Adsorption-photocatalytic degradation of organic pollutants in water is an advantageous method for environmental purification.Herein,a feasible strategy is developed to construct a novel dual S-scheme heterojunctions Cu_(7)S_(4)-TiO_(2)-conjugated polymer with a donor-acceptor structure.There are abundant adsorption active sites for adsorption in the porous structure of the composites,which can rapidly capture pollutants through hydrogen bonding and π-π interactions.In addition,the dual S-scheme heterojunctions effectively improve carrier separation while maintaining a strong redox ability.Thus,the optimized 1.5% CST-130 catalysts can adsorb 71% of 20 ppm BPA in 15 min and completely remove it within 30 min with high adsorption capacity and photodegradation efficiency.Therefore,this study provides a new inspiration for synergistic adsorption and degradation of BPA and the construction of dual S-scheme heterojunction.
Wanjun XuXunxun LiDongyun ChenNajun LiQingfeng XuHua LiJianmei Lu
Photoinitiators of the oxime ester(OXE)or ketoxime ester(OXE-CO)type can rapidly undergo N—O bond cleavage and generate free radicals to initiate photopolymerization under LED excitation,occupying an important position in the field of photocuring.However,the commercial OXEs,e.g.,OXE 01 and 02 withλ_(max)'s at 326 and 344 nm,respectively,still do not well match the emission spectra of LEDs.Developing novel OXEs/OXE-COs with high photosensitivity for long-wavelength LEDs has great significance.Here,four new OXEs/OXE-COs with nitro-carbazole-styrene conjugated chromophore were designed,synthesized,and used as photoinitiators.Results demonstrated that all photoinitiators had strong absorption within the UV–vis range(λ_(max):381—392 nm,ε_(max):8200—11500 M^(−1)·cm^(−1)).Molecular design of the oxime ester cleavage to produce a small volume methyl group and a methacryl group with an unsaturated double bond brings high activity and low migration,respectively,in one-photon polymerization under 365—450 nm LEDs excitation.Moreover,OXEs/OXE-COs with PETA exhibited a wide processing window,high resolution(line accuracy~100 nm)and good nano-patterning capability under 780 nm femtosecond laser irradiation in two-photon polymerization,indicating their great potential in 2D/3D microfabrication technologies.
Jie XieYonghui WangXiaobin WangXuefeng FangQinyan ZhuChun CaoMing Jin
Hydrogen-bonded organic frameworks(HOFs)are a promising candidate for optical sensing,but the lack of effective design strategies poses significant challenges to the construction of HOFs for organic acid sensing.In this work,the first HOF for organic acid sensing is reported by constructing a multiplepyridine carbazole-based dense HOF,namely HOF-FJU-206,from a tripyridine-carbazole molecular 3,6-bis(pyridin-4-yl)-9-(4-(pyridin-4-yl)phenyl)-9H-carbazole(CPPY)with carbazole center for luminescence,pyridyl sites for its responsive of hydrogen proton,and narrow channels in the dense framework for the diffusion of hydrogen protons.HOF-FJU-206 exhibits differential responsively fluorescence sensing and recovery properties to formic,acetic,and propionic acids with different molecular sizes and p Kavalue(acid dissociation constant).The dissociation degree of various acids can be determined by analyzing the slope of changes in both peak wavelength and intensity of in-situ fluorescence,which easily enables the dual-corrective recognition of different acids.The varying degree of protonation at pyridine sites is proved to be the reason for differential sensing of various acids,as demonstrated by1H NMR spectra,X-ray photoelectron spectroscopy(XPS)characterization,and modeling studies.
Conventional self-assembled monolayer(SAM)hole transporters in organic solar cells(OSCs)generally suffer from poor uniformity and limited thickness tolerance,hindering their large-scale production.To overcome these limitations,we introduce a novel polymeric hole transporter synthesized by polymerizing carbazole phosphonic acid(PACz).The resultant Poly-2PACz material exhibits exceptional conductivity,high tolerance for variations in layer thickness,and improved film uniformity compared with conventional SAMs.Consequently,the OSCs utilizing Poly-2PACz achieve a remarkable power conversion efficiency of 19.1%and a high fill factor of 81.2%,surpassing the devices based on 2PACz.Moreover,Poly-2PACz-based OSCs demonstrate excellent operational stability,retaining over 80%of their initial efficiency after 1,400 h of continuous light exposure in ambient conditions.This work presents a novel strategy for designing hole transporters,paving the way for more efficient and stable OSCs.
