A novel metal-free porous covalent organic polymer for efficient room-temperature photocatalytic CO_(2) reduction via dry-reforming of methane

At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.

Progress in the research on organic piezoelectric catalysts for dye decomposition

Organic contaminants have posed a direct and substantial risk to human wellness and the environment.In recent years,piezo-electric catalysis has evolved as a novel and effective method for decomposing these contaminants.Although piezoelectric materials offer a wide range of options,most related studies thus far have focused on inorganic materials and have paid little attention to organic materi-als.Organic materials have advantages,such as being lightweight,inexpensive,and easy to process,over inorganic materials.Therefore,this paper provides a comprehensive review of the progress made in the research on piezoelectric catalysis using organic materials,high-lighting their catalytic efficiency in addressing various pollutants.In addition,the applications of organic materials in piezoelectric cata-lysis for water decomposition to produce hydrogen,disinfect bacteria,treat tumors,and reduce carbon dioxide are presented.Finally,fu-ture developmental trends regarding the piezoelectric catalytic potential of organic materials are explored.

Metal-Free 2D/2D van der Waals Heterojunction Based on Covalent Organic Frameworks for Highly Efficient Solar Energy Catalysis

Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.

Visible-light degradation of azo dyes by imine-linked covalent organic frameworks

Covalent organic frameworks(COFs)are nanoporous crystalline polymers with densely conjugated structures.This work discovers that imine-linked COFs exhibit remarkable photodegradation efficiency to azo dyes dissolved in water.Visible light generates different types of radicals from COFs,and superoxide radicals break N=N bonds in dye molecules,resulting in 100%degradation of azo dyes within 1 h.In contrast,these dyes cannot be degraded by conventionally used photocatalysts,for example,TiO2.Importantly,the COF photocatalysts can be recovered from the dye solutions and re-used to degrade azo dyes for multiple times without loss of degradation efficiency.This work provides an efficient strategy to degrade synthetic dyes,and we expect that COFs with designable structures may use as new photocatalysts for other important applications.

Synthesis of nano-MoS_2/bentonite composite and its application for removal of organic dye

A nano-MoS2/bentonite composite was synthesized by calcinating MoS3 deposited on bentonite in H2. The obtained composite was characterized using thermogravimetric analysis, X-ray diffractometer, scanning electron microscope and transmission electron microscope. The results show that nano-MoS2 particles are distributed on the surface of bentonite and form layered structures with layer distance of about 0.64 nm. The composite presents an excellent performance for the removal of methyl orange. Some operation conditions affect the removal efficiency of methyl orange, such as dosage of composite, initial concentration of methyl orange, temperature and pH value. However, light source does not influence the removal efficiency. The removal mechanism is attributed to the adsorption of methyl orange on the nano-MoS2/bentonite composite. The adsorption of methyl orange on the composite is in accordance with the pseudo-second-order kinetic model.

Quasi-Three-Dimensional Cyclotriphosphazene-Based Covalent Organic Framework Nanosheet for Efficient Oxygen Reduction

Metal-free carbon-based materials are considered as promising oxygen reduction reaction(ORR)electrocatalysts for clean energy conversion,and their highly dense and exposed carbon active sites are crucial for efficient ORR.In this work,two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks(Q3CTP-COFs)and their nanosheets were successfully synthesized and applied as ORR electrocatalysts.The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites,and the unique bilayer stacking of[6+3]imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR.In particular,bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets(NSs)due to the weak interlayerπ-πinteractions.Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity(half-wave potential of 0.72 V vs.RHE in alkaline electrolyte),which is one of the best COF-based ORR electrocatalysts reported so far.Furthermore,Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries(delivered power density of 156 mW cm-2 at 300 mA cm^(-2)).This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.

