Three diamine monomers with different derivatives of imidazole heterocyclic ring, aryl ethers and electron withdrawing trifluoromethyl groups in the backbone were synthesized and used in polycodensation reaction with ...Three diamine monomers with different derivatives of imidazole heterocyclic ring, aryl ethers and electron withdrawing trifluoromethyl groups in the backbone were synthesized and used in polycodensation reaction with various aliphatic and aromatic dicarboxylic acids for preparation of a series of novel polyamides （PAs）. The PAs were obtained in high yields and possessed inherent viscosities in the range of 0.26-0.75 dL/g. All of the polymers were amorphous in nature, showed outstanding solubility and could be easily dissolved in amide-type polar aprotic solvents. They showed good thermal stability with glass transition temperatures between 162-302 ℃. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 421 ℃in N2 atmospheres. All the PAs presented fluorescence upon irradiation with ultraviolet light and thus showed promise for applications in electroluminescent devices. The monomers and PAs were also screened for antibacterial activity against Gram positive and Gram negative bacteria.展开更多
Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two...Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two cyclic TOCs are reported,namely,[Ti_(6)(μ_(3)-O)_(2)(Oi-Pr)_(8))(LA)_(2)]·i-PrOH(S1)and[Ti_(6)(μ_(3)-O)2(Oi-Pr)_(8))(LV)_(2)]·i-PrOH(S2),which are functionalized by photoactive naphthalene diimide(NDI)chromophores.Their molecular structures and photophysical and photochemical properties were systematically studied.As shown by ultraviolet-visible(UV-vis)spectra and photocurrent study results,the band gap and the photocurrent response of S1 and S2 were derived from NDI ligands which extend the absorption edge of S1 and S2 approaching 500 nm and afford high photocurrent densities of 2.12μA/cm^(2)and 1.95μA/cm^(2)for S1 and S2,respectively,demonstrating the significance of the photoactive ligand in modulating photoresponse of TOCs.This work is expected to enrich the structural library of photoactive TOCs and provide insights into understanding the structure-property relationships of sensitized clusters.展开更多
The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications.Donoracceptor(D...The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications.Donoracceptor(D-A)conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties.In addition,the well-defined cavities in such D-A macrocycles endow them with versatile host-vip properties.In this review,we provide a comprehensive summary of D-A conjugated macrocycle chemistry,detailing recent progress in the area of synthetic methods,optical properties,host-vip chemistry and applications of the underlying chemistry to chemical sensors,bioimaging and photoelectronic devices.Our objective is to provide not only a review of the fundamental findings,but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.展开更多
Influence of annealing temperature and thickness on the optical characteristics of the blend of poly (3-hexylthiophene) (P3HT) and Phenyl C61 butyric acid methylester (PCBM) layer has been investigated in this report....Influence of annealing temperature and thickness on the optical characteristics of the blend of poly (3-hexylthiophene) (P3HT) and Phenyl C61 butyric acid methylester (PCBM) layer has been investigated in this report. Photoactive polymer material (P3HT:PCBM) was deposited on indium tin oxide (ITO) substrate by spin-coating. The morphology of P3HT:PCBM composite layer was investigated by Atomic Force Microscope (AFM). The surface roughness was found to reduce after heat treatment. The absorption of the composite layer was found to increase with its number of layer (thickness). On the other hand, the photoluminescence (PL) quenching, which indicates efficient charge separation in the bulk heterojunction, was found higher for the thinner layer. Absorption was also found to increase with the annealing temperature. Therefore, to optimize the thickness of the P3HT:PCBM photoactive layer that will provide best absorption while providing efficient charge separation, annealing at optimized temperature might be an effective tool.展开更多
Particles of TiO2 modified with poly 3-(2-thienyl) aniline (PThA) and occluded in poly 2,2 bithiophene (PBTh), were subjected to optical, electrochemical impedance spectroscopic (EIS) and photoelectrochemical (PEC) in...Particles of TiO2 modified with poly 3-(2-thienyl) aniline (PThA) and occluded in poly 2,2 bithiophene (PBTh), were subjected to optical, electrochemical impedance spectroscopic (EIS) and photoelectrochemical (PEC) investigation in aqueous, acetate, citrate, and phosphate electrolytes. EIS studies revealed that the assembly film of TiO2/PThA/PBTh possess porous-type structure. They also confirmed the approximate value of Ef obtained from electrochemical studies. Both EIS and optical studies indicated that ac conductivity is much greater than dc conductivity. Guided by the properties of PBTh, no large changes in the energy band structure occurred due to occlusion of TiO2 in PBTh films. Occlusion of TiO2/PThA into the network structure of PBTh inhibits the energy dissipation process and impeded charge polarization process of the material. Photoelectrochemical outcome suggested possible band alignments between the organic film and TiO2 and formation of hybrid sub-bands. Inclusion of TiO2 in the thiophene-based polymers enhanced the charge separation and consequently charge transfer processes and widen the absorption in visible light range.展开更多
Evidence for the long period of a sustainable function of a thermoplastic gel electrolyte (TPGE) consists of polyethylene glycol (PEG)/I<sub>2</sub>/I<span style="color:#4f4f4f;"><sup>...Evidence for the long period of a sustainable function of a thermoplastic gel electrolyte (TPGE) consists of polyethylene glycol (PEG)/I<sub>2</sub>/I<span style="color:#4f4f4f;"><sup>-</sup></span> in propylene carbonate (PC) was recorded. The studied photoactive assembly consists of PBTH/FTO/TPGE I<sub>2</sub>/I<span style="color:#4f4f4f;"><sup>-</sup></span>/Platinized FTO. The study showed that the assembly regenerates the expected photoelectrochemical (PEC) quantities such as photocurrent, and other dielectric properties with infrequent use through an elapsed period of 18 months. The behavior of PBTh/occluded with CdS was mentored during this period and showed a similar result. PEC studies indicated the presence of p-p type hole accumulations interface, evident from the initial sharp rise in photocurrent. The change of open circuit potential (d<i>V<sub>oc</sub></i>) indicates that the shortest electron lifetime is 100 ms. The behavioral outcome of the assemblies within the period of study refracts stability of the electrode and the long life cycle of the electrolyte.展开更多
