A synergistically directed assembly approach to distinctive metal-organic frameworks utilizing both donor-acceptor (D-A) interaction from aromatic systems and coordination interactions is presented.Based on such an ap...A synergistically directed assembly approach to distinctive metal-organic frameworks utilizing both donor-acceptor (D-A) interaction from aromatic systems and coordination interactions is presented.Based on such an approach,the coronene-tpt (tpt =2,4,6-tri(4-pyridyl)-1,3,5-triazine) stacks based coronene-MOF-1-4 have been successfully fabricated.Their structural discrepancies with coroneneabsent control products,1'-4',illustrate clearly the significance of coronene-tpt based D-A interactions in these architectures.All these coronene-MOFs contain varied coronene-tpt stacks as organic secondary building blocks (SBUs),which are closely interrelated with the coordination based framework structures.Moreover,porous coronene-MOF-1 and-2 exhibit high physicochemical stability and significant light hydrocarbons storage and separation performances.展开更多
SOME small dye molecules can bond with proteins, the spectrum of which has a characteristic of energy transferring, i.e. enhancement or quenching of fluorescence. Much information can be obtained from this phenomenon,...SOME small dye molecules can bond with proteins, the spectrum of which has a characteristic of energy transferring, i.e. enhancement or quenching of fluorescence. Much information can be obtained from this phenomenon, and can be used to determine the distance between the macrobiomolecules and some groups, such as the distance between aromatic amino acid of proteins and ligands. So they are often called 'a spectroscopic ruler'. We deduced the theoreti-展开更多
The efficient production of ammonia by reducing nitrates at room temperature and ambient pressure is a promising alternative to the Haber-Bosch process and can effectively overcome the attendant water pollution issues...The efficient production of ammonia by reducing nitrates at room temperature and ambient pressure is a promising alternative to the Haber-Bosch process and can effectively overcome the attendant water pollution issues.Herein,a new idea has been realized for rational and selective construction of the sp-carbon-metal-carbon interface,comprised of electronic-donating triple bonds in graphdiyne and electron-withdrawing iron carbides,for a highly efficient nitrate reduction reaction.The as-prepared sp-carbon-metal-carbon interfacial structures greatly increase the charge transfer ability and electrical conductivity of the system.The proposed concept of incomplete charge transfer has demonstrated significantly high selectivity,activity,and stability in catalytic system.The catalyst exhibits high Faradaic efficiency of over>95%and a NH3 yield rate up to 205.5μmolNH_(3) cm^(-2) h^(-1) in dilute nitrate conditions without any contaminant.展开更多
Four polymers based on perylenediimide co-polymerized with thiophene, bithiophene, selenophone and thieno[3,2-b]thiophene were investigated as the acceptor materials in all-polymer solar cells. Two different donor pol...Four polymers based on perylenediimide co-polymerized with thiophene, bithiophene, selenophone and thieno[3,2-b]thiophene were investigated as the acceptor materials in all-polymer solar cells. Two different donor polymers, poly[4,8-bis（5-（2-ethylhexyl）thiophen-2-yl）benzo[ 1,2-b;4,5-b＇]dithiophene-2,6-diyl-alt-（4-（2-ethylhexyl）-3-fluorothieno[3,4- b]thiophene）-2-carboxylate-2,6-diyl] （PTB7-Th） and poly[（5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl）-alt-（3,3＇-di（2- dodecyltetradecyl）-2,2＇;5＇,2＂;5＂,2＇-quaterthiophen-5,5＇＂-diyl）] （PffBT4T-2DT）, with suitably complementary absorption spectra and energy levels were applied and examined. Among all different donor-acceptor pairs studied here, the combination of PTB7-Th：poly[NN-bis（1-hexylheptyl）-3,4,9,10-pery,enediimide-1,6/1,7-diyl-alt-2,5-thiophene] （PDI-Th） exhibited the best power conversion efficiency （PCE） of 5.13%, with open-circuit voltage （Vo：） = 0.79 lV, short-circuit current density （Jsc） = 12.35 mA.cm-2 and fill-factor （FF） = 0.52. The polymer of PDI-Th acceptor used here had a regio-irregular backbone, conveniently prepared from a mixture of 1,6- and 1,7-dibromo-PDI. It is also noteworthy that neither additive nor post- treatment is required for obtaining such a cell performance.展开更多