Building on the recent systematic research on 1Hbenzo[f]indole(Bd),an important advancement in constructing ultralong organic room temperature(UORTP)materials with a universal strategy via a readily obtained unit(7H-Benzo[c]carbazole,BCz)is proposed in this work.Pure powders of BCz and its derivatives merely exhibit blue fluorescence at ambient condition.However,when BCz and its derivatives are dispersed into polymer or powder matrixes,strong photo-activated green UORTP can be observed from their doped systems at room temperature.Moreover,the UORTP color can be tuned between green and yellow depending on the matrix.The ultralong phosphorescence originates from the generation of charge-separated states via radicals.The matrixes play a key role in both stabilizing charge-separated states and controlling UORTP color.More interestingly,when using polymethyl methacrylate as matrix,the doped films achieve stronger photo-activated ultralong phosphorescence underwater than in air at room temperature.Comparedwith Bd,BCz achieves better performance not only in ultralong phosphorescence properties but also in practical applications.This work gains a deeper insight into the mechanism of UORTP and paves a new approach to applying organic phosphorescent materials to underwater coating and imaging.
Chen QianXue ZhangZhimin MaXiaohua FuZewei LiHuiwen JinMingxing ChenHong JiangZhiyong Ma
Efficient multi-resonance thermally activated delayed fluorescence(MR-TADF)materials hold significant potential for applications in organic light-emitting diodes(OLEDs)and ultra-high-definition displays.However,the stringent synthesis conditions and low yields typically associated with these materials pose substantial challenges for their practical applications.In this study,we introduce an innovative strategy that involves peripheral modification with sulfur and selenium atoms for two materials,CFDBNS and CFDBNSe.This approach enables a directed one-shot borylation process,achieving synthesis yields of 66%and 25%,respectively,while also enhancing reverse intersystem crossing rates.Both emitters exhibit ultra-narrowband sky-blue emissions centered around 474 nm,with full width at half maximum(FWHM)values as narrow as 19 nm in dilute toluene solutions,along with high photoluminescence quantum yields of 98%and 99%in doped films,respectively.The OLEDs based on CFDBNS and CFDBNSe display sky-blue emissions with peaks at 476 and 477 nm and exceptionally slender FWHM values of 23 nm.Furthermore,the devices demonstrate remarkable performances,achieving maximum external quantum efficiencies of 24.1%and 27.2%.This work presents a novel and straightforward approach for the incorporation of heavy atoms,facilitating the rapid construction of efficient MR-TADF materials for OLEDs.
Carbazole is an irreplaceable basic organic chemical raw material and intermediate in industry.The separation of carbazole from anthracene oil by environmental benign solvents is important but still a challenge in chemical engineering.Deep eutectic solvents (DESs) as a sustainable green separation solvent have been proposed for the separation of carbazole from model anthracene oil.In this research,three quaternary ammonium-based DESs were prepared using ethylene glycol (EG) as hydrogen bond donor and tetrabutylammonium chloride (TBAC),tetrabutylammonium bromide or choline chloride as hydrogen bond acceptors.To explore their extraction performance of carbazole,the conductor-like screening model for real solvents (COSMO-RS) model was used to predict the activity coefficient at infinite dilution (γ^(∞)) of carbazole in DESs,and the result indicated TBAC:EG (1:2) had the stronger extraction ability for carbazole due to the higher capacity at infinite dilution (C^(∞)) value.Then,the separation performance of these three DESs was evaluated by experiments,and the experimental results were in good agreement with the COSMO-RS prediction results.The TBAC:EG (1:2) was determined as the most promising solvent.Additionally,the extraction conditions of TBAC:EG (1:2) were optimized,and the extraction efficiency,distribution coefficient and selectivity of carbazole could reach up to 85.74%,30.18 and 66.10%,respectively.Moreover,the TBAC:EG (1:2) could be recycled by using environmentally friendly water as antisolvent.In addition,the separation performance of TBAC:EG (1:2) was also evaluated by real crude anthracene,the carbazole was obtained with purity and yield of 85.32%,60.27%,respectively.Lastly,the extraction mechanism was elucidated byσ-profiles and interaction energy analysis.Theoretical calculation results showed that the main driving force for the extraction process was the hydrogen bonding ((N–H...Cl) and van der Waals interactions (C–H...O and C–H...π),which corresponding to the blue and green isosurfaces