The incorporation of photoactive units into metal–organic frameworks(MOFs)is of particular interest due to their ability to endow the MOFs with additional properties such as photomagnetism,photomodulated electrical c...The incorporation of photoactive units into metal–organic frameworks(MOFs)is of particular interest due to their ability to endow the MOFs with additional properties such as photomagnetism,photomodulated electrical conductivity,and photocatalytic properties.Perylenediimides(PDIs),as a class of organic dye molecules with strong visible-light absorption ability and high photochemical activity,have attracted considerable interest because of their consecutive photoinduced electron transfer processes for the generation of energetic PDI radical anions.In this context,a novel photoactive MOF based on a perylenediimide derivative,Zn_(2)(diPyPI-Cl_(4))(NDC)_(2)·3DMF(MOF 1)(diPyPI-Cl_(4)=N,N’-bis(pyridyl)-1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxy bisimide,H_(2)NDC=2,6-naphthalenedicarboxylic acid),has been successfully constructed,which exhibits a porous three-dimensional framework with a pcu topology.MOF 1 that acts as an efficient and recyclable electron-transfer photocatalyst is applied for boosting the iodoperfluoroalkylation of alkenes and oxidation of amines to imines under mild conditions with high yields and excellent substrate application ranges.This photocatalyst has the advantages of high efficiency,low catalytic loading and easy availability,which is highly feasible from a synthetic point of view.展开更多
[2.2]Paracyclophane(pCp)scaffolds,unlike manyπ-conjugated building blocks,have been rarely explored in supramolecular self-assembly.Herein we report the synthesis and characterization of two ligands,pCpd3py and pCpd4...[2.2]Paracyclophane(pCp)scaffolds,unlike manyπ-conjugated building blocks,have been rarely explored in supramolecular self-assembly.Herein we report the synthesis and characterization of two ligands,pCpd3py and pCpd4py,composed of a pCp core functionalized at its 7-and 15-positions respectively with 3-pyridyl and 4-pyridyl units.The self-assembly of pCpd4py with Pd^(2+)metal ions afforded a[Pd_(3)(pCpd4py)_(6)]^(6+)cage structure,pCpd4py-Pd,where the six pCpd4py ligands doubly bridge each edge of the Pd_(3)triangular core.The ligand pCpd4py and the palladium cage pCpd4py-Pd have been characterized by NMR spectroscopy,ESI-MS spectrometry and X-ray diffraction analyses and their photophysical properties investigated by steady-state and time-resolved emission spectroscopy as well as time-dependent density functional theory calculations.展开更多
The authors regret that there was an error in the funding acknowledgements in the original article.The correct acknowledgement section should read as follows:The authors sincerely acknowledge the SERB(CRG/2021/001118)...The authors regret that there was an error in the funding acknowledgements in the original article.The correct acknowledgement section should read as follows:The authors sincerely acknowledge the SERB(CRG/2021/001118)and SERB(CRG/2021/005556)for funding.The authors are thankful to IISER Kolkata and NIBMG for infrastructural facilities and financial support.SR thanks DST-INSPIRE;PM,SG and MM thank the CSIR;SA thanks the UGC and NM thanks IISER-K for their research fellowships.展开更多
On transition metals such as iron rests lots of hope to replace precious metal catalysts in the field of photochemistry for a more sustainable future.Indeed,significant progress has been made in recent years in terms ...On transition metals such as iron rests lots of hope to replace precious metal catalysts in the field of photochemistry for a more sustainable future.Indeed,significant progress has been made in recent years in terms of lifetime extension and emerging applications in catalysis.For this reason,recent synthetic strategies of new photoactive iron compounds,which have proved to show particularly promising properties,are reviewed here.The lifetime of the excited state serves as a key parameter for comparison with the standard ruthenium complex,[Ru(bpy)_(3)]^(2+),to discuss the potential and performance of the iron complexes.This approach is complemented by a more holistic examination of the sustainability of such a substitution strategy in order to answer the question:when or at which point can we assume that iron represents a more sustainable alternative for noble metals in photochemical applications?展开更多
Mono-axial functionalised octahedral diazido Pt(IV)complexes trans,trans,trans-[Pt(py)_(2)(N_(3))_(2)(OR_(1))(OR_(2))](OR_(1)=OH and OR_(2)=anticancer agent coumarin-3 carboxylate(cou,2a),pyruvate dehydrogenase kinase...Mono-axial functionalised octahedral diazido Pt(IV)complexes trans,trans,trans-[Pt(py)_(2)(N_(3))_(2)(OR_(1))(OR_(2))](OR_(1)=OH and OR_(2)=anticancer agent coumarin-3 carboxylate(cou,2a),pyruvate dehydrogenase kinase(PDK)inhibitors 4-phenylbutyrate(PhB,2b)or dichloroacetate(DCA,2c)),and their di-axial functionalised analogues with OR_(1)=DCA and OR_(2)=cou(3a),PhB(3b),or DCA(3c)have been synthesised and characterised,including the X-ray crystal structures of complexes 2a,3a,3b and 3c.These complexes exhibit dark stability and have the potential to generate cytotoxic Pt(II)species and free radicals selectively in cancer cells when irradiated.Mono-functionalised complexes 2a-2c showed higher aqueous solubility and more negative reduction potentials.Mono-and di-functionalised complexes displayed higher photocytotoxicity with blue light(1 h,465 nm,4.8 mW cm^(-2))than the parent dihydroxido complex 1(OR_(1)=OR_(2)=OH)in A2780 human ovarian(IC_(50)0.9-2.9μM for 2a-2c;0.11-0.39μM for 3a-3c)and A549 human lung cancer cells(5.4-7.8μM for 2a-2c;1.2-2.6μM for 3a-3c)with satisfactory dark stability.Notably,no apparent dark cytotoxicity was observed in healthy lung MRC-5 fibroblasts for all complexes(IC_(50)>20μM).Significantly higher platinum cellular accumulation and photo-generated ROS levels were observed for the di-functionalised complexes compared with their mono-functionalised analogues when cancer cells were treated under the same concentrations.展开更多
