Here we report an in situ assembly growth method that controls the growth of NiTCNQ on the surface of graphdiyne(GDY).The catalytic system of donor–acceptor–donor(GDY/TCNQ/Ni)structure with multiple charge transfer(...Here we report an in situ assembly growth method that controls the growth of NiTCNQ on the surface of graphdiyne(GDY).The catalytic system of donor–acceptor–donor(GDY/TCNQ/Ni)structure with multiple charge transfer(CT)was achieved by controlling the growth of NiTCNQ on the surface of GDY.Significantly,a controlled double layer interface of GDY/TCNQ/Ni was formed.This system implemented simultaneously the two elements we expected(1)an incomplete CT,and(2)the infinite distribution of active sites originating from highly asymmetric surface charge distribution.The high conductivity and typical semiconductor characteristics of the catalyst endows it with high catalytic activity.We found that an electrolytic cell consisting of the CT salt as a catalyst provided a 1.40 V ultra-small cell voltage up to 10 mA cm−2 and the outer GDY film effectively prevented the corrosion of the catalyst.Our study is the first to introduce CT complexes to a novel catalytic material platform for high selectivity of catalysts,and undoubtedly demonstrates the high selectivity,stability,and activity of such catalytic systems,which provides a new space for the development of novel conceptual catalysts.展开更多
Achieving a high carrier migration efficiency by constructing built-in electric field is one of the promising approaches for promoting photocatalytic activity. Herein, we have designed a donor-acceptor(D-A) crystallin...Achieving a high carrier migration efficiency by constructing built-in electric field is one of the promising approaches for promoting photocatalytic activity. Herein, we have designed a donor-acceptor(D-A) crystalline carbon nitride(APMCN) with 4-amino-2,6-dihydroxypyrimidine(AP) as electron donor, in which the pyrimidine ring was well embedded in the heptazine ring via hydrogen-bonding effect during hydrothermal process. The APMCN shows superior charge-transfer due to giant built-in electric field(5.94times higher than pristine carbon nitride), thereby exhibiting excellent photocatalytic H_(2) evolution rate(1350 μmol/h) with a high AQY(62.8%) at 400 nm. Mechanistic analysis based on detailed experimental investigation together with theoretical analysis reveals that the excellent photocatalytic activity is attributed to the promoted charge separation by the giant internal electric field originated from the D–A structure.展开更多
有机室温磷光(room temperature phosphorescence,RTP)材料凭借制备简单、类型丰富、毒性低等特点,以及在显示、传感、生物成像等方面广阔的应用前景而备受关注.一般的有机RTP材料,其磷光寿命<10 ms,而具有长寿命(τ>100 ms)有机...有机室温磷光(room temperature phosphorescence,RTP)材料凭借制备简单、类型丰富、毒性低等特点,以及在显示、传感、生物成像等方面广阔的应用前景而备受关注.一般的有机RTP材料,其磷光寿命<10 ms,而具有长寿命(τ>100 ms)有机RTP材料其磷光衰减过程裸眼可见,因而具有更广阔的应用前景.本文总结了近年来兼具高效率和长寿命有机RTP材料的分子设计策略,包括引入重原子、形成主-客体材料、构筑H聚集、形成氢键和设计成DonorAcceptor(D-A)结构.展开更多
Near infrared(NIR)fluorescence imaging guided photodynamic therapy(PDT)is a technique which has been developed in many clinical trials due to its advantage of real-time optical monitoring,specific spatiotemporal selec...Near infrared(NIR)fluorescence imaging guided photodynamic therapy(PDT)is a technique which has been developed in many clinical trials due to its advantage of real-time optical monitoring,specific spatiotemporal selectivity,and minimal invasiveness.For this,photosensitizers with NIR fluorescence emission and high^(1)O_(2)generation quantum yield are highly desirable.Herein,we designed and synthesized a"donor-acceptor"(D-A)structured semiconductor polymer(SP),which was then wrapped with an amphiphilic compound(Pluronic■F127)to prepare water-soluble nanoparticles(F-SP NPs).The obtained F-SP NPs exhibit good water solubility,excellent particle size stability,strong absorbance at deep red region,and strong NIR fluorescent emission characteristics.The maximal mass extinction coe±cient and fluorescence quantum yield of these F-SPs were calculated to be 21.7 L/(g·cm)and 6.5%,respectively.Moreover,the^(1)O_(2)quantum yield of 89%for F-SP NPs has been achieved under 635 nm laser irradiation,which is higher than Methylene Blue,Ce6,and PpIX.The outstanding properties of these F-SP NPs originate from their unique D-A molecular characteristic.This work should help guide the design of novel semiconductor polymer for NIR fluorescent imaging guided PDT applications.展开更多