Platanus orientalis leaves based hierarchical porous carbon microspheres as high efficiency adsorbents for organic dyes removal

Water contamination caused by hazardous organic dyes has drawn considerable attention, among all of the techniques released, adsorption has been widely used, which however to a large degree is dependent on the development of high efficiency adsorbents. Waste biomass based porous carbon is becoming the new star class of adsorbents, and thus contribute more to the sustainable development of the society. In this work, for the first time to the best of our knowledge, abundant waste fallen Platanus orientalis leaves are employed as the raw material for hierarchical activated porous carbon(APC) microspheres via a mild hydrothermal carbonization(210 ℃,12.0 h) followed by one-step calcination(750 ℃, 1.0 h). The APC microspheres exhibit a specific surface area of 1355.53 m^2·g^-1 and abundant functional groups such as O—H and C=O. Furthermore, the APC microspheres are used as the adsorbents for removal of Rh B and MO, with the maximum adsorption capabilities of 557.06 mg·g^-1 and 327.49 mg·g^-1, respectively, higher than those of the most porous carbon originated from biomass. The adsorption rates rapidly approach to 98.2%(RhB) and 95.4%(MO) within 10 min. The adsorption data can be well fitted by Langmuir isotherm model and the pseudo-second-order kinetic model, meanwhile the intra-particle diffusion and Boyd models simultaneously indicate that the diffusion within the pores is the main rate-limiting step. Besides, the APC microspheres also demonstrate good recyclability, and may also be applied to other areas such as heterogeneous catalysis and energy storage.

Synthesis and characterization of carboxymethyl cellulose/organic montmorillonite nanocomposites and its adsorption behavior for Congo Red dye

A series of carboxymethyl cellulose/organic montmorillonite （CMC/OMMT） nanocomposites with different weight ratios of carboxymethyl cellulose （CMC） to organic montmorillonite （OMMT） were synthesized under different conditions. The nanocomposites were characterized by the Fourier transform infrared （FT-IR） spectrophotometer, X-ray diffraction （XRD） method, transmission electron microscope （TEM）, scanning electron microscope （SEM）, and thermal gravimetric （TG） analysis. The results showed that the introduction of CMC may have different influences on the physico-chemical properties of OMMT and intercalated-exfoliated nanostructures were formed in the nanocomposites. The effects of different reaction conditions on the adsorption capacity of samples for Congo Red （CR） dye were investigated by controlling the amount ofhexadecyl trimethyl ammonium bromide （CTAB）, the weight ratio of CMC to OMMT, the reaction time, and the reaction temperature. Results from the adsorption experiment showed that the adsorption capacity of the nanocomposites can reach 171.37 rag/g, with the amount of CTAB being 1.0 cation exchange capacity （CEC） of MMT, the weight ratio of CMC to OMMT being l：l, the reaction time being 6 h, and the reaction temperature being 60~C. The CMC/OMMT nanocomposite can be used as a potential adsorbent to remove CR dye from an aqueous solution.

Biosynthesis of copper nanoparticles supported on manganese dioxide nanoparticles using Centella asiatica L. leaf extract for the efficient catalytic reduction of organic dyes and nitroarenes

In this study we designed a novel,cost‐efficient and green method for the synthesis of copper nanoparticles(Cu NPs)supported on manganese dioxide(MnO2)NPs,using Centella asiatica L.leaf extract as a naturally‐sourced reducing agent,without stabilizers or surfactants.This synthetic process is environmentally‐friendly and avoids the use of toxic reducing agents.Phenolic hydroxyl groups in the leaf extract are believed to reduce Cu2+in solution to generate Cu NPs that are subsequently stabilized on the MnO2NP surfaces.The resulting Cu/MnO2nanocomposite was fully characterized using X‐ray diffraction,transmission electron microscopy,field emission scanning electron microscopy,energy‐dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy.This material was found to function as a highly active,efficient and recyclable heterogeneous catalyst for the reduction of Congo red,rhodamine B and methylene blue as well as nitro compounds such as2,4‐dinitrophenylhydrazine and4‐nitrophenol in the presence of NaBH4in aqueous media at ambient temperature.The high stability of the Cu/MnO2nanocomposite also allows the catalyst to be separated and reused several times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Enhancement of electroluminescent properties of organic optoelectronic integrated device by doping phosphorescent dye

