Approaches to Improving Selectivity During Photoelectrochemical Transformation of Small Molecules

Photoelectrochemical (PEC) small-molecule oxidation can selectively transform substrates into high-value-added fine chemicals and increase the rate of cathode hydrogen evolution. Nevertheless, achieving high-selectivity PEC oxidation of small molecules to produce specific products is a very challenging task. In general, selectivity can be improved by changing the surface catalyticsites of the photoanode and modulating the interfacial environments of the reactions. Herein, recent advances in approaches to improving selective PEC oxidation of small molecules are introduced. We first briefly discuss the basic concept and fundamentals of small-molecule PEC oxidation. The reported approaches to improving the performance of selective PEC oxidation of small molecules are highlighted from two aspects: (1) changing the surface properties of photoanodes by selecting suitable materials or modifying the photoanodes and (2) mediating the oxidation reactions using redox mediators. The PEC oxidation mechanism of these studies is emphasized. We also discuss the challenges in this research direction and offer a perspective on the further development of selective PEC-based small-molecule transformation.

Electro‑copolymerized film of ruthenium catalyst and redox mediator for electrocatalytic water oxidation

Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.

Engineering Spin States of Isolated Copper Species in a Metal-Organic Framework Improves Urea Electrosynthesis

The catalytic activities are generally believed to be relevant to the electronic states of their active center, but understanding this relationship is usually difficult. Here, we design two types of catalysts for electrocatalytic urea via a coordination strategy in a metal–organic frameworks: Cu^(Ⅲ)-HHTP and Cu^(Ⅱ)-HHTP. Cu^(Ⅲ)-HHTP exhibits an improved urea production rate of 7.78 mmol h^(−1)g^(−1) and an enhanced Faradaic efficiency of 23.09% at-0.6 V vs. reversible hydrogen electrode, in sharp contrast to Cu^(Ⅱ)-HHTP.Isolated CuⅢspecies with S = 0 spin ground state are demonstrated as the active center in Cu^(Ⅲ)-HHTP, different from Cu^(Ⅱ) with S = 1/2 in Cu^(Ⅱ)-HHTP. We further demonstrate that isolated Cu^(Ⅲ)with an empty dx2-y20orbital in Cu^(Ⅲ)-HHTP experiences a single-electron migration path with a lower energy barrier in the C–N coupling process, while Cu^(Ⅱ)with a single-spin state( d_(x2-y2)^(1)) in Cu^(Ⅱ)-HHTP undergoes a two-electron migration pathway.

Nitrogen-doping boosts ^(*)CO utilization and H_(2)O activation on copper for improving CO_(2) reduction to C_(2+) products

To improve the electrocatalytic transformation of carbon dioxide (CO_(2)) to multi-carbon (C_(2+)) products is of great importance.Here we developed a nitrogen-doped Cu catalyst,by which the maximum C_(2+) Faradaic efficiency can reach 72.7%in flow-cell system,with the partial current density reaching 0.62 A cm^(-2).The in situ Raman spectra demonstrate that the *CO adsorption can be strengthened on such a N-doped Cu catalyst,thus promoting the *CO utilization in the subsequent C–C coupling step.Simultaneously,the water activation can be well enhanced by N doping on Cu catalyst.Owing to the synergistic effects,the selectivity and activity for C_(2+) products over the N-deoped Cu catalyst are much improved.

Effect of dye-metal complexation on photocatalytic decomposition of the dyes on TiO_2 under visible irradiation

The photocatalytic degradation of dyes （Acid Chrome Blue K （ACBK） and Alizarin Red （AR）） with strong complexation ability was investigated in the presence of metal ions under visible light irradiation. It was found that, at low dye-metal ratio, the photodegradation of ACBK was markedly inhibited by the addition of high oxidative potential Cu2＋. However, at high dye-metal ratio, the presence of Cu2＋ enhanced the photodegradation of ACBK. The negtive effect of Cu2＋ on the photodegradation of AR was observed for all dyemetal ratios. The relative chemical inert Zn2＋ tended to enhance the photodegradation of both anionic dyes. The mechanism underlying the different effect of Cu2＋ was discussed from the different roles of surface-adsorbed and dye-coordinated Cu2＋ in the photodegradation of dyes.

Preparation and performance of dye-sensitized solar cells based on ZnO-modified TiO_2 electrodes

The ZnO-modified TiO2 electrode was prepared by adding Zn（CH3COO）2·2H2O to the TiO2 colloid during the sol-gel production process, and was used in dye-sensitized solar cells （DSCs）. The open circuit voltage （Voc） and fill factor （if） of the cells were improved sig- nificantly. The performances of the ZnO-modified TiO2 electrode such as dark current, transient photocurrent, impedance, absorption spectra, and fiat band potential （Vfb） were investigated. It is found that the interface charge recombination impedance increases and Vfb shifts about 200 mV toward the cathodic potential. The effect mechanism of ZnO modification on the performance of DSCs may be that ZnO occupies the surface states of the TiO2 film.