H+modulated charge-transfer in photoexcited covalent polyoxometalate-bodipy conjugates is described.The hybrid organic/inorganic molecular photoactive dyads are based on Keggin-type polyoxometalates(POMs,where KM=[PM1...H+modulated charge-transfer in photoexcited covalent polyoxometalate-bodipy conjugates is described.The hybrid organic/inorganic molecular photoactive dyads are based on Keggin-type polyoxometalates(POMs,where KM=[PM11O39]and M=Mo or W)covalently grafted via an organotin linker to a bodipy(BOD)photosensitizer.The relative potentials of the photosensitizer and POM are aligned such that lightinduced electron transfer from BOD to POM is permitted for the polyoxomolybdate KMo Sn[BOD]but not effective for the polyoxotungstate analogue K^(W) _(Sn)[BOD].In both cases,the addition of acid shifts the redox potential of the POM only,to increase the driving force for electron transfer.This leads to chargeseparation being switched on for K^(W) _(Sn)[BOD]in the presence of acid.The addition of acid to KMo Sn[BOD]accelerates charge-separation by an order of magnitude(from 2 ns to 200 ps)and is accompanied by a deceleration of charge recombination,leading to a charge-separated state lifetime of up to 1.3μs.This behaviour is consistent with proton coupled electron transfer,which has previously been observed electrochemically for POMs,but this study shows,for the first time,the impact of protonation on photoinduced electron transfer.展开更多
Tetra-coordinate boron-based fluorescent materials hold considerable promise across chemistry,biology and materials science due to their unique and precisely tunable optoelectronic properties.The incorporation of the ...Tetra-coordinate boron-based fluorescent materials hold considerable promise across chemistry,biology and materials science due to their unique and precisely tunable optoelectronic properties.The incorporation of the heteroatom boron(B)enables these materials to exhibit high luminescence quantum yields,adjustable absorption and emission wavelengths,and exceptional photostability.This review examines the molecular design and applications of tetra-coordinate boron-based photoactive molecules,highlighting their roles in fluorescence sensing,anticounterfeiting,and imaging.We outline how structural features impact their properties and discuss strategies for enhancing their performance,including ligand modification and the extension of conjugation length,among others.Additionally,future research focus in this field is also addressed including strategies for diversifying molecular structures and enhancing molecular stability,which is believed to pave the way for innovative solutions to the challenges in areas such as sensing,imaging and information security.展开更多
Photoactive complexes of nonprecious transition metals,mainly including those in the first-row and partially the second-row of the Periodic table of elements,have received increasing attention in view of their low cos...Photoactive complexes of nonprecious transition metals,mainly including those in the first-row and partially the second-row of the Periodic table of elements,have received increasing attention in view of their low cost and long-term sustainability.They are recognized as promising alternatives to noble transition metal complex congeners that have been extensively studied in optoelectronic devices,artificial photosynthesis,photocatalysis,biodiagnostics,and therapeutics,etc.This review is devoted to a comprehensive summary on the classical and recent advances on photoactive nonprecious transition metal complexes,including photoactive Zr,V,Cr,Mo,and W complexes,Mn complexes and hybrids,Fe,Co,Ni,and Cu complexes,and Zn and Cd complexes and hybrids.A particular focus is given on the molecular design,modulation of photophysical and photochemical properties,and applications of the representative and lately-developed nonprecious metal complexes.In addition,a perspective on the future development in this field is provided at the end of this review.展开更多
Highly efficient photo-assisted electrocatalysis for methanol oxidation reaction(MOR)realizes the conversion of solar and chemical energy into electric energy simultaneously.Here we report a Pt-MXene-TiO2 composite fo...Highly efficient photo-assisted electrocatalysis for methanol oxidation reaction(MOR)realizes the conversion of solar and chemical energy into electric energy simultaneously.Here we report a Pt-MXene-TiO2 composite for highly efficient MOR via a photoactive cascaded electro-catalytic process.With light(UV and visible light)irradiation,MXene-TiO2 serves as the photo active centre(photoinduced hole)to activate the methanol molecules,while Pt particles are the active centre for the following electro-catalytic oxidation of those activated methanol molecules.Pt-MXene-TiO2 catalyst exhibits a lower onset potential(0.33 V)and an impressive mass activity of 2,750.42 mA·mg^−1 Pt under light illumination.It represents the highest MOR activity ever reported for photo-assisted electrocatalysts.Pt-MXene-TiO2 also shows excellent CO tolerance ability and stability,in which,after long-term(5,000 s)reaction,still keeps a high mass activity of 1,269.81 mA·mg−1Pt(62.66%of its initial activity).The photo-electro-catalytic system proposed in this work offers novel opportunities for exploiting photo-assisted enhancement of highly efficient and stable catalysts for MOR.展开更多
Organic solar cells(OSCs)have unique advantages of light weight,low-cost solution processing,and capability to be fabricated into flexible and semitransparent devices,which are widely recognized as a promising photovo...Organic solar cells(OSCs)have unique advantages of light weight,low-cost solution processing,and capability to be fabricated into flexible and semitransparent devices,which are widely recognized as a promising photovoltaic technology.Photoactive layers of the OSCs are composed of a blend of a p-type organic semiconductor as a donor(D)and an n-type organic semiconductor as acceptor(A).The morphology of the active layer with D/A nano-scaled aggregation and face-onπconjugated packing,and D/A interpenetrating network is crucial for achieving high photovoltaic performance of the OSCs.Therefore,great efforts have been devoted to control and optimize morphology of the active layers.This perspective focuses on the morphological control by solvent/solid processing additives and the morphology optimization by postdeposition treatment with thermal annealing and/or solvent vapor annealing,which have been extensively adopted and exhibit promising positive effect in optimizing the morphology.Representative examples are given and discussed to understand the foundation of the postdeposition treatments on tuning the morphology.Insights into the role of the postdeposition treatments and additive treatments on the morphology optimization will be beneficial to further improvement in morphology optimization for practical organic photovoltaic application.展开更多
