Influence of oxidation time on semiconductive behaviour of thermally grown oxide films on AISI 304L

The oxide films formed on AISI 304L stainless steel at 300 °C in the oxidation time range between 2 and 4 h have been studied by photoelectrochemistry. Photocurrents were investigated as a function of the wavelength of the incident light and the electrode potential. The investigation allowed the determination of the semiconductive properties of the oxides. The oxide films showed n-type behaviour. A duplex structure of the oxide films has been suggested on the basis of the photocurrent spectra, with an internal oxide layer having an optical gap (E_g2 = 2.16-2.3 eV) depending on the applied potential and oxidation time, higher to that of the external oxide layer (E_g1 ≈ 1.9 eV). Significant variations in the amplitude of the photocurrent were detected as a function of the applied potential and the oxidation time.     

Study of the influence of substituents on spectroscopic and photoelectric properties of zinc phthalocyanines

In this paper we describe conversion of light energy into electric energy in a photoelectrochemical cell containing zinc phthalocyanine (ZnPc) dyes. For all dyes investigated in liquid polyvinyl alcohol with dimethyl sulfoxide solution and located in the photoelectrochemical cell the following measurements have been done: absorption, fluorescence, photoacoustic spectra, photovoltaic spectra, kinetics of photocurrent and current–voltage characteristics. It has been shown that all dyes located in the photoelectrochemical cell are able to convert light into electric energy but with different effectiveness. The influence of substituted different peripheral groups to ZnPc core and the correlation between the molecular structure and effectiveness of solar to electric energy conversion were observed and described. The unique behavior of ZnPc substituted with fluorines was indicated.     

Photovoltaic and spectral properties of tetraphenyloporphyrin and metallotetraphenyloporphyrin dyes

Spectroscopical properties and photocurrent (or photovoltage) of tetraphenyloporphyrins and metallotetraphenyloporphyrins in nematic liquid crystal have been studied. Photoelectric response has been measured in an electrochemical cell made of the semitransparent semiconducting and golden electrodes with porphyrin dyes embedded in liquid crystal. Fluorescence, time-resolved luminescence in microsecond time scale and photoacoustic spectra have also been measured. The competition between radiative, non-radiative processes and charge transfer is discussed. It has been shown that effectivity of porphyrins for photocurrent generation depends on the presence/absence of central metal in the macrocycle of porphyrin skeleton and the kind of metal. The schematic model of the contributions of the dye molecule and semiconducting electrode in the electron transfer process is shown.     

Sensitively probing the cofactor redox species and photo-induced electron transfer of wild-type and pheophytin-replaced photosynthetic proteins reconstituted in self-assembled monolayers

An ultrathin, ordered, and packed protein film, consisting of the 2-mercaptoacetic acid (MAA), polydimethyldiallylammonium chloride (PDDA), and wild-type (WT) photosynthetic reaction center (RC; termed as WT-RC) or its pheophytin (Phe)-replaced counterpart (termed as Phe-RC), was fabricated by self-assembling technique onto gold electrode for facilitating the electron transfer (ET) between RC and the electrode surface. Near-infrared (NIR)-visible (Vis) absorption and fluorescence (FL) emission spectra revealed the influence of pigment substitution on the cofactors arrangement and excitation relaxation of the proteins, respectively. Square wave voltammetry (SWV) and photoelectric tests were employed to systematically address the differences between the WT-RC films and mutant ones on the direct and photo-induced ET. The electrochemical results demonstrated that ET initiated by the oxidation of the primary donor (P) was obviously slowed down, and the formed P⁺ had more population as well as more positive redox potential in the Phe-RC films compared with those in the WT ones. The photoelectrochemical results displayed the dramatically enhanced photoelectric performances of the mutant ones, further suggesting the slow-down formation of final charge-separated state in Phe-RC. The functionalized protein films introduced in this paper provided an efficient approach to sensitively probe the redox cofactors and ET differences resulting from only minor changes in pigment arrangement in the pigment–protein complex. The favored ET process observed for the membrane proteins RC was potentially valuable for a deep understanding of the multi-step biological ET process and development of versatile bioelectronic devices.     

Photoinduced electron transfer at liquid|liquid interfaces. Part VII. Correlation between self-organisation and structure of water-soluble photoactive species

The self-organisation of a variety of dyes at the water|1,2-dichloroethane interface was studied by admittance measurements, photocurrent–potential curves and light polarisation anisotropy of the photocurrent. The heterogeneous photo-oxidation of ferrocene was studied at interfaces sensitised by Sn(IV) meso-tetra-(4-carboxyphenyl) porphyrin dichloride (SnTPPC), chlorin e-6, protoporphyrin IX (protoIX) and Fe(III) protoporphyrin IX chloride (Fe-protoIX). Cyclic voltammograms and capacitance voltage curves exhibit different features associated with the self-assembly of the dye species at the liquid|liquid boundary. In the case of SnTPPC, the capacitance curves displayed the characteristic responses commonly associated with the specific adsorption of ionic species. On the other hand, chlorin e-6, protoIX and Fe-protoIX show rather complex behaviour suggesting not only changes in the excess charge but also in the dielectric permittivity of the interface. Differences in the photocurrent efficiency were also observed under the same experimental conditions. The relative magnitude of the photocurrent responses were rationalised in terms of the phenomenological electron transfer rate constant, the photon capture cross-sections and the lifetime of the triplet state as obtained from nanosecond flash photolysis. Finally, the average molecular orientation of the adsorbed photoactive species was estimated from the photocurrent dependence on the angle of light polarisation in total internal reflection. The results show a clear correlation between the orientation of the transition dipole and the distribution of the peripheral carboxyl groups responsible for the hydrophilic nature of the dyes.     