Light-driven activation of carbon-halogen bonds by readily available amines for photocatalytic hydrodehalogenation

A straightforward protocol using readily available aromatic amines,N,N,N',N'-tetramethyl-p-phenylenediamine or N,N,N',N'-tetramethylbenzidine,as photocatalysts was developed for theefficient hydrodehalogenation of organic halides,such as 4'-bromoacetophenone,polyfluoroarenes,cholorobenzene,and 2,2',4,4'-tetrabromodiphenyl ether(a resistant and persistent organic pollu-tant).The strongly reducing singlet excited states of the amines enabled diffusion-controlled disso-ciative electron transfer to effectively cleave carbon-halogen bonds,followed by radical hydrogena-tion.Diisopropylethylamine served as the terminal electron/proton donor and regenerated theamine sensitizers.

Electrochemical impedance analysis of nanoporous TiO_2 electrode at low bias potential

TiO2 colloid was prepared by the sol-gel method and was bladed on transparent conduction glass to made nanoporous electrode. The impedance performance of TiO2 electrode was studied at various bias potential.A simplified equivalent circuit was proposed to investigate the charge transport impedance of TiO2 film and good fitting results were obtained.

Investigation of Mechanisms of Enhanced Open-Circuit Photovoltage of Dye-Sensitized Solar Cells Based the Electrolyte Containing 1-Hexyl-3-Methylimidazolium Iodide

The open-circuit photovoltage is improved by adding 1-hexyl-3-methylimidazolium iodide （HMImI） into the electrolyte. To investigate the mechanisms of the increase of the open-circuit photovoltage, we take the MottSchottky analysis and time-resolved mid-infrared absorption spectroscopy to study the band edge movement of TiO2 and the rate of back electron transfer, respectively. The results indicate that the negative shift of the conduction band of TiO2 is a predominant factor to increase the open-circuit photovoltage for the electrolyte containing HMImI,

Electrodeposition of SnO_2 nanocrystalline thin film using butyl-rhodamine B as a structure-directing agent

Porous SnO2 nanocrystalline thin films were successfully electrodeposited from an oxygen-saturated acid aqueous solution of SnCl2 containing different concentrations of butyl-rhodamine B（BRhB） at 70℃.BRhB with substitute of amidocyanogen can be dissolved in the acid deposition solution,where HCl was added to suppress hydrolysis of SnCl2.So it was used as a structure-directing agent to promote the crystal growth of SnO_2.The formed porous morphology and tetragonal rutile crystalline structure of the electrodeposited thin films were controlled by the addition of BRhB with different amounts.

Drug-delivery and multifunction possibilities of hypocrellin photosensitizers

Photodynamic therapy(PDT)has been a routine treatment of tumors and some microvascular diseases,but clinically available photosensitizers are still scarce.Among all kinds of photo-sensitizers,hypocellins possess the most characteristics of ideal photosensitizers,such as,high photo-activity but low dark toxicity,fast clearance from tssues.This review is focused on two main topics,drug-delivery problem of hypocrellins and how the environment-sensitive fluorescence of bypecrellins was used for recognition of various biomolecules.Drug-delivery of hypocrellins was mainly achieved in two strategies一preparing the drugdelivery vehicles and finding quantitatively amphiphilic derivatives.Hypocrellin fAuorescence originated from the intramolecular proton transfer is very distinct from other kinds of photosensitizers.Recently,it was proved that quan-titative hypocrellin ftuorescence could not only reoognize various biomolecules,including proteins,polysaocharides and lipids,but also distinguish the specific binding from nonspedifie binding with some kind of biomolecules.Meantime,hypocrellin fluorescence was pH sensitive.It is known that tumor cells or tses have the features of a large amount of lipid,neonatal collagen,over expression of polysaccharides,and lower pH values compared to normal tissues.According to the relative but not absolute specifcity,further studies on quantitative recognition of various biomolecules at a cellular level,may find a new clue to treat tumors by joint usage of photodynamic diagnosis(PDD)and PDT.

Synthesis,characterization,and activity of a covalently anchored heterogeneous perylene diimide photocatalyst

The consecutive two‐photon photocatalytic behavior of perylene diimide(PDI)enables it to catalyze photoreduction reactions that are thermodynamically unfavorable via single‐photon processes.In this work,we developed a heterogeneous PDI photocatalyst by covalently binding PDI molecules on the surface of nanosilica.This photocatalyst structure overcomes the intrinsic limitation of the low solubility of PDI,but retains its consecutive two‐photon photocatalytic property.Detailed characterization of the photocatalyst by techniques such as thermogravimetric analysis,solid‐state nuclear magnetic resonance spectroscopy,and Fourier transform infrared spectroscopy indicated that the PDI molecules were anchored covalently on the surface of nanosilica.The obtained photocatalyst reduced aryl halides under visible‐light irradiation in polar organic solvent and in water.The present study provides a promising strategy to realize two‐photon activity of PDI in common solvents for photocatalytic applications.

