Study on photoconductivity of dye-polymer-based solid-state thin film

In this article, we describe a solid-state photoelectrochemical cell for light detection. Safranine-T dye mixed with polyvinyl alcohol (PVA) solution was deposited on a conducting and transparent indium-tin-oxide (ITO)-coated glass that was used as one electrode and another ITO-coated glass as the counterelectrode. A solid polymeric electrolyte consisting of polyethylene oxide-ammonium perchlorate-ethylene carbonate and propylene carbonate with suitable weight ratio was prepared and sandwiched between these two ITO-coated glass electrodes, which were separated by a Teflon spacer about 50 μm thick. The cell was biased with a direct current source to make the dye and PVA-coated ITO as the anode and the other ITO as the cathode. On illumination by a tungsten lamp, from the cathode side, the change of photocurrent was measured. The dark current-voltage characteristics and the growth and decay of the photocurrent for steady and pulsed illumination were studied.     

Photo-electrochemical water splitting system with three-layer n-type organic semiconductor film as photoanode under visible irradiation

A three-layer structure of n-type organic semiconductors(PTCDA/PTCDA:PCBM/PCBM) is successfully identified as photoanode for photoelectrochemical water oxidation during the overall splitting of water into hydrogen/oxygen in a nearly stoichiometric ratio(H2:O2=2:1) under visible irradiation(λ > 420 nm).A possible charge separation mechanism under visible light illumination was also proposed.     

DOPANT EFFECTS OF SQUARYLIUM CYANINE DYES ON FUNCTIONAL DEVICES

本文初步研究了方酸菁染料在功能器件中的应用,并探讨了相关机理。我们用方酸菁掺杂8羟基喹啉铝发光层,获得了红光有机电致发光器件;用掺杂方酸菁的联吡啶钌作光敏剂修饰TiO₂纳晶薄膜电极,有效地弥补了联吡啶钌在600nm以上红光区采光能力的不足,从而大大提高了光电化学太阳电池的总体光电转换效率。     

Ene-Reductase: A Multifaceted Biocatalyst in Organic Synthesis

Biocatalysis integrate microbiologists, enzymologists, and organic chemists to access the repertoire of pharmaceutical and agrochemicals with high chemoselectivity, regioselectivity, and enantioselectivity. The saturation of carbon-carbon double bonds by biocatalysts challenges the conventional chemical methodology as it bypasses the use of precious metals (in combination with chiral ligands and molecular hydrogen) or organocatalysts. In this line, Ene-reductases (ERs) from the Old Yellow Enzymes (OYEs) family are found to be a prominent asymmetric biocatalyst that is increasingly used in academia and industries towards unparalleled stereoselective trans-hydrogenations of activated C=C bonds. ERs gained prominence as they were used as individual catalysts, multi-enzyme cascades, and in conjugation with chemical reagents (chemoenzymatic approach). Besides, ERs’ participation in the photoelectrochemical and radical-mediated process helps to unlock many scopes outside traditional biocatalysis. These up-and-coming methodologies entice the enzymologists and chemists to explore, expand and harness the chemistries displayed by ERs for industrial settings. Herein, we reviewed the last five year's exploration of organic transformations using ERs.     

Application of Novel Calix[4]arene Metal-free Sensitizers in Dye-sensitized Photoelectrochemical Cells for Water Splitting

A series of novel calix[4]arene metal-free dyes, featuring macrocyclic structure and unique conical conformation, has been introduced into photoanode-based dye-sensitized electrochemical cell system as photosensitizers. The electrochemical properties of the corresponding sensitized photoanodes were systematically studied in the absence/presence of water oxidation catalyst(WOC). Furthermore, the visible-light-driven overall water-splitting reactions were conducted by fully assembled devices, obtaining a performance trend of Calix-3 > Calix-2 > Calix-1. The corresponding device of Calix-3 exhibited the best photoactivity, giving an initial photocurrent density of ca. 300 μA/cm², an IPEC peak value of ca. 9.0% at 365 nm and a wide photo-respond band up to ca. 620 nm. The best performance of Calix-3 can be attributed to its most effective light-harvesting ability, best ICT transition property, highest oxidation potential and thus best ability of activating WOC. This work offers an inspiration for the application of new-type effective metal-free sensitizers in photocatalytic water-splitting device.     