A new kind of photoactive electrodes with nanocrystalline TiO2(nano-TiO2)secondary structure is successfully prepared via a simple method of adding a small amount of TiCl4 2-propanol solution in conventional nano-TiO2...A new kind of photoactive electrodes with nanocrystalline TiO2(nano-TiO2)secondary structure is successfully prepared via a simple method of adding a small amount of TiCl4 2-propanol solution in conventional nano-TiO2 paste to form micro-sized nano-TiO2 aggregates.The benefits of this special structure include improved optical absorption,increased light scattering ability,and enhanced electron transport and collection efficiency.Dye-sensitized solar cells(DSCs)based on these photoactive electrodes show improved performance.The power conversion efficiency of the cells can be increased from 5.03%to 7.30%by substituting 6μm conventional nano-TiO2 thin film with the same thickness of as-prepared nano-TiO2 aggregates film in the photoactive electrodes.A higher power conversion efficiency of the cells can be obtained by further increasing the thickness of the nano-TiO2 aggregates film.展开更多
We reported enhanced performance of polymer solar cells, based on poly(3-hexylthiophene):[6,6]-phenylC_(61)-butyric acid methyl ester(P3HT:PC_(61)BM) and polythieno[3,4-b]-thiophene-co-benzodithiophene:[6,6]-phenylC_(...We reported enhanced performance of polymer solar cells, based on poly(3-hexylthiophene):[6,6]-phenylC_(61)-butyric acid methyl ester(P3HT:PC_(61)BM) and polythieno[3,4-b]-thiophene-co-benzodithiophene:[6,6]-phenylC_(71)-butyric acid methyl ester(PTB7:PC_(71)BM) photovoltaic systems, by a two-step dissolution treatment of photoactive blends. Optical and morphological characterization revealed that the composition of the ordered polymer and donor/acceptor phase structure in the photoactive layer can be optimized using a two-step dissolution treatment. In addition, time-resolved photoluminescence indicated that exciton dissociation efficiency could be increased using this method. Current density-voltage(J-V) measurements showed that power conversion efficiencies(PCE) of the two-step dissolution treated devices were higher than those of one-step treated devices by 24% and 8% for P3HT:PC61BM and PTB7:PC_(71)BM systems, respectively. Therefore, this two-step dissolution treatment further optimizes the performance of polymer solar cells.展开更多
In recent times,solar energy has become one of the largest available sources of renewable energy at our disposal.However,the design of highly efficient solar cells is increasingly becoming crucial as there has been a ...In recent times,solar energy has become one of the largest available sources of renewable energy at our disposal.However,the design of highly efficient solar cells is increasingly becoming crucial as there has been a surge for economically viable alternative energy sources with the lowest cost.Significant advances have been made through different routes to make photovoltaic(PV)/solar technologies economically viable,eco-friendly and consequently scalable.As a result,cellulose nanomaterials have become one of the emerging technologies in this regard because of the advantages of high-value bio-based nanostructured materials,such as their abundance and sustainability.Nanocellulose-based photoactive nanocomposite materials can be made by integrating conducting photoactive and electroconductive materials with hydrophilic biocompatible cellulose.Inorganic nanoparticles,such as graphene/reduced graphene oxide cadmium sulphide quantum dots,amongst others,can be introduced into the nanocellulose matrix and can be applied either as charge transporters or photoactive materials in different types of solar cells.Thus,in this review,we highlight the optoelectronic properties of different photoactive materials,particularly nanocellulose-based graphene nanocomposites;their efficiencies and drawbacks were X-rayed.The effect of doping each PV material on the PV performance is also discussed.It is anticipated that the novel material would result in a reduction in the cost of solar cells,jointly enhancing their efficacy in generating environmentally friendly electricity.Since the fabrication techniques and equipment play a crucial role in the development of solar cells,the fabrication techniques of bulk-heterojunction(BHJ)cells containing a nanocellulose-based graphene composite and case studies of already fabricated BHJ PV cells with nanocellulose-based graphene composite are discussed.展开更多
CONSPECTUS:This Account aims to concisely summarize recent advancements in the field of photocatalysis,with a particular focus on dimension-reduced metal−organic nanomaterials,including coordination cages and 2D struc...CONSPECTUS:This Account aims to concisely summarize recent advancements in the field of photocatalysis,with a particular focus on dimension-reduced metal−organic nanomaterials,including coordination cages and 2D structures.Metal−organic frameworks(MOFs),known for their high crystallinity,porosity,and well-determined structures,are at the forefront of this research.They offer a unique confined environment that is optimal for enhancing host−vip interactions.展开更多
基金partially financially supported by the Research Affairs Division of University of Kurdistan(UOK),Sanandaj(Iran)
文摘Three diamine monomers with different derivatives of imidazole heterocyclic ring, aryl ethers and electron withdrawing trifluoromethyl groups in the backbone were synthesized and used in polycodensation reaction with various aliphatic and aromatic dicarboxylic acids for preparation of a series of novel polyamides （PAs）. The PAs were obtained in high yields and possessed inherent viscosities in the range of 0.26-0.75 dL/g. All of the polymers were amorphous in nature, showed outstanding solubility and could be easily dissolved in amide-type polar aprotic solvents. They showed good thermal stability with glass transition temperatures between 162-302 ℃. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 421 ℃in N2 atmospheres. All the PAs presented fluorescence upon irradiation with ultraviolet light and thus showed promise for applications in electroluminescent devices. The monomers and PAs were also screened for antibacterial activity against Gram positive and Gram negative bacteria.
