance due to the optimal lightharvesting and charge separation. Compared with the holeinduced photocorrosion, the electrochemical oxidation at high anodic potentials resulted in severer performance degradation of Ta3N5. Although the surface oxide layer on deteriorated Ta3N5 photoanodes could be removed by NH3 re-treatment,the PEC performance was only partially recovered. As an alternative, anchoring a dual-layer Co(OH)x/Co OOH co-catalyst shell on the porous Ta3N5 NAs demonstrated substantially enhanced PEC performance and stability. Overall, this work provides reference to controllably fabricate 3D nanoporous Ta3N5-based photoanodes for efficient and stable PEC water splitting via optimizing the light absorption, hole extraction,charge separation and utilization.

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.

Grey hematite photoanodes decrease the onset potential in photoelectrochemical water oxidation

Photoelectrochemical(PEC)water splitting for solar energy conversion into chemical fuels has attracted intense research attention.The semiconductor hematite(α-Fe_(2)O_(3)),with its earth abundance,chemical stability,and efficient light harvesting,stands out as a promising photoanode material.Unfortunately,its electron affinity is too deep for overall water splitting,requiring additional bias.Interface engineering has been used to reduce the onset potential of hematite photoelectrode.Here we focus instead on energy band engineering hematite by shrinking the crystal lattice,and the water-splitting onset potential can be decreased from 1.14 to 0.61 V vs.the reversible hydrogen electrode.It is the lowest record reported for a pristine hematite photoanode without surface modification.X-ray absorption spectroscopy and magnetic properties suggest the redistribution of 3d electrons in the as-synthesized grey hematite electrode.Density function theory studies herein show that the smaller-lattice-constant hematite benefits from raised energy bands,which accounts for the reduced onset potential.

The intensification of luminol electrochemiluminescence by metallic oxide nanoparticles

In this work, the intensification of luminol electrochemiluminescence (ECL) by metallic oxide nanoparticles (MONPs), as ZnO, MnO2,In2O3 and TiO2 , under alkaline condition is reported and the related mechanism is studied. It is found that all four types of those MONPs exhibit the effect toward the ECL intensification of luminol. Furthermore, the silica sol-gel film is taken to immobilize the MONPs onto the platinum electrodes. The so-obtained modified electrodes also show the enhanced ECL and better signal/noise ratio, as well improved signal stability. Finally, the ECL reagent, luminol, is immobilized together with the MONPs onto the electrode surface to perform as the ECL sensor. On resulting sensors, good linear responses are obtained toward hydrogen peroxide. The mechanism of intensification of luminol ECL by MONPs is discussed in this paper. It is proposed that the ECL intensification can be attributed to the production of reactive oxygen species, as well as the adsorption of luminol on surface of MONPs.

A thin-layer spectroelectrochemical study of 3,3',5,5'-tetramethylbenzidine at SnO_2:F film optically transparent electrode

The electrooxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) is dependent on the pH value of Britton-Robinson (B-R) buffer solution. In this work, the electrooxidation behavior of TMB was investigated with a SnO2:F film optically transparent thin-layer spectroelectrochemical cell. TMB underwent one two-electron electrooxidation process in the pH range from 2.0 to < 4.0, and two successive one-electron electrooxidation processes in the pH range from 4.0 to < 7.0 in the B-R buffer solution. At pH 6.5, the electrooxidative product of TMB generated a subsequent chemical reaction to yield an azo compound. Several spectroelectrochemical techniques, such as thin-layer cyclic voltammetry, thin-layer cyclic voltabsorptometry, thin-layer potential-controlled electrolysis absorptometry, thin-layer single-potential-step chronoabsorptometry, thin-layer dou-ble-potential-step chronoabsorptometry, thin-layer single-potential-step open-circuit relaxation chronoabsorptometry, were applied to this investigation. The formal potential E0’ and the electron transfer number corresponding to the electrooxidation of TMB in B-R buffer solution, and the reaction rate constant of the subsequent chemical reaction were determined.