Organic donor-acceptor semiconductors exhibit great potential in photothermal conversion.However,it is still challenging to achieve pure organic materials with broad absorption comparable with inorganic materials such...Organic donor-acceptor semiconductors exhibit great potential in photothermal conversion.However,it is still challenging to achieve pure organic materials with broad absorption comparable with inorganic materials such as graphene.Herein,two D-AD type DPA-BT-O4 and NDI-TPA-O4 and three D-A-π-A-D type Th-O4,Th2-O4,and IDT-O4 were readily prepared via two high-yield steps and simple air oxidization.The stability can be attributed to their multiple resonance structures based on the aromatic nitric acid radical mechanism.Compared with the D-A-D radicals,the conjugation extension of the D-A-π-A-D radicals endows them with a narrowed band gap and broad absorption in powder.Interestingly,the IDT-O4 powder with aggregation-induced radical effect exhibits broad absorption between 300 and 2500 nm,which is comparable with graphene and other inorganic materials.Under irradiation of 0.9 W/cm^(2)(808 nm),the temperature of IDT-O4 powder rises to 250℃within 60 s.The water evaporation conversion efficiency of 94.38%and an evaporation rate of 1.365 kg/m^(2)h^(−1)under one sun illumination were achieved.IDT-O4 stands as one of the most efficient photothermal conversion materials among pure organic materials via a rational design strategy.展开更多
Modulating reversible isomerization of hydrophobic dyes in aqueous solutions is greatly desired. Here we report on reversible isomerization of solvatochromic donor-acceptor Stenhouse adducts(DASAs) in water through th...Modulating reversible isomerization of hydrophobic dyes in aqueous solutions is greatly desired. Here we report on reversible isomerization of solvatochromic donor-acceptor Stenhouse adducts(DASAs) in water through the confinement from dendritic oligoethylene glycols(OEGs). Dendronization of DASAs with dendritic OEGs affords them characteristic thermoresponsiveness. These dendronized DASAs spontaneously isomerize in water from hydrophobic linear state into hydrophilic cyclic state at room temperature due to the strong hydration. However, hydrophobic microenvironment through thermally dehydration and collapse of the dendritic OEGs at elevated temperatures confines hydration of the DASA moieties and mediates their interactions with the collapsed hydrophobic OEG domains, affording their isomerization recovery in water efficiently from the hydrophilic cyclic state into the hydrophobic linear state. The confinement-mediated reversible isomerization of DASA moieties in water can be repeated through alternative photo-irradiation and thermal dehydrations, exhibiting excellent fatigue resistance.展开更多
A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHP...A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.展开更多
The development of non-platinum group metal(non-PGM)and efficient multifunctional electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER)with high activi...The development of non-platinum group metal(non-PGM)and efficient multifunctional electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER)with high activity and stability remains a great challenge.Herein,by in-situ transforming silver manganese composite oxide heterointerface into boosted Mott-Schottky heterointerface through a facile carbon reduction strategy,a nanorod-like silver/manganese oxide with superior multifunctional catalytic activities for ORR,OER and HER and stability was obtained.The nanorod-like silver/manganese oxide with Mott-Schottky heterointerface(designated as Ag/Mn_(3)O_(4))exhibits an ORR half-wave potential of 0.831 V(vs.RHE)in 0.1 M KOH,an OER overpotential of 338 mV and a HER overpotential of 177 mV at the current density of 10 mA·cm^(-2)in 1 M KOH,contributing to its noble-metal benchmarks comparable performance in aqueous aluminum-air(Al-air)battery and laboratorial overall water splitting electrolytic cell.Moreover,in-situ electrochemical Raman and synchrotron radiation spectroscopic measurements were conducted to further illustrate the catalytic mechanism of Ag/Mn_(3)O_(4)Mott-Schottky heterointerface towards various electrocatalytic reactions.At the heterointerface,the Ag phase serves as the electron donor and the active phase for ORR and HER,while the Mn_(3)O_(4)phase serves as the electron acceptor and the active phase for OER,respectively.This work deepens the understanding of the Mott-Schottky effect on electrocatalysis and fills in the gap in fundamental physical principles that are behind measured electrocatalytic activity,which offers substantial implications for the rational design of cost-effective multifunctional electrocatalysts with Mott-Schottky effect.展开更多