Recent Progress in LDH@Graphene and Analogous Heterostructures for Highly Active and Stable Photocatalytic and Photoelectrochemical Water Splitting

Photocatalytic (PC) and photoelectrochemical (PEC) water splitting is a plethora of green technological process, which transforms copiously available photon energy into valuable chemical energy. With the augmentation of modern civilization, developmental process of novel semiconductor photocatalysts proceeded at a sweltering rate, but the overall energy conversion efficiency of semiconductor photocatalysts in PC/PEC is moderately poor owing to the instability ariseing from the photocorrosion and messy charge configuration. Particularly, layered double hydroxides (LDHs) as reassuring multifunctional photocatalysts, turned out to be intensively investigated owing to the lamellar structure and exceptional physico-chemical properties. However, major drawbacks of LDHs material are its low conductivity, sluggish mass transfer and structural instability in acidic media, which hinder their applicability and stability. To surmount these obstacles, the formation of LDH@graphene and analogus heterostructures could proficiently amalgamate multi-functionalities, compensate distinct shortcomings, and endow novel properties, which ensure effective charge separation to result in stability and superior catalytic activities. Herein, we aim to summarize the currently updated synthetic strategies used to design heterostructures of 2D LDHs with 2D/3D graphene and graphene analogus material as graphitic carbon nitride (g-C₃N₄), and MoS₂ as mediator, or interlayer support, or co-catalyst or vice versa for superior PC/PEC water splitting activities along with long-term stabilities. Furthermore, latest characterization technique measuring the stability along with variant interface mode for imparting charge separation in LDH@graphene and graphene analogus heterostructure has been identified in this field of research with understanding the intrinsic structural features and activities.     

A Titanium‐Doped SiOx Passivation Layer for Greatly Enhanced Performance of a Hematite‐Based Photoelectrochemical System

This study introduces an in situ fabrication of nanoporous hematite with a Ti‐doped SiO_x passivation layer for a high‐performance water‐splitting system. The nanoporous hematite with a Ti‐doped SiO_x layer (Ti‐(SiO_x/np‐Fe₂O₃)) has a photocurrent density of 2.44 mA cm^?2 at 1.23 V_RHE and 3.70 mA cm^?2 at 1.50 V_RHE. When a cobalt phosphate co‐catalyst was applied to Ti‐(SiO_x/np‐Fe₂O₃), the photocurrent density reached 3.19 mA cm^?2 at 1.23 V_RHE with stability, which shows great potential of the use of the Ti‐doped SiO_x layer with a synergistic effect of decreased charge recombination, the increased number of active sites, and the reduced hole‐diffusion pathway from the hematite to the electrolyte.     

Dual Oxygen and Tungsten Vacancies on a WO3 Photoanode for Enhanced Water Oxidation

Alleviating charge recombination at the electrode/electrolyte interface by introducing an overlayer is considered an efficient approach to improve photoelectrochemical (PEC) water oxidation. A WO₃ overlayer with dual oxygen and tungsten vacancies was prepared by using a solution‐based reducing agent, LEDA (lithium dissolved in ethylenediamine), which improved the PEC performance of the mesoporous WO₃ photoanode dramatically. In comparison to the pristine samples, the interconnected WO₃ nanoparticles surrounded by a 2–2.5 nm thick overlayer exhibited a photocurrent density approximately 2.4 times higher and a marked cathodic shift of the onset potential, which is mainly attributed to the facilitative effect on interface charge transfer and the improved conductivity by enhanced charge carrier density. This simple and effective strategy may provide a new path to improve the PEC performance of other photoanodes.     

Full Characterization and Photoelectrochemical Behavior of Pyrene‐fused Octaazadecacene and Tetraazaoctacene

The preparation of large azaacenes is very important because of their great potential in organic electronics. In this report, we successfully synthesized and fully characterized two stable pyrene‐fused large azaacenes: octaazadecacene and tetraazaoctacene through employing a relatively moderate aromatic unit pyrene as imbedded species in the backbone of azaacenes to ensure large conjugation and stability. The photoelectrochemical (PEC) studies indicate that both azaacenes display n‐type semiconductor behavior.     

有机化合物表面光电压谱的研究

<正> 半导体与金属接触处产生表面势垒,当光照射在样品与金属的接触界面上时,在光照面和非光照面之间建立起电位差,记录这个电位差和入射光波长的关系得到表面光电压谱。表面光电压谱反映材料的光吸收性质和电子的带-带跃迁,同时又受到光生载流子寿命的影响。应用表面光电压技术已经测量了单晶半导体的光伏效应,少数载流子的扩散长度以及表面态等。近来,王德军等用表面光电压谱的方法研究了无机半导体粉末光催化剂的活性。