基金National Natural Science Foundation of China(Nos.92161111,21901037 and 21901038)。
文摘Photoactive functionalized titanium-oxo clusters(TOCs)are regarded as an important model compound for dye-sensitized titanium dioxide solar cells.However,the dyes used for sensitizing TOCs are still limited.Herein,two cyclic TOCs are reported,namely,[Ti_(6)(μ_(3)-O)_(2)(Oi-Pr)_(8))(LA)_(2)]·i-PrOH(S1)and[Ti_(6)(μ_(3)-O)2(Oi-Pr)_(8))(LV)_(2)]·i-PrOH(S2),which are functionalized by photoactive naphthalene diimide(NDI)chromophores.Their molecular structures and photophysical and photochemical properties were systematically studied.As shown by ultraviolet-visible(UV-vis)spectra and photocurrent study results,the band gap and the photocurrent response of S1 and S2 were derived from NDI ligands which extend the absorption edge of S1 and S2 approaching 500 nm and afford high photocurrent densities of 2.12μA/cm^(2)and 1.95μA/cm^(2)for S1 and S2,respectively,demonstrating the significance of the photoactive ligand in modulating photoresponse of TOCs.This work is expected to enrich the structural library of photoactive TOCs and provide insights into understanding the structure-property relationships of sensitized clusters.
基金supported by the National Natural Science Foundation of China(Nos.21971041 and 22001039)Natural Science Foundation of Fujian Province(No.2020J01447).
文摘The design and synthesis of photoactive macrocyclic molecules continue to attract attention because such species play important roles in supramolecular chemistry as well as photoelectronic applications.Donoracceptor(D-A)conjugated macrocycles are an emerging class of photoactive molecules due to their D-A conjugated structural characteristics and tunable optical properties.In addition,the well-defined cavities in such D-A macrocycles endow them with versatile host-vip properties.In this review,we provide a comprehensive summary of D-A conjugated macrocycle chemistry,detailing recent progress in the area of synthetic methods,optical properties,host-vip chemistry and applications of the underlying chemistry to chemical sensors,bioimaging and photoelectronic devices.Our objective is to provide not only a review of the fundamental findings,but also to outline future research directions where D-A conjugated macrocycles and their constructs may have a role to play.
文摘Influence of annealing temperature and thickness on the optical characteristics of the blend of poly (3-hexylthiophene) (P3HT) and Phenyl C61 butyric acid methylester (PCBM) layer has been investigated in this report. Photoactive polymer material (P3HT:PCBM) was deposited on indium tin oxide (ITO) substrate by spin-coating. The morphology of P3HT:PCBM composite layer was investigated by Atomic Force Microscope (AFM). The surface roughness was found to reduce after heat treatment. The absorption of the composite layer was found to increase with its number of layer (thickness). On the other hand, the photoluminescence (PL) quenching, which indicates efficient charge separation in the bulk heterojunction, was found higher for the thinner layer. Absorption was also found to increase with the annealing temperature. Therefore, to optimize the thickness of the P3HT:PCBM photoactive layer that will provide best absorption while providing efficient charge separation, annealing at optimized temperature might be an effective tool.
文摘Particles of TiO2 modified with poly 3-(2-thienyl) aniline (PThA) and occluded in poly 2,2 bithiophene (PBTh), were subjected to optical, electrochemical impedance spectroscopic (EIS) and photoelectrochemical (PEC) investigation in aqueous, acetate, citrate, and phosphate electrolytes. EIS studies revealed that the assembly film of TiO2/PThA/PBTh possess porous-type structure. They also confirmed the approximate value of Ef obtained from electrochemical studies. Both EIS and optical studies indicated that ac conductivity is much greater than dc conductivity. Guided by the properties of PBTh, no large changes in the energy band structure occurred due to occlusion of TiO2 in PBTh films. Occlusion of TiO2/PThA into the network structure of PBTh inhibits the energy dissipation process and impeded charge polarization process of the material. Photoelectrochemical outcome suggested possible band alignments between the organic film and TiO2 and formation of hybrid sub-bands. Inclusion of TiO2 in the thiophene-based polymers enhanced the charge separation and consequently charge transfer processes and widen the absorption in visible light range.
文摘Evidence for the long period of a sustainable function of a thermoplastic gel electrolyte (TPGE) consists of polyethylene glycol (PEG)/I<sub>2</sub>/I<span style="color:#4f4f4f;"><sup>-</sup></span> in propylene carbonate (PC) was recorded. The studied photoactive assembly consists of PBTH/FTO/TPGE I<sub>2</sub>/I<span style="color:#4f4f4f;"><sup>-</sup></span>/Platinized FTO. The study showed that the assembly regenerates the expected photoelectrochemical (PEC) quantities such as photocurrent, and other dielectric properties with infrequent use through an elapsed period of 18 months. The behavior of PBTh/occluded with CdS was mentored during this period and showed a similar result. PEC studies indicated the presence of p-p type hole accumulations interface, evident from the initial sharp rise in photocurrent. The change of open circuit potential (d<i>V<sub>oc</sub></i>) indicates that the shortest electron lifetime is 100 ms. The behavioral outcome of the assemblies within the period of study refracts stability of the electrode and the long life cycle of the electrolyte.