The combination of donor-acceptor(D-A)structures presents a viable strategy for fabricating covalent organic frameworks(COFs)with exceptional photocatalytic performances.Nevertheless,the selection of functional groups...The combination of donor-acceptor(D-A)structures presents a viable strategy for fabricating covalent organic frameworks(COFs)with exceptional photocatalytic performances.Nevertheless,the selection of functional groups on donor or acceptor building blocks and their effect on the macroscopic properties of COFs are ambiguous.In this study,we tactfully synthesized a pair of Py-DBT-COFs from the same pyrene(Py)donor and 4,7-diphenylbenzo[c][1,2,5]thiadiazole(DBT)acceptor cores with distinct primitive functional groups.The primitive functional groups of building units determine the photocatalytic properties of corresponding Py-DBT-COFs.Specifically,Py-C-DBT-COF synthesized from Py-4CHO and DBT-2NH_(2)showcases a splendid H_(2)evolution rate as high as 21,377.7μmol/(g·h)(with 5 wt.%Pt)originating from better charge transfer capacity,which is significantly superior to that of Py-N-DBT-COF constructed from Py-4NH_(2)and DBT-2CHO.The distinct photocatalytic performances of the two COFs are demonstrated to originate from the different charge separation and transfer capabilities.This work supplies a new avenue for optimizing the photocatalytic performance of D-A COFs from the perspective of primitive functional group selections.展开更多
Perovskite solar cells(PSCs)have been proven to be a promising option for photovoltaic conversion.With the aim to achieve efficient and stable PSCs,it is essential to explore dopant-free hole-transporting materials(HT...Perovskite solar cells(PSCs)have been proven to be a promising option for photovoltaic conversion.With the aim to achieve efficient and stable PSCs,it is essential to explore dopant-free hole-transporting materials(HTMs)with high hole mobility.Herein,HTMs bearing electron donor(D)-electron acceptor(A)-electron donor(D)structures have been constructed with strong intramolecular charge transfer(ICT)effect,based on rational combination of dibenzo[a,c]phenazine and pyridine as electronic acceptors and anchoring groups to perovskite layer.Accordingly,high hole mobility(7.31×10^(-5) cm^(2)·V^(-1)·s^(-1))and photoelectric conversion efficiency(20.45%)have been achieved by dopant-free DPyP-based PSC.It afforded an efficient way to design HTMs with high hole mobility by adjustment of molecular configurations and electronic property of conjugated systems.展开更多
Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally di...Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally diverseα,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with N-hydroxyphthalimide(NHPI)esters and cyanoarenes or aryl aldehydes has been developed.The use of vinyl azide as a precursor to a primary aminewas enabled by the dual role of the Hantzsch ester to form an electron donor-acceptor complex and serve as a sacrificial reductant.This strategy provides a modular synthesis ofα-tertiary primary amines,including unprotected 1,2-amino alcohols,from simple materials with excellent functional group tolerance.The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines.Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by heteroradical cross-coupling betweenα-amino radicals and aryl anion radicals or ketyl anion radicals.展开更多
Photocatalytic hydrogen generation from hydrogen storage media is an effective and promising approach for the green hydrogen industry as well as for achieving carbon neutrality goals.However,the lower photocatalytic e...Photocatalytic hydrogen generation from hydrogen storage media is an effective and promising approach for the green hydrogen industry as well as for achieving carbon neutrality goals.However,the lower photocatalytic efficiency due to the limited light trapping capacity,low electron transfer rate,and severe aggregation of nanoparticles caused by high surface energy seriously restricts their practical application.Herein,we constructed a series of donor–acceptor(D–A)type covalent organic frameworks to confine ultrafine bimetallic Pt-based nanoclusters for photocatalytic hydrogen generation from ammonia borane(AB)hydrolysis.Under visible light irradiation at 20℃,PtCo_(2)@covalent organic framework(COF)showed the highest photocatalytic activity with a turnover frequency(TOF)of 486 min−1.Experiments and density functional theory(DFT)calculations reveal that the high catalytic activity is mainly attributed to the strong electronic interactions between D–A type COF and ultrafine PtCo_(2)nanoclusters.Specifically,the D–A type COF can significantly enhance the light-trapping ability by fine-tuning the electron-acceptor type in the framework,and accelerate the photogenerated electron transfer from D–A type COF to PtCo_(2)nanocluster,which promotes the adsorption and activation of H_(2)O and AB molecules and accelerates hydrogen release.Furthermore,PtCo_(2)@COF also exhibited ultra-high durability due to the significantly enhanced resistance to nanocluster aggregation caused by the nanopore confinement effect of D–A type COF.We believe that this work will provide a theoretical guide for the rational design of efficient D–A COFbased catalysts for photocatalysis.展开更多