Low temperature fabrication of flexible carbon counter electrode on ITO-PEN for dye-sensitized solar cells

A novel low temperature method was used to prepare the mesoporous carbon（MC） counter electrode（CE） on indium-doped tin oxide coated polyethylene naphthalate（ITO-PEN） for flexible dye-sensitized solar cells（DSSCs）.The obtained flexible MC CEs with carbon loading of 280μg cm^（-2） were characterized by SEM,XRD and electrochemical impedance.The light-to-electricity conversion efficiency of the DSSC fabricated with the prepared flexible MC CE was 86%of that of DSSC based on the decomposited Pt CE.

Electron transport properties of TiO_2 shell on Al_2O_3 core in dye-sensitized solar cells

The performance of dye-sensitized solar cells （DSSCs） is strongly affected by the properties of semiconductor nanoparticles. In this work, we used TiO2 particles prepared by TiC14 hydrolysis n times on A1203 films （A/T（n））, and investigated morphology, photoelectric, and electron transport properties of A/T（n）. The TiO2 shell was composed of 10-20 nm nanoparticles and the number of nanoparticles increased with increasing TIC14 treatment times. The highest photoelectric conversion efficiency of 3.23% was obtained as A/T（4）. IMPS results indicated that electron transport rate was high enough to conduct current, and was not the dominating effect to limit the Jsc. Jsc was mainly determined by dye loading on TiO2 and the interconnection of TiO2. These may provide a new strategy for preparing semiconductor working electrodes for DSSC.

High-pressure dynamic,thermodynamic properties,and hardness of CdP_2

Using a pseudopotential plane-waves method,we calculate the phonon dispersion curves,thermodynamic properties,and hardness values of α-CdP;and β-CdP;under high pressure.From the studies of the phonon property and enthalpy difference curves,we discuss a phase transform from β-CdP;to a-CdP;in a pressure range between 20 GPa and 25 GPa.Then,the thermodynamic properties,Debye temperatures,and heat capacities are investigated at high pressures.What is more,we employ a semiempirical method to evaluate the pressure effects on the hardness for these two crystals.The results show that the hardness values of both α-CdP;and β-CdP;increase as pressure is increased.The influence mechanism of the pressure effect on the hardness of CdP;is also briefly discussed.

Dye-sensitized solid-state solar cells fabricated by screen-printed TiO_2 thin film with addition of polystyrene balls

The screen-printed nanoporous TiO2 thin film was employed to fabricate dye-sensitized solid-state solar cells using CuI as hole-transport materials. The solar cell based on nanoporous TiO2 thin film with large pores formed by the addition of polystyrene balls with diameter of 200 nm to the TiO2 paste exhibits photovoltaic performance enhancement, which is attributed to the good contact of CuI with surface of dye-sensitized thin film due to easy penetration of CuI in the film with large pores.

Explanation of Effect of Added Water on Dye-Sensitized Nanocrystalline TiO2 Solar Cell： Correlation between Performance and Carrier Relaxation Kinetics

Time-resolved mid-IR transient absorption spectroscopy is employed to explore the mechanism of improving the performance of dye-sensitized TiO2 solar cell （DSSC） when a certain amount of H2 0 is added into the electrolyte. The relaxation kinetics of dye-sensitized TiO2 nanocrystalline film and the corresponding DSSC performance are investigated under different conditions. It is found that the interracial charge recombination is retarded and electron injection efficiency is increased in the water vapour and in the electrolyte when D20 is added. The values of open-circuit photovoltage Voc and the short-circuit photocarrent Jsc of the cells are linearly correlated to the product of the two decay time constants. We also observed that Voc well correlates with electron injection efficiency. It provides a preliminary microscopic account for the function of the added water in improving the performance of DSSCs.

Effect of Poly（Ether Urethane） Introduction on the Performance of Polymer Electrolyte for All-Solid-State Dye-Sensitized Solar Cells

The introduction of poly（ether urethane） （PEUR） into polymer electrolyte based on poly（ethylene oxide）, LiI and I2, has significantly increased the ionic conductivity by nearly two orders of magnitudes. An increment of I3- diffusion coefficient is also observed. All-solid-state dye-sensitized solar cells are constructed using the polymer electrolytes. It was found that PEUR incorporation has a beneficial effect on the enhancement of open circuit voltage VOC by shifting the band edge of TiO2 to a negative value. Scanningelectron microscope images indicate the perfect interfacial contact between the TiO2 electrode and the blend electrolyte.

Investigation of third-order nonlinear optical properties of two azo-nickel chelate compounds

This paper investigates the third-order nonlinear optical properties of two azo-nickel chelate compounds by the optical Kerr gate method at 830 nm wavelength with pulse duration of 120 fs. Both of the two compounds exhibited large third-order optical nonlinearity. The second-order hyperpolarizability,γ, of Compound 1 is of 1.0 × 10^-31 esu. Due to the charge transfer, the γ of Compound 2 with electron donor and acceptor group is 4.9 × 10^-31 esu, which is a four-time enhancement in comparison with Compound i. The absorption spectra show that the electron push-pull effect, which induces intramolecular charge transfer, leads to the increased optical nonlinearity.