基金supported by the National Natural Science Foundation of China(No.21961030)the Application Basis Research Project of Yunnan Province Science and Technology Department(202101AU070004)the Yunnan Province Thousand Youth Talents Plan,the Program of Innovative Research Team(in science and technology)in University of Yunnan Province and the Scientific and Technological Innovation Team for Green Catalysis and Energy Material in Yunnan Institutions of Higher Learning.
文摘The incorporation of photoactive units into metal–organic frameworks(MOFs)is of particular interest due to their ability to endow the MOFs with additional properties such as photomagnetism,photomodulated electrical conductivity,and photocatalytic properties.Perylenediimides(PDIs),as a class of organic dye molecules with strong visible-light absorption ability and high photochemical activity,have attracted considerable interest because of their consecutive photoinduced electron transfer processes for the generation of energetic PDI radical anions.In this context,a novel photoactive MOF based on a perylenediimide derivative,Zn_(2)(diPyPI-Cl_(4))(NDC)_(2)·3DMF(MOF 1)(diPyPI-Cl_(4)=N,N’-bis(pyridyl)-1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxy bisimide,H_(2)NDC=2,6-naphthalenedicarboxylic acid),has been successfully constructed,which exhibits a porous three-dimensional framework with a pcu topology.MOF 1 that acts as an efficient and recyclable electron-transfer photocatalyst is applied for boosting the iodoperfluoroalkylation of alkenes and oxidation of amines to imines under mild conditions with high yields and excellent substrate application ranges.This photocatalyst has the advantages of high efficiency,low catalytic loading and easy availability,which is highly feasible from a synthetic point of view.
基金the University of St Andrews and EPSRC(EP/M02105X/1)for financial support.
文摘[2.2]Paracyclophane(pCp)scaffolds,unlike manyπ-conjugated building blocks,have been rarely explored in supramolecular self-assembly.Herein we report the synthesis and characterization of two ligands,pCpd3py and pCpd4py,composed of a pCp core functionalized at its 7-and 15-positions respectively with 3-pyridyl and 4-pyridyl units.The self-assembly of pCpd4py with Pd^(2+)metal ions afforded a[Pd_(3)(pCpd4py)_(6)]^(6+)cage structure,pCpd4py-Pd,where the six pCpd4py ligands doubly bridge each edge of the Pd_(3)triangular core.The ligand pCpd4py and the palladium cage pCpd4py-Pd have been characterized by NMR spectroscopy,ESI-MS spectrometry and X-ray diffraction analyses and their photophysical properties investigated by steady-state and time-resolved emission spectroscopy as well as time-dependent density functional theory calculations.
文摘The authors regret that there was an error in the funding acknowledgements in the original article.The correct acknowledgement section should read as follows:The authors sincerely acknowledge the SERB(CRG/2021/001118)and SERB(CRG/2021/005556)for funding.The authors are thankful to IISER Kolkata and NIBMG for infrastructural facilities and financial support.SR thanks DST-INSPIRE;PM,SG and MM thank the CSIR;SA thanks the UGC and NM thanks IISER-K for their research fellowships.
基金Financial support from the Deutsche Forschungsgemeinschaft[DFG,Priority Program SPP 2102“Light-controlled reactivity of metal complexes”(BA 4467/7-1)]is gratefully acknowledgedthe Fonds der Chemischen Industrie for a Kekulégrant+1 种基金The German BMBF is acknowledged for funding in frame of project Syn-XAS(FKZ 05K18PPA)FocusPP64(FKZ 05K19PP1).
文摘On transition metals such as iron rests lots of hope to replace precious metal catalysts in the field of photochemistry for a more sustainable future.Indeed,significant progress has been made in recent years in terms of lifetime extension and emerging applications in catalysis.For this reason,recent synthetic strategies of new photoactive iron compounds,which have proved to show particularly promising properties,are reviewed here.The lifetime of the excited state serves as a key parameter for comparison with the standard ruthenium complex,[Ru(bpy)_(3)]^(2+),to discuss the potential and performance of the iron complexes.This approach is complemented by a more holistic examination of the sustainability of such a substitution strategy in order to answer the question:when or at which point can we assume that iron represents a more sustainable alternative for noble metals in photochemical applications?
基金support from the EPSRC(EP/G006792,EP/F034210/1 for PJS)University of Warwick(Chancellor’s International PhD Scholarship for HS)Anglo-American Platinum(HS)and Wellcome Trust(grant no 209173/Z/17/Z,Sir Henry Wellcome Fellowship for CI).
文摘Mono-axial functionalised octahedral diazido Pt(IV)complexes trans,trans,trans-[Pt(py)_(2)(N_(3))_(2)(OR_(1))(OR_(2))](OR_(1)=OH and OR_(2)=anticancer agent coumarin-3 carboxylate(cou,2a),pyruvate dehydrogenase kinase(PDK)inhibitors 4-phenylbutyrate(PhB,2b)or dichloroacetate(DCA,2c)),and their di-axial functionalised analogues with OR_(1)=DCA and OR_(2)=cou(3a),PhB(3b),or DCA(3c)have been synthesised and characterised,including the X-ray crystal structures of complexes 2a,3a,3b and 3c.These complexes exhibit dark stability and have the potential to generate cytotoxic Pt(II)species and free radicals selectively in cancer cells when irradiated.Mono-functionalised complexes 2a-2c showed higher aqueous solubility and more negative reduction potentials.Mono-and di-functionalised complexes displayed higher photocytotoxicity with blue light(1 h,465 nm,4.8 mW cm^(-2))than the parent dihydroxido complex 1(OR_(1)=OR_(2)=OH)in A2780 human ovarian(IC_(50)0.9-2.9μM for 2a-2c;0.11-0.39μM for 3a-3c)and A549 human lung cancer cells(5.4-7.8μM for 2a-2c;1.2-2.6μM for 3a-3c)with satisfactory dark stability.Notably,no apparent dark cytotoxicity was observed in healthy lung MRC-5 fibroblasts for all complexes(IC_(50)>20μM).Significantly higher platinum cellular accumulation and photo-generated ROS levels were observed for the di-functionalised complexes compared with their mono-functionalised analogues when cancer cells were treated under the same concentrations.