The ability to selectively introduce diverse functionality onto hydrocarbons is of substantial value in the synthesis of both small molecules and pharmaceuticals.In this endeavour,as a photocatalyst-and metalfree proc...The ability to selectively introduce diverse functionality onto hydrocarbons is of substantial value in the synthesis of both small molecules and pharmaceuticals.In this endeavour,as a photocatalyst-and metalfree process,the electron donor–acceptor(EDA)strategy has not been well explored.Here we report an approach to aliphatic carbon-hydrogen bond diversification through an EDA complex constituted by HCl and S^(IV)=O groups.As an efficient hydrogen atom transfer(HAT)reagent,chlorine radical can be produced via a proton-coupled electron transfer process in this system.Based on this unusual path,a photopromoted versatile aliphatic C–H functionalization is developed without photo-and metal-catalysts,including thiolation,arylation,alkynylation,and allylation.This conversion has concise and ambient reaction conditions,good functional group tolerance,and substrate diversity,and provides an alternative solution for the high value-added utilization of bulk light alkanes.展开更多
The development of host-guest MOF luminescent composites has attracted considerable attention. However,it is still a challenge to reasonably design large scale conjugated polycarboxylic acids metal-organic framework (...The development of host-guest MOF luminescent composites has attracted considerable attention. However,it is still a challenge to reasonably design large scale conjugated polycarboxylic acids metal-organic framework (MOF) and modulate donor-acceptor interaction. Herein,a series of isostructural 3D porous lanthanide MOF [Ln_(2)(BINDI)0.5(NO_(3))(DMA)(H_(2)O)]∙DMA∙2.5H_(2)O (Ln = La (1),Ce (2),Pr (3) and Nd (4);H_(4)BINDI (N,N’-bis(5-isophthalic acid)-1,4,5,8-naphthalenediimide) were synthesized. Considering the electron-deficient performances of Ln-BINDI MOFs,D-A type composites Ln-MOFs (1—4@H_(4)TBAPy) were prepared via the incorporation of electron-rich H_(4)TBAPy (1,3,6,8-tetrakis(p-benzoic acid) pyrene),which more improved the luminescence performance of complexes 1—4 and can be used as fluorescence sensors for the detection of nitro compounds and aldehydes. High sensitivity of 1@H_(4)TBAPy towards pNBA,pNA PNP,DNP,and TNP could be achieved through hydrogen bond interactions between MOF and analytes,as well as the π-π interaction between H_(4)TBAPy and the naphthalene ring of BINDI,thus the fluorescence quenching efficiency of 1@H_(4)TBAPy was better than that of the complex 1. In addition,it is found that 1@H_(4)TBAPy has high selectivity and sensitivity to aromatic aldehyde SA,5-Mesal and HMBA. Such strategy to enhance the emission of NDI based Ln-BINDI MOFs,will open up an avenue to obtain more fluorescent MOFs for sensing.展开更多
Donor-Acceptor(D-A)alignment is considered a productive strategy to improve the charge separation efficiency of covalent organic frameworks(COFs)and enhance the charge-transfer yield(CTY)of COFs.Moreover,organic molec...Donor-Acceptor(D-A)alignment is considered a productive strategy to improve the charge separation efficiency of covalent organic frameworks(COFs)and enhance the charge-transfer yield(CTY)of COFs.Moreover,organic molecules containing heteroatoms can produce coordination interaction with PbI2 of perovskite precursor to affect the crystallization process,thereby impeding the decomposition and improving the stability of perovskite materials.Herein,a thiazolo[5,4-d]thiazole(TZ)-based D-A type COF_(TPDA-TZDA) was designed and synthesized from N,N,N′,N′-tetrakis(4-aminophenyl)-1,4-benzenediamine(TPDA)and 4,4′-(thiazolo[5,4-d]thiazole-2,5-diyl)dibenzaldehyde(TZDA).Upon incorporation into the FAPbI3 layer,COF_(TPDA-TZDA) not only restrained the perovskite defects and enhanced the grain size of perovskite films through the coordination effect of the N atoms of TZDA but also ameliorated the charge transport within the perovskite film,which was the benefit of the D-A structure of COF_(TPDA-TZDA).As a result,incorporation of COF_(TPDA-TZDA) into the perovskite solar cells(PSCs)led to a remarkable power conversion efficiency(PCE)of up to 23.51%.Furthermore,even after being stored in high relative humidity(RH≈60%)for 480 h,these PSCs maintained over 90.55%of their original PCE.This work sets the foundation for the development of highly efficient and stable PSCs by utilizing TZ-based D-A type COFs.展开更多
基金This work was supported by the National Natural Science Foundation of China (Nos. 21421001, 21531005, 91856124, and 21875115)the Programme of Introducing Talents of Discipline to Universities (B18030)the General Financial Grant from the China Postdoctoral Science Foundation (No. 2017M621056).