Organic optoelectronic integrated devices（OIDs） with ultraviolet（UV） photodetectivity and different color emitting were constructed by using a thermally activated delayed fluorescence（TADF） material 4, 5-bis（carbazol-9-yl）-1, 2-dicyanobenzene（2 CzPN） as host. The OIDs doping with typical red phosphorescent dye [tris（1-phenylisoquinoline）iridium（Ⅲ）, Ir（piq）3], orange phosphorescent dye {bis[2-（4-tertbutylphenyl）benzothiazolato-N,C-（2＇）]iridium（acetylacetonate）,（tbt）2 Ir（acac）}, and blue phosphorescent dye [bis（2, 4-di-fluorophenylpyridinato）-tetrakis（1-pyrazolyl）borate iridium（Ⅲ）, FIr6] were investigated and compared. The（tbt）2 Ir（acac）-doped orange device showed better performance than those of red and blue devices, which was ascribed to more effective energy transfer. Meanwhile, at a low dopant concentration of 3 wt.%, the（tbt）2 Ir（acac）-doped OIDs showed the maximum luminance, current efficiency, power efficiency of 70786 cd/m^2, 39.55 cd/A, and 23.92 lm/W, respectively, and a decent detectivity of 1.07 × 10^11 Jones at a bias of -2 V under the UV-350 nm illumination. This work may arouse widespread interest in constructing high efficiency and luminance OIDs based on doping phosphorescent dye.

Amperometric Biosensors Sensitive to Organic Peroxides Based on Immobilization of Redox Organic Dyes and Horseradish Peroxidase in Polyester Ionomer Film

Simple and effective organic biosensors sensitive to organic peroxides such as 2 butanone per oxide and tertbutyl hydroperoxide are constructed by immobilizing a series of redox organic dyes and horseradish peroxidase in Eastman AQ polymer film. The organic dyes are methylene blue, methylene green, meldola blue, new methylene blue N and N methyl phenazine methosulphate. The biosensors display high sensitivity and fast response to tertbutyl hydroperoxide and 2 butanone peroxide because of high efficiency of electron transfer between immobilized horseradish peroxidase and the electrode via the redox organic dyes. The comparison of the biosensors employing different organic dyes is made in formal potential, linear range and response time.

Syntheses of Some Organic Fluorescent Dyes for Security Tickers

Five organic fluorescence dyes were synthesized by two- or three-step reactions. These synthetic methods have an advantage of the simple processes, low costs and high yields. The compositions of the five compounds are characterized by IR, 1H NMR, elemental analyses and fluorescence spectroscopies. The quantum yields of fluorescence were measured.

Enhancement of Two-photon Absorption by Ce^(3+) Sensitization in Organic Dyes

The two-photon absorption（TPA）and TPA-induced frequency upconversion emission properties of the dyes 4-[P-（dicyanoethylamino）crystal]-N-methypyrdinium iodide and the complex of 4-[P-（dicyanoethylamino）crystal]-N-methypyrdinium iodide and Ce（NO3）3 were experimentally studied.It was found that the TPA cross section for the dye sensitized by Ce3＋ is two factors larger than that of the dye without being sensitized.A three-level system model of the dye molecules was used to analyze the enhancement of TPA by the sensitizer Ce3＋,which indicated that the sensitizer results in the increase of the transition dipole moment from the one-photon allowed excited state（1Bu）to the two-photon allowed excited state（2Ag）.

Detailed analysis of ultrathin fluorescent red dye interlayer for organic photovoltaic cells

The influence of an ultrathin 4-（dicyanomethylene）-2-t-butyl-6-（1,1,7,7-tetramethyljulolidyl-9-enyl）-4H-pyran （DCJTB） fluorescent dye layer at donor/acceptor heterojunction on the performance of small-molecule organic photovoltaic （OPV） cell is studied. The structure of OPV cell is of indium-tin oxide （ITO）/copper phthalocyanine （CuPc）/DCJTB/fullerene （C60）/bathophenantbroline （Bphen）/Ag. The results show that open circuit voltage （Voc） increases to 0.57 V as the film thickness of DCJTB layer increases from 0.2 to 2.0 nm. By using an equivalent circuit model, the enhancement of VOC is found to be attributed to the reduced reverse saturation current density （Js） which is due to the lower highest occupied molecular orbital （HOMO） level in DCJTB than that in CuPc. Also, the short circuit current density （JSC） is affected when the DCJTB layer becomes thicker, resulting from the high series resistance RsA due to the low charge carrier mobility of fluorescent red dye.

The Up-conversion Laser Properties of a Non-polar Organic Dye and the Influence of Solvents and Pumping Wavelengths

A non-polar organic dye, E, E-1, 4-bis[4＇-（N,N-dibutylamino）styryl]-2,5-dimethoxybenzene （DBASDMB）, has been synthesized and characterized, and its structure has been determined. Pumped with a 200fs pulse this dye showed the up-conversion laser properties. The influences of various organic solvents and different pumping wavelength on the laser properties have been demonstrated.