The single crystal structure of the donor-acceptor ferrocenyl derivativeC18H15ClFe (Mr = 322. 62 ) has been determined, belonging to orthorhombic crystalsystem, space group P212121 with lattice parameters a= 11. 307 (...The single crystal structure of the donor-acceptor ferrocenyl derivativeC18H15ClFe (Mr = 322. 62 ) has been determined, belonging to orthorhombic crystalsystem, space group P212121 with lattice parameters a= 11. 307 (2), b= 8. 471 (2 ), c=15. 427(3) A, V= 1477. 7(9) A3, Z=4, D.= 1. 45 g. cm-3, λ(MoKα) =0. 71073A,μ= 11. 9 cm-1, F(000) = 664. The final R value for 1534 observed [I>3σ(I)] reflec-tions is 0. 060. The configuration of the C =C double bond is trans. The C5H4CH =CHC6H4Cl fragrnent is almost planar. The rings of ferrocene are almost in the eclipsedpositions with each other.展开更多
X-ray single-crystal structure analysis,UV-Vis,and photoluminescent properties of organic compound,9-(4-(5-(6-methylpyridin-2-yl)-3-phenyl-1H-1,2,4-triazol-1-yl)phenyl)-9H-carbazole(compound 1)were studied.Compound 1 ...X-ray single-crystal structure analysis,UV-Vis,and photoluminescent properties of organic compound,9-(4-(5-(6-methylpyridin-2-yl)-3-phenyl-1H-1,2,4-triazol-1-yl)phenyl)-9H-carbazole(compound 1)were studied.Compound 1 crystallizes in monoclinic system,space group P2(1/c)with a=16.0434(9),b=17.920(1),c=8.3453(5)A,β=94.142(5)°,V=2393.0(2),Z=4,Mr=477.55,Dc=1.326 g/cm^3,F(000)=1000,μ=0.080 mm^–1,GOOF=1.025,the final R=0.0505 and wR=0.1226 for 4921 observed reflections with I>2σ(I).Compound 1 is a donor-acceptor type molecule,in which the carbazolyl group(cz)acts as an electron donor,and the group of 2-(1,3-diphenyl-1H-1,2,4-triazol-5-yl)-6-methylpyridine(MePyTz)as an electron acceptor.In methylene chloride,compound 1 exhibits deep blue luminescence with maximum at 440 nm,lifetime of 4.2 ns under N2 and quantum yield ofф=0.18 at room temperature.The experimental and computational results show that the emission of compound 1 originates from the lowest singlet excited state(S1)with charge transfer character.展开更多
Although doped hole-transport materials(HTMs)off er an effi ciency benefi t for perovskite solar cells(PSCs),they inevi-tably diminish the stability.Here,we describe the use of various chlorinated small molecules,spec...Although doped hole-transport materials(HTMs)off er an effi ciency benefi t for perovskite solar cells(PSCs),they inevi-tably diminish the stability.Here,we describe the use of various chlorinated small molecules,specifi cally fl uorenone-triphenylamine(FO-TPA)-x-Cl[x=para,meta,and ortho(p,m,and o)],with diff erent chlorine-substituent positions,as dopant-free HTMs for PSCs.These chlorinated molecules feature a symmetrical donor-acceptor-donor structure and ideal intramolecular charge transfer properties,allowing for self-doping and the establishment of built-in potentials for improving charge extraction.Highly effi cient hole-transfer interfaces are constructed between perovskites and these HTMs by strategi-cally modifying the chlorine substitution.Thus,the chlorinated HTM-derived inverted PSCs exhibited superior effi ciencies and air stabilities.Importantly,the dopant-free HTM FO-TPA-o-Cl not only attains a power conversion effi ciency of 20.82% but also demonstrates exceptional stability,retaining 93.8%of its initial effi ciency even after a 30-day aging test conducted under ambient air conditions in PSCs without encapsulation.These fi ndings underscore the critical role of chlorine-substituent regulation in HTMs in ensuring the formation and maintenance of effi cient and stable PSCs.展开更多
基金by a generous grant from the National Key Research and Development Project of China(no.2018YFA0703501)the National Nature Science Foundation of China(nos.21790050,21790051,and 22021002)the Key Program of the Chinese Academy of Sciences(no.XDPB13).