文摘A synergistically directed assembly approach to distinctive metal-organic frameworks utilizing both donor-acceptor (D-A) interaction from aromatic systems and coordination interactions is presented.Based on such an approach,the coronene-tpt (tpt =2,4,6-tri(4-pyridyl)-1,3,5-triazine) stacks based coronene-MOF-1-4 have been successfully fabricated.Their structural discrepancies with coroneneabsent control products,1'-4',illustrate clearly the significance of coronene-tpt based D-A interactions in these architectures.All these coronene-MOFs contain varied coronene-tpt stacks as organic secondary building blocks (SBUs),which are closely interrelated with the coordination based framework structures.Moreover,porous coronene-MOF-1 and-2 exhibit high physicochemical stability and significant light hydrocarbons storage and separation performances.
文摘SOME small dye molecules can bond with proteins, the spectrum of which has a characteristic of energy transferring, i.e. enhancement or quenching of fluorescence. Much information can be obtained from this phenomenon, and can be used to determine the distance between the macrobiomolecules and some groups, such as the distance between aromatic amino acid of proteins and ligands. So they are often called 'a spectroscopic ruler'. We deduced the theoreti-
基金This research was made possible as a result of a generous grant from the National Natural Science Foundation of China(grant nos.21790050,21790051,and 22021002)the National Key Research and Development Project of China(grant no.2018YFA0703501)the Key Program of the Chinese Academy of Sciences(grant no.XDPB13).
文摘The efficient production of ammonia by reducing nitrates at room temperature and ambient pressure is a promising alternative to the Haber-Bosch process and can effectively overcome the attendant water pollution issues.Herein,a new idea has been realized for rational and selective construction of the sp-carbon-metal-carbon interface,comprised of electronic-donating triple bonds in graphdiyne and electron-withdrawing iron carbides,for a highly efficient nitrate reduction reaction.The as-prepared sp-carbon-metal-carbon interfacial structures greatly increase the charge transfer ability and electrical conductivity of the system.The proposed concept of incomplete charge transfer has demonstrated significantly high selectivity,activity,and stability in catalytic system.The catalyst exhibits high Faradaic efficiency of over>95%and a NH3 yield rate up to 205.5μmolNH_(3) cm^(-2) h^(-1) in dilute nitrate conditions without any contaminant.
基金financially supported by the National Natural Science Foundation of China(Nos.21674001 and 51473003)
文摘Four polymers based on perylenediimide co-polymerized with thiophene, bithiophene, selenophone and thieno[3,2-b]thiophene were investigated as the acceptor materials in all-polymer solar cells. Two different donor polymers, poly[4,8-bis（5-（2-ethylhexyl）thiophen-2-yl）benzo[ 1,2-b;4,5-b＇]dithiophene-2,6-diyl-alt-（4-（2-ethylhexyl）-3-fluorothieno[3,4- b]thiophene）-2-carboxylate-2,6-diyl] （PTB7-Th） and poly[（5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl）-alt-（3,3＇-di（2- dodecyltetradecyl）-2,2＇;5＇,2＂;5＂,2＇-quaterthiophen-5,5＇＂-diyl）] （PffBT4T-2DT）, with suitably complementary absorption spectra and energy levels were applied and examined. Among all different donor-acceptor pairs studied here, the combination of PTB7-Th：poly[NN-bis（1-hexylheptyl）-3,4,9,10-pery,enediimide-1,6/1,7-diyl-alt-2,5-thiophene] （PDI-Th） exhibited the best power conversion efficiency （PCE） of 5.13%, with open-circuit voltage （Vo：） = 0.79 lV, short-circuit current density （Jsc） = 12.35 mA.cm-2 and fill-factor （FF） = 0.52. The polymer of PDI-Th acceptor used here had a regio-irregular backbone, conveniently prepared from a mixture of 1,6- and 1,7-dibromo-PDI. It is also noteworthy that neither additive nor post- treatment is required for obtaining such a cell performance.