Facile design of poly(3,4-ethylenedioxythiophene)-tris(2,2′-bipyridine)ruthenium (II) composite film suitable for a three-dimensional light-harvesting system

It has been confirmed that octasulfonatocalix[8]arene (Calx-S8) and tris(2,2′-bipyridine)ruthenium (II) (Ru(bpy)₃²⁺) can form a stable host-guest complex in aqueous solution. The binding constant for 1:1 [Calx-S8⁸⁻·Ru(bpy)₃²⁺]⁶⁻ complex formation was estimated to be (2.4±0.8)×10⁴ dm³ mol⁻¹ by fluorescence titration, which indicates that the [Calx-S8⁸⁻·Ru(bpy)₃²⁺]⁶⁻ complex is the main species in 1:1 molar ratio aqueous solution of Calx-S8 and Ru(bpy)₃²⁺. In situ UV-Vis spectroscopic measurements indicated that Ru(bpy)₃²⁺ complexes can be readily deposited onto ITO electrode through electrochemical polymerization of 3,4-ethylenedioxythiophene (EDOT) using [Calx-S8⁸⁻·Ru(bpy)₃²⁺]⁶⁻ host-guest complex as a dopant anion owing to the electrostatic interaction between the cationic conductive polymer and the anionic host-guest complex. The loading degree of the composite film with Ru(bpy)₃²⁺ can be determined by Lambert-Beer law modified for the two-dimensional concentration. The obtained composite film showed good photoelectric conversion properties in response to visible light irradiation. This is a novel photocurrent generation system in which the photoexcited state energy is efficiently collected by the conductive polymeric layer.     

铜在3%NaCl溶液中腐蚀行为的光电化学研究

Cu以其优异的导电性、导热性和易加工性广泛用于工农业生产中．自然Cu的腐蚀和防腐成为人们很关注的问题．人们已经注意到，Cl-对Cu的腐蚀有影响，并进行过一些研究．但目前使用光电化学方法研究这一问题的文章尚不多见，特别是利用测量开路光电压及其瞬态波形这一现场的、无损的、灵敏的监测方法研究户对Cu电极腐蚀全过程的文章尚未见到．本文正是利用如上方法及XPS，AES方法，研究了Cl-对Cu电极腐蚀的全过程，取得了一些有意义的结果．1实验方法Cu电极用99．99％（质量分数）的Cu制成，面积约为39mm2；电极底部由Cu导线焊接引出，…     

The high response organic ultraviolet photodetectors based on 2-TNATA as donor

Organic ultraviolet photodetectors (OUV-PDs) were fabricated utilizing 2-TNATA as an electron donor with Bphen and TPBi as electron acceptors. A high sensitivity of OUV-PDs to UV light was obtained in the range of 300–420 nm. The optimized OUV-PDs composed of Bphen as the acceptor offered a photocurrent density up to 336 µA/cm² at ?8 V with 365 nm UV light at a power of 1.2 mW/cm². The high response is attributed to the excellent electron transport ability of Bphen and the matched energy level between 2-TNATA and Bphen.     

On the photon-drag effect of photocurrent of surface states of topological insulators

The photocurrent of surface states of topological insulator due to photon-drag effect is computed, being based on pure Dirac model of surface states. The scattering by disorder is taken into account to provide a relaxation mechanism for the photocurrent. The Keldysh–Schwinger formalism has been employed for the systematic calculation of photocurrent. The helicity dependent photocurrent of sizable magnitude transverse to the in-plane photon momentum is found, which is consistent with experimental data. Other helicity independent photocurrents with various polarization states are also calculated.     

Synthesis of Z-scheme g-C3N4 nanosheets/Ag3PO4 photocatalysts with enhanced visible-light photocatalytic performance for the degradation of tetracycline and dye

Graphene-like C3N4/Ag3PO4 photocatalysts are synthesized by calcination and solutions precipitating method.The obtained g-C3N4/Ag3PO4 composites display excellent photocatalytic activity for the degradation of methylene orange(MO),rhodamine B(RhB)and tetracycline(TC)under visible light irradiation.The solutions containing RhB(10 mg/L)and MO(10 mg/L)can be efficiently degraded within15 min and 30 min.Especially,nearly 80%of TC(50 mg/L)is degraded within 20 min.which are much better than those of pure g-C3N4 nanosheets and Ag3PO4,implying that strong interaction and reasonable energy band alignment in the contact interface can effectively transfer the carries.Furthermore,the g-C3N4/Ag3PO4 composites exhibit the improved stability,and only a slight decrease is observed after three recycling runs.Moreover,the impact of inorganic ions and PH values on the degradation performance is rather small.The Z-scheme photocatalytic mechanism of the g-C3N4/Ag3PO4 composites based on the active species trapping experimental is proposed.This work demonstrates the promising applications of the g-C3N4/Ag3PO4 composites in environmental issues.