文摘Here we report an in situ assembly growth method that controls the growth of NiTCNQ on the surface of graphdiyne(GDY).The catalytic system of donor–acceptor–donor(GDY/TCNQ/Ni)structure with multiple charge transfer(CT)was achieved by controlling the growth of NiTCNQ on the surface of GDY.Significantly,a controlled double layer interface of GDY/TCNQ/Ni was formed.This system implemented simultaneously the two elements we expected(1)an incomplete CT,and(2)the infinite distribution of active sites originating from highly asymmetric surface charge distribution.The high conductivity and typical semiconductor characteristics of the catalyst endows it with high catalytic activity.We found that an electrolytic cell consisting of the CT salt as a catalyst provided a 1.40 V ultra-small cell voltage up to 10 mA cm−2 and the outer GDY film effectively prevented the corrosion of the catalyst.Our study is the first to introduce CT complexes to a novel catalytic material platform for high selectivity of catalysts,and undoubtedly demonstrates the high selectivity,stability,and activity of such catalytic systems,which provides a new space for the development of novel conceptual catalysts.
基金supported by the Basic Science Center Program for Ordered Energy Conversion of the National Natural Science Foundation of China (No.51888103)the National Natural Science Foundation of China (Nos.52376209 and 52172248)+1 种基金China Postdoctoral Science Foundation (Nos.2020M673386 and 2020T130503)China Fundamental Research Funds for the Central Universities。
文摘Achieving a high carrier migration efficiency by constructing built-in electric field is one of the promising approaches for promoting photocatalytic activity. Herein, we have designed a donor-acceptor(D-A) crystalline carbon nitride(APMCN) with 4-amino-2,6-dihydroxypyrimidine(AP) as electron donor, in which the pyrimidine ring was well embedded in the heptazine ring via hydrogen-bonding effect during hydrothermal process. The APMCN shows superior charge-transfer due to giant built-in electric field(5.94times higher than pristine carbon nitride), thereby exhibiting excellent photocatalytic H_(2) evolution rate(1350 μmol/h) with a high AQY(62.8%) at 400 nm. Mechanistic analysis based on detailed experimental investigation together with theoretical analysis reveals that the excellent photocatalytic activity is attributed to the promoted charge separation by the giant internal electric field originated from the D–A structure.
基金supported by the National Natural Science Foundation of China (52072374,52322204 and 51832008)the Ministry of Science and Technology of China (2022YFA1205900)the Youth Innovation Promotion Association of Chinese Academy of Sciences (CAS,Y2022015)。
文摘有机室温磷光(room temperature phosphorescence,RTP)材料凭借制备简单、类型丰富、毒性低等特点,以及在显示、传感、生物成像等方面广阔的应用前景而备受关注.一般的有机RTP材料,其磷光寿命<10 ms,而具有长寿命(τ>100 ms)有机RTP材料其磷光衰减过程裸眼可见,因而具有更广阔的应用前景.本文总结了近年来兼具高效率和长寿命有机RTP材料的分子设计策略,包括引入重原子、形成主-客体材料、构筑H聚集、形成氢键和设计成DonorAcceptor(D-A)结构.
基金This work was supported by National Natural Science Foundation of China(Nos.61805287 and 62175262)The Open Fund of the State Key Laboratory of Luminescent Materials and Devices(South China University of Technology,No.2021-skllmd-10)+1 种基金The Open Sharing Fund for Large-scale Instruments and Equipment of Central South University(CSUZC202218),Fundamental Research Funds for the Central South Universities(Nos.2020CX021,2020zzts387,and 2020zzts404)Key R&D plan of Hunan Province(No.2022SK2101).
文摘Near infrared(NIR)fluorescence imaging guided photodynamic therapy(PDT)is a technique which has been developed in many clinical trials due to its advantage of real-time optical monitoring,specific spatiotemporal selectivity,and minimal invasiveness.For this,photosensitizers with NIR fluorescence emission and high^(1)O_(2)generation quantum yield are highly desirable.Herein,we designed and synthesized a"donor-acceptor"(D-A)structured semiconductor polymer(SP),which was then wrapped with an amphiphilic compound(Pluronic■F127)to prepare water-soluble nanoparticles(F-SP NPs).The obtained F-SP NPs exhibit good water solubility,excellent particle size stability,strong absorbance at deep red region,and strong NIR fluorescent emission characteristics.The maximal mass extinction coe±cient and fluorescence quantum yield of these F-SPs were calculated to be 21.7 L/(g·cm)and 6.5%,respectively.Moreover,the^(1)O_(2)quantum yield of 89%for F-SP NPs has been achieved under 635 nm laser irradiation,which is higher than Methylene Blue,Ce6,and PpIX.The outstanding properties of these F-SP NPs originate from their unique D-A molecular characteristic.This work should help guide the design of novel semiconductor polymer for NIR fluorescent imaging guided PDT applications.