基金National Natural Science Foundation of China,Grant/Award Number:51973063Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program,Grant/Award Number:2019TQ05C890+3 种基金Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of EducationJianghan University,Grant/Award Number:JDGD-202010Pearl River S&T Nova Program of Guangzhou,Grant/Award Number:201710010194Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates,Grant/Award Number:2019B030301003。
文摘Organic donor-acceptor semiconductors exhibit great potential in photothermal conversion.However,it is still challenging to achieve pure organic materials with broad absorption comparable with inorganic materials such as graphene.Herein,two D-AD type DPA-BT-O4 and NDI-TPA-O4 and three D-A-π-A-D type Th-O4,Th2-O4,and IDT-O4 were readily prepared via two high-yield steps and simple air oxidization.The stability can be attributed to their multiple resonance structures based on the aromatic nitric acid radical mechanism.Compared with the D-A-D radicals,the conjugation extension of the D-A-π-A-D radicals endows them with a narrowed band gap and broad absorption in powder.Interestingly,the IDT-O4 powder with aggregation-induced radical effect exhibits broad absorption between 300 and 2500 nm,which is comparable with graphene and other inorganic materials.Under irradiation of 0.9 W/cm^(2)(808 nm),the temperature of IDT-O4 powder rises to 250℃within 60 s.The water evaporation conversion efficiency of 94.38%and an evaporation rate of 1.365 kg/m^(2)h^(−1)under one sun illumination were achieved.IDT-O4 stands as one of the most efficient photothermal conversion materials among pure organic materials via a rational design strategy.
基金supported by the National Natural Science Foundation of China (21971160, 21971161, 22271183 and 22371179)the Program for Professor of Special Appointment (Eastern Scholar TP2019039) at Shanghai Institutions of Higher Learning。
文摘Modulating reversible isomerization of hydrophobic dyes in aqueous solutions is greatly desired. Here we report on reversible isomerization of solvatochromic donor-acceptor Stenhouse adducts(DASAs) in water through the confinement from dendritic oligoethylene glycols(OEGs). Dendronization of DASAs with dendritic OEGs affords them characteristic thermoresponsiveness. These dendronized DASAs spontaneously isomerize in water from hydrophobic linear state into hydrophilic cyclic state at room temperature due to the strong hydration. However, hydrophobic microenvironment through thermally dehydration and collapse of the dendritic OEGs at elevated temperatures confines hydration of the DASA moieties and mediates their interactions with the collapsed hydrophobic OEG domains, affording their isomerization recovery in water efficiently from the hydrophilic cyclic state into the hydrophobic linear state. The confinement-mediated reversible isomerization of DASA moieties in water can be repeated through alternative photo-irradiation and thermal dehydrations, exhibiting excellent fatigue resistance.
基金supported by the National Natural Science Foundation of China(22201087)the National Key R&D Program of China(2022YFA1503200)Guangdong Basic and Applied Basic Research Foundation(2022A1515012507)。
文摘A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.
基金supported by the National Natural Science Foundation of China(No.52274302)Natural Science Foundation of Shanghai(Nos.21ZR1429400,22ZR1429700).
文摘The development of non-platinum group metal(non-PGM)and efficient multifunctional electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER)with high activity and stability remains a great challenge.Herein,by in-situ transforming silver manganese composite oxide heterointerface into boosted Mott-Schottky heterointerface through a facile carbon reduction strategy,a nanorod-like silver/manganese oxide with superior multifunctional catalytic activities for ORR,OER and HER and stability was obtained.The nanorod-like silver/manganese oxide with Mott-Schottky heterointerface(designated as Ag/Mn_(3)O_(4))exhibits an ORR half-wave potential of 0.831 V(vs.RHE)in 0.1 M KOH,an OER overpotential of 338 mV and a HER overpotential of 177 mV at the current density of 10 mA·cm^(-2)in 1 M KOH,contributing to its noble-metal benchmarks comparable performance in aqueous aluminum-air(Al-air)battery and laboratorial overall water splitting electrolytic cell.Moreover,in-situ electrochemical Raman and synchrotron radiation spectroscopic measurements were conducted to further illustrate the catalytic mechanism of Ag/Mn_(3)O_(4)Mott-Schottky heterointerface towards various electrocatalytic reactions.At the heterointerface,the Ag phase serves as the electron donor and the active phase for ORR and HER,while the Mn_(3)O_(4)phase serves as the electron acceptor and the active phase for OER,respectively.This work deepens the understanding of the Mott-Schottky effect on electrocatalysis and fills in the gap in fundamental physical principles that are behind measured electrocatalytic activity,which offers substantial implications for the rational design of cost-effective multifunctional electrocatalysts with Mott-Schottky effect.