基金The North East Centre for Energy Materials EP/R021503/1ERC starting grant,p-TYPE 715354 and LaserLab Europe LLC002553+1 种基金G.I.,A.P.,S.B.and Y.B.M’B.thank the French National Research Agency for Grant ANR PhotoCarb(ANR-16-CE05-0025)T.P.P.C.acknowledge financial support from the Swedish Energy Agency,Crafoord Foundation and the Swedish Research Council.
文摘H+modulated charge-transfer in photoexcited covalent polyoxometalate-bodipy conjugates is described.The hybrid organic/inorganic molecular photoactive dyads are based on Keggin-type polyoxometalates(POMs,where KM=[PM11O39]and M=Mo or W)covalently grafted via an organotin linker to a bodipy(BOD)photosensitizer.The relative potentials of the photosensitizer and POM are aligned such that lightinduced electron transfer from BOD to POM is permitted for the polyoxomolybdate KMo Sn[BOD]but not effective for the polyoxotungstate analogue K^(W) _(Sn)[BOD].In both cases,the addition of acid shifts the redox potential of the POM only,to increase the driving force for electron transfer.This leads to chargeseparation being switched on for K^(W) _(Sn)[BOD]in the presence of acid.The addition of acid to KMo Sn[BOD]accelerates charge-separation by an order of magnitude(from 2 ns to 200 ps)and is accompanied by a deceleration of charge recombination,leading to a charge-separated state lifetime of up to 1.3μs.This behaviour is consistent with proton coupled electron transfer,which has previously been observed electrochemically for POMs,but this study shows,for the first time,the impact of protonation on photoinduced electron transfer.
基金support from the National Natural Science Foundation of China(22427802,22132002)the National Key Research and Development Program of China(2022YFA1205502)the 111 project(B14041)for this work.
文摘Tetra-coordinate boron-based fluorescent materials hold considerable promise across chemistry,biology and materials science due to their unique and precisely tunable optoelectronic properties.The incorporation of the heteroatom boron(B)enables these materials to exhibit high luminescence quantum yields,adjustable absorption and emission wavelengths,and exceptional photostability.This review examines the molecular design and applications of tetra-coordinate boron-based photoactive molecules,highlighting their roles in fluorescence sensing,anticounterfeiting,and imaging.We outline how structural features impact their properties and discuss strategies for enhancing their performance,including ligand modification and the extension of conjugation length,among others.Additionally,future research focus in this field is also addressed including strategies for diversifying molecular structures and enhancing molecular stability,which is believed to pave the way for innovative solutions to the challenges in areas such as sensing,imaging and information security.
基金supported by the National Natural Science Foundation of China(21925112,22175181,22371063,22175191,22075027,and 22475002)。
文摘Photoactive complexes of nonprecious transition metals,mainly including those in the first-row and partially the second-row of the Periodic table of elements,have received increasing attention in view of their low cost and long-term sustainability.They are recognized as promising alternatives to noble transition metal complex congeners that have been extensively studied in optoelectronic devices,artificial photosynthesis,photocatalysis,biodiagnostics,and therapeutics,etc.This review is devoted to a comprehensive summary on the classical and recent advances on photoactive nonprecious transition metal complexes,including photoactive Zr,V,Cr,Mo,and W complexes,Mn complexes and hybrids,Fe,Co,Ni,and Cu complexes,and Zn and Cd complexes and hybrids.A particular focus is given on the molecular design,modulation of photophysical and photochemical properties,and applications of the representative and lately-developed nonprecious metal complexes.In addition,a perspective on the future development in this field is provided at the end of this review.
基金National MCF Energy R&D Program(No.2018YFE0306105)Innovative Research Group Project of the National Natural Science Foundation of China(No.51821002)+3 种基金the National Natural Science Foundation of China(Nos.51725204,21771132,51972216,and 52041202)Natural Science Foundation of Jiangsu Province(Nos.BK20190041 and BK20190828)Key-Area Research and Development Program of GuangDong Province(No.2019B010933001)Collaborative Innovation Center of Suzhou Nano Science&Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD),and the 111 Project.
文摘Highly efficient photo-assisted electrocatalysis for methanol oxidation reaction(MOR)realizes the conversion of solar and chemical energy into electric energy simultaneously.Here we report a Pt-MXene-TiO2 composite for highly efficient MOR via a photoactive cascaded electro-catalytic process.With light(UV and visible light)irradiation,MXene-TiO2 serves as the photo active centre(photoinduced hole)to activate the methanol molecules,while Pt particles are the active centre for the following electro-catalytic oxidation of those activated methanol molecules.Pt-MXene-TiO2 catalyst exhibits a lower onset potential(0.33 V)and an impressive mass activity of 2,750.42 mA·mg^−1 Pt under light illumination.It represents the highest MOR activity ever reported for photo-assisted electrocatalysts.Pt-MXene-TiO2 also shows excellent CO tolerance ability and stability,in which,after long-term(5,000 s)reaction,still keeps a high mass activity of 1,269.81 mA·mg−1Pt(62.66%of its initial activity).The photo-electro-catalytic system proposed in this work offers novel opportunities for exploiting photo-assisted enhancement of highly efficient and stable catalysts for MOR.