Study on Photocatalytic Degradation of Organic Dye by Titanium Dioxide Nanotube Array

Titanium based titanium dioxide （TiO2） nanotube arrays were prepared by electrochemical oxidation method, their microstructures were characterized, and the effects of sintering temperature and initial dye concentration and pH value on degradation performance of TiO2 nanotubc arrays wcrc investigated with methyl orange as a degradation object. The results showed that TiO2 nanotube arrays prepared by sintering at 500 ℃ exhibited good morphology and the highest photocata- lyric degradation efficiency; the degradation efficiency of the TiO2 nano material （500 ℃ ） to high concentration dye was higher than that to low concentration dye; the TiO2 nanotube array （500 ℃ ） exhibited higher degradation efficiency on dye solution at the pH of 3 than on that at the pH of 5.77 ; and the degradation efficien- cy of the TiO2 nanotube array （500 ℃） to 10 mg/L methyl orange solution （pH =3） reached 85.2%.

Synthesis of Three-Dimensional Hierarchical Flower-Like Mg–Al Layered Double Hydroxides with Excellent Adsorption Performance for Organic Anionic Dyes

In this work,a facile and effective strategy to prepare three-dimensional(3D)hierarchical flower-like Mg–Al layered double hydroxides(3D-LDH)was developed via a one-step double-drop coprecipitation method usingγ-Al 2O 3particles as a template.The characterization and experimental results showed that the calcined product,3D-LDO,features a large specific surface area of 204.2 m^(2)/g,abundant active sites,and excellent adsorption performance for Congo red(CR),methyl orange(MO),and methyl blue(MB).The maximum adsorption capacities of 3D-LDO for CR,MO,and MB were 1428.6,476.2,and 1666.7 mg/g,respectively;such performance is superior to that of most reported adsorbents.The adsorption mechanism of organic anionic dyes by 3D-LDO was extensively investigated and attributed to surface adsorption,the memory effect of 3D-LDO,and the unique 3D hierarchical flower-like structure of the adsorbent.Recycling performance tests revealed that3D-LDO has satisfactory reusability for the three organic anionic dyes.

Charge and Energy Transfer in the Metal-free Indoline Dyes for Dye-sensitized Solar Cells

Metal-free indoline dyes for dye-sensitized solar cells were studied by employing quantum chemistry methods. Comparative study of the properties of both ground and excited states of metal-free indoline dyes for dye-sensitized solar cells revealed： （i） as the number of rhodanine rings increases, the energy difference between HOMO and LUMO decreases and there is a red shift in the absorption spectrum with the binding energy increased, and the transition dipole moment decreased; （ii） Based on an analysis of charge differential density, we observed that the charge and energy are transfered from the phenylethenyl to the indoline and rhodanine rings; （iii） The electron-hole coherences are mainly on the indoline and rhodanine rings, and the exciton sizes are 30 and 40 atoms for indoline dyes with one and two rhodanline rings, respectively. These results serve as a good example of computer-aided design in metal-free indoline dyes for dye-sensitized solar cells.

THE STUDY OF PHOTOELECTROCHEHICAL CELLS BASED ON CHLOROPHYLL AND ORGANIC DYES

Tetraiodofluorescein(TIF)and safranine T(ST)had great effects on the photovoltaic parameters of the cells.The Voc of the cells was about 3-5 times higher than that of the cells without TIK and ST,Isc increased 1 to 2 orders of magnitude.The Voc and Isc could be increased greatly only when Voc and Isc of the cell with Pt as WE properly combined with the Voc and Isc produced by chla in the original cell.According to absorption spectra and output characters,the results were elucidated.

Green Light-Emitting Organic Electroluminescent Device with a New Fluorescent Dye Dispersed in Poly(N-vinylcarbazole) Emitter Layer

Double-layer organic electroluminescent devices have been constructed. A new fluorescent dye, 9,10-bis(phenylethynyl)anthracence, was chosen as the dopant which was molecularly dispersed in the polymer film, and green light was observed from the device with luminance of 130cd/m(2) at 17V.