基金the National Natural Science Foundation of China(Nos.22201063 and U21A2085)Science and Technology Research and Development Plan Joint Fund of Henan Province(No.225200810083)+3 种基金Science and Technology Research and Development Program of Henan Province(No.232102230083)High-level talents international training project of Henan Province(K2306Y)Project of Scientific and Technological Innovation Team in University of Henan Province,China(No.20IRTSTHN001)the Zhongyuan High-Level Talents Special Support Plan of China(No.204200510009).
文摘The combination of donor-acceptor(D-A)structures presents a viable strategy for fabricating covalent organic frameworks(COFs)with exceptional photocatalytic performances.Nevertheless,the selection of functional groups on donor or acceptor building blocks and their effect on the macroscopic properties of COFs are ambiguous.In this study,we tactfully synthesized a pair of Py-DBT-COFs from the same pyrene(Py)donor and 4,7-diphenylbenzo[c][1,2,5]thiadiazole(DBT)acceptor cores with distinct primitive functional groups.The primitive functional groups of building units determine the photocatalytic properties of corresponding Py-DBT-COFs.Specifically,Py-C-DBT-COF synthesized from Py-4CHO and DBT-2NH_(2)showcases a splendid H_(2)evolution rate as high as 21,377.7μmol/(g·h)(with 5 wt.%Pt)originating from better charge transfer capacity,which is significantly superior to that of Py-N-DBT-COF constructed from Py-4NH_(2)and DBT-2CHO.The distinct photocatalytic performances of the two COFs are demonstrated to originate from the different charge separation and transfer capabilities.This work supplies a new avenue for optimizing the photocatalytic performance of D-A COFs from the perspective of primitive functional group selections.
基金supported by the National Natural Science Foundation of China(51973162,22235006,and 22122504)Foundation of Hubei Scientific Committee(2022BAA015,2022EHB010)+1 种基金the Fundamental Research Funds for the Central Universities(2042020kf2058)the Knowledge Innovation Projectof Wuhan City(whkxjsjo14).
文摘Perovskite solar cells(PSCs)have been proven to be a promising option for photovoltaic conversion.With the aim to achieve efficient and stable PSCs,it is essential to explore dopant-free hole-transporting materials(HTMs)with high hole mobility.Herein,HTMs bearing electron donor(D)-electron acceptor(A)-electron donor(D)structures have been constructed with strong intramolecular charge transfer(ICT)effect,based on rational combination of dibenzo[a,c]phenazine and pyridine as electronic acceptors and anchoring groups to perovskite layer.Accordingly,high hole mobility(7.31×10^(-5) cm^(2)·V^(-1)·s^(-1))and photoelectric conversion efficiency(20.45%)have been achieved by dopant-free DPyP-based PSC.It afforded an efficient way to design HTMs with high hole mobility by adjustment of molecular configurations and electronic property of conjugated systems.
基金This research was made possible as a result of a generous grant from NSFC(grant nos.21971101 and 22171127)Guangdong Basic and Applied Basic Research Foundation(grant no.2022A1515011806)+3 种基金Department of Education of Guangdong Province(grant nos.2022JGXM054 and 2021KTSCX106)Shenzhen Science and Technology Innovation Committee(grant no.JCYJ20220519201425001)Thousand Talents Program for Young Scholars,The Pearl River Talent Recruitment Program(grant no.2019QN01Y261)Guangdong Provincial Key Laboratory of Catalysis(grant no.2020B121201002).
文摘Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally diverseα,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with N-hydroxyphthalimide(NHPI)esters and cyanoarenes or aryl aldehydes has been developed.The use of vinyl azide as a precursor to a primary aminewas enabled by the dual role of the Hantzsch ester to form an electron donor-acceptor complex and serve as a sacrificial reductant.This strategy provides a modular synthesis ofα-tertiary primary amines,including unprotected 1,2-amino alcohols,from simple materials with excellent functional group tolerance.The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines.Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by heteroradical cross-coupling betweenα-amino radicals and aryl anion radicals or ketyl anion radicals.
基金supported by the National Natural Science Foundation of China(No.22178266)the Fundamental Research Funds for the Central Universities,and China Postdoctoral Science Foundation(Nos.2021M691754 and 2023T160369).