文摘The single crystal structure of the donor-acceptor ferrocenyl derivativeC18H15ClFe (Mr = 322. 62 ) has been determined, belonging to orthorhombic crystalsystem, space group P212121 with lattice parameters a= 11. 307 (2), b= 8. 471 (2 ), c=15. 427(3) A, V= 1477. 7(9) A3, Z=4, D.= 1. 45 g. cm-3, λ(MoKα) =0. 71073A,μ= 11. 9 cm-1, F(000) = 664. The final R value for 1534 observed [I>3σ(I)] reflec-tions is 0. 060. The configuration of the C =C double bond is trans. The C5H4CH =CHC6H4Cl fragrnent is almost planar. The rings of ferrocene are almost in the eclipsedpositions with each other.
基金supported by the China Postdoctoral Science Foundation(2018M632498)the Zhejiang Provincial Postdoctoral fellowship,China(Z71101009)+1 种基金the National Natural Science Foundation of China(51603185,51673174)the Zhejiang Provincial Natural Science Foundation,China(LY17E030001)~~
基金the National Natural Science Foundation of China(51672271,21671190)。
文摘X-ray single-crystal structure analysis,UV-Vis,and photoluminescent properties of organic compound,9-(4-(5-(6-methylpyridin-2-yl)-3-phenyl-1H-1,2,4-triazol-1-yl)phenyl)-9H-carbazole(compound 1)were studied.Compound 1 crystallizes in monoclinic system,space group P2(1/c)with a=16.0434(9),b=17.920(1),c=8.3453(5)A,β=94.142(5)°,V=2393.0(2),Z=4,Mr=477.55,Dc=1.326 g/cm^3,F(000)=1000,μ=0.080 mm^–1,GOOF=1.025,the final R=0.0505 and wR=0.1226 for 4921 observed reflections with I>2σ(I).Compound 1 is a donor-acceptor type molecule,in which the carbazolyl group(cz)acts as an electron donor,and the group of 2-(1,3-diphenyl-1H-1,2,4-triazol-5-yl)-6-methylpyridine(MePyTz)as an electron acceptor.In methylene chloride,compound 1 exhibits deep blue luminescence with maximum at 440 nm,lifetime of 4.2 ns under N2 and quantum yield ofф=0.18 at room temperature.The experimental and computational results show that the emission of compound 1 originates from the lowest singlet excited state(S1)with charge transfer character.
基金This study was supported by the National Nat-ural Science Foundation of China(No.22379105)the Natural Sci-ence Foundation of Shanxi Province(Nos.20210302123110 and 202303021211059)the Open Fund Project of Ningxia Sinostar Display Material Co.,Ltd.
文摘Although doped hole-transport materials(HTMs)off er an effi ciency benefi t for perovskite solar cells(PSCs),they inevi-tably diminish the stability.Here,we describe the use of various chlorinated small molecules,specifi cally fl uorenone-triphenylamine(FO-TPA)-x-Cl[x=para,meta,and ortho(p,m,and o)],with diff erent chlorine-substituent positions,as dopant-free HTMs for PSCs.These chlorinated molecules feature a symmetrical donor-acceptor-donor structure and ideal intramolecular charge transfer properties,allowing for self-doping and the establishment of built-in potentials for improving charge extraction.Highly effi cient hole-transfer interfaces are constructed between perovskites and these HTMs by strategi-cally modifying the chlorine substitution.Thus,the chlorinated HTM-derived inverted PSCs exhibited superior effi ciencies and air stabilities.Importantly,the dopant-free HTM FO-TPA-o-Cl not only attains a power conversion effi ciency of 20.82% but also demonstrates exceptional stability,retaining 93.8%of its initial effi ciency even after a 30-day aging test conducted under ambient air conditions in PSCs without encapsulation.These fi ndings underscore the critical role of chlorine-substituent regulation in HTMs in ensuring the formation and maintenance of effi cient and stable PSCs.
基金supported by the National Natural Science Foundation of China(62175262)the Fundamental Research Funds for the Central Universities(2020CX021)the Key R&D plan of Hunan Province(2022SK2101)。