基金National Natural Science Foundation of China,Grant/Award Numbers:22022509,51873140,51820105003。
文摘Organic solar cells(OSCs)have unique advantages of light weight,low-cost solution processing,and capability to be fabricated into flexible and semitransparent devices,which are widely recognized as a promising photovoltaic technology.Photoactive layers of the OSCs are composed of a blend of a p-type organic semiconductor as a donor(D)and an n-type organic semiconductor as acceptor(A).The morphology of the active layer with D/A nano-scaled aggregation and face-onπconjugated packing,and D/A interpenetrating network is crucial for achieving high photovoltaic performance of the OSCs.Therefore,great efforts have been devoted to control and optimize morphology of the active layers.This perspective focuses on the morphological control by solvent/solid processing additives and the morphology optimization by postdeposition treatment with thermal annealing and/or solvent vapor annealing,which have been extensively adopted and exhibit promising positive effect in optimizing the morphology.Representative examples are given and discussed to understand the foundation of the postdeposition treatments on tuning the morphology.Insights into the role of the postdeposition treatments and additive treatments on the morphology optimization will be beneficial to further improvement in morphology optimization for practical organic photovoltaic application.
基金supported by the National Natural Science Foundation of China (U1205112,51002053)the Key Project of the Chinese Ministry of Education (212206)+1 种基金the Programs for Prominent Young Talents and New Century Excellent Talents in Fujian Province Universitythe Promotion Program for Yong and Middle-aged Teacher in Science and Technology Research of Huaqiao University (ZQN- YX102)
文摘A new kind of photoactive electrodes with nanocrystalline TiO2(nano-TiO2)secondary structure is successfully prepared via a simple method of adding a small amount of TiCl4 2-propanol solution in conventional nano-TiO2 paste to form micro-sized nano-TiO2 aggregates.The benefits of this special structure include improved optical absorption,increased light scattering ability,and enhanced electron transport and collection efficiency.Dye-sensitized solar cells(DSCs)based on these photoactive electrodes show improved performance.The power conversion efficiency of the cells can be increased from 5.03%to 7.30%by substituting 6μm conventional nano-TiO2 thin film with the same thickness of as-prepared nano-TiO2 aggregates film in the photoactive electrodes.A higher power conversion efficiency of the cells can be obtained by further increasing the thickness of the nano-TiO2 aggregates film.
基金supported by the National Natural Science Foundation of China(21603020,61505018 and 51503022)the Scientific and Technological Research Program of Chongqing Municipal Education Commission(KJ1501116 and KJ1401122)+2 种基金the Basic and Frontier Research Program of Chongqing Municipality(cstc2016jcyjA0451,cstc2015jcyjA90020 and cstc2016jcyjA0140)the Introduction of Talent Projects of Chongqing University of Arts and Sciences(R2014CJ05 and R2012CH09)The study was also supported by NPRP grant#NPRP7227-1-034 from Qatar National Research Fund
文摘We reported enhanced performance of polymer solar cells, based on poly(3-hexylthiophene):[6,6]-phenylC_(61)-butyric acid methyl ester(P3HT:PC_(61)BM) and polythieno[3,4-b]-thiophene-co-benzodithiophene:[6,6]-phenylC_(71)-butyric acid methyl ester(PTB7:PC_(71)BM) photovoltaic systems, by a two-step dissolution treatment of photoactive blends. Optical and morphological characterization revealed that the composition of the ordered polymer and donor/acceptor phase structure in the photoactive layer can be optimized using a two-step dissolution treatment. In addition, time-resolved photoluminescence indicated that exciton dissociation efficiency could be increased using this method. Current density-voltage(J-V) measurements showed that power conversion efficiencies(PCE) of the two-step dissolution treated devices were higher than those of one-step treated devices by 24% and 8% for P3HT:PC61BM and PTB7:PC_(71)BM systems, respectively. Therefore, this two-step dissolution treatment further optimizes the performance of polymer solar cells.
文摘In recent times,solar energy has become one of the largest available sources of renewable energy at our disposal.However,the design of highly efficient solar cells is increasingly becoming crucial as there has been a surge for economically viable alternative energy sources with the lowest cost.Significant advances have been made through different routes to make photovoltaic(PV)/solar technologies economically viable,eco-friendly and consequently scalable.As a result,cellulose nanomaterials have become one of the emerging technologies in this regard because of the advantages of high-value bio-based nanostructured materials,such as their abundance and sustainability.Nanocellulose-based photoactive nanocomposite materials can be made by integrating conducting photoactive and electroconductive materials with hydrophilic biocompatible cellulose.Inorganic nanoparticles,such as graphene/reduced graphene oxide cadmium sulphide quantum dots,amongst others,can be introduced into the nanocellulose matrix and can be applied either as charge transporters or photoactive materials in different types of solar cells.Thus,in this review,we highlight the optoelectronic properties of different photoactive materials,particularly nanocellulose-based graphene nanocomposites;their efficiencies and drawbacks were X-rayed.The effect of doping each PV material on the PV performance is also discussed.It is anticipated that the novel material would result in a reduction in the cost of solar cells,jointly enhancing their efficacy in generating environmentally friendly electricity.Since the fabrication techniques and equipment play a crucial role in the development of solar cells,the fabrication techniques of bulk-heterojunction(BHJ)cells containing a nanocellulose-based graphene composite and case studies of already fabricated BHJ PV cells with nanocellulose-based graphene composite are discussed.
基金supported by the Robert A.Welch Foundation through a Welch Endowed Chair to H.-C.Z.(A0030).
文摘CONSPECTUS:This Account aims to concisely summarize recent advancements in the field of photocatalysis,with a particular focus on dimension-reduced metal−organic nanomaterials,including coordination cages and 2D structures.Metal−organic frameworks(MOFs),known for their high crystallinity,porosity,and well-determined structures,are at the forefront of this research.They offer a unique confined environment that is optimal for enhancing host−vip interactions.