文摘Photocatalytic hydrogen generation from hydrogen storage media is an effective and promising approach for the green hydrogen industry as well as for achieving carbon neutrality goals.However,the lower photocatalytic efficiency due to the limited light trapping capacity,low electron transfer rate,and severe aggregation of nanoparticles caused by high surface energy seriously restricts their practical application.Herein,we constructed a series of donor–acceptor(D–A)type covalent organic frameworks to confine ultrafine bimetallic Pt-based nanoclusters for photocatalytic hydrogen generation from ammonia borane(AB)hydrolysis.Under visible light irradiation at 20℃,PtCo_(2)@covalent organic framework(COF)showed the highest photocatalytic activity with a turnover frequency(TOF)of 486 min−1.Experiments and density functional theory(DFT)calculations reveal that the high catalytic activity is mainly attributed to the strong electronic interactions between D–A type COF and ultrafine PtCo_(2)nanoclusters.Specifically,the D–A type COF can significantly enhance the light-trapping ability by fine-tuning the electron-acceptor type in the framework,and accelerate the photogenerated electron transfer from D–A type COF to PtCo_(2)nanocluster,which promotes the adsorption and activation of H_(2)O and AB molecules and accelerates hydrogen release.Furthermore,PtCo_(2)@COF also exhibited ultra-high durability due to the significantly enhanced resistance to nanocluster aggregation caused by the nanopore confinement effect of D–A type COF.We believe that this work will provide a theoretical guide for the rational design of efficient D–A COFbased catalysts for photocatalysis.
基金supported by the National Key Research and Development Program of China(2022YFC2804105)the Joint Fund of Shandong Natural Science Foundation(ZR2021LSW013)+5 种基金Natural Science Foundation of Shandong Province(ZR2020QB044,ZR2020QH364,ZR2023MH245,and ZR2022QB090)Postdoctoral Science Foundation of China(2020M682157)Qingdao Emerging Industry Cultivation Project in 2023(23-1-4-xxgg-19-nsh)Shandong Provincial Science and Technology SME Innovation Capacity Improvement Project(2022TSGC2204)the National Natural Science Foundation of China(82003787)Postdoctoral Innovation Project of Shandong Province。
文摘The ability to selectively introduce diverse functionality onto hydrocarbons is of substantial value in the synthesis of both small molecules and pharmaceuticals.In this endeavour,as a photocatalyst-and metalfree process,the electron donor–acceptor(EDA)strategy has not been well explored.Here we report an approach to aliphatic carbon-hydrogen bond diversification through an EDA complex constituted by HCl and S^(IV)=O groups.As an efficient hydrogen atom transfer(HAT)reagent,chlorine radical can be produced via a proton-coupled electron transfer process in this system.Based on this unusual path,a photopromoted versatile aliphatic C–H functionalization is developed without photo-and metal-catalysts,including thiolation,arylation,alkynylation,and allylation.This conversion has concise and ambient reaction conditions,good functional group tolerance,and substrate diversity,and provides an alternative solution for the high value-added utilization of bulk light alkanes.
基金supported by Postgraduate Education Reform Project of Liaoning Province(No.394)the Fund of Liaoning Provincial Department of Education(LJKMZ 20221403)the grants of the National Natural Science Foundation of China(No.21571091).
文摘The development of host-guest MOF luminescent composites has attracted considerable attention. However,it is still a challenge to reasonably design large scale conjugated polycarboxylic acids metal-organic framework (MOF) and modulate donor-acceptor interaction. Herein,a series of isostructural 3D porous lanthanide MOF [Ln_(2)(BINDI)0.5(NO_(3))(DMA)(H_(2)O)]∙DMA∙2.5H_(2)O (Ln = La (1),Ce (2),Pr (3) and Nd (4);H_(4)BINDI (N,N’-bis(5-isophthalic acid)-1,4,5,8-naphthalenediimide) were synthesized. Considering the electron-deficient performances of Ln-BINDI MOFs,D-A type composites Ln-MOFs (1—4@H_(4)TBAPy) were prepared via the incorporation of electron-rich H_(4)TBAPy (1,3,6,8-tetrakis(p-benzoic acid) pyrene),which more improved the luminescence performance of complexes 1—4 and can be used as fluorescence sensors for the detection of nitro compounds and aldehydes. High sensitivity of 1@H_(4)TBAPy towards pNBA,pNA PNP,DNP,and TNP could be achieved through hydrogen bond interactions between MOF and analytes,as well as the π-π interaction between H_(4)TBAPy and the naphthalene ring of BINDI,thus the fluorescence quenching efficiency of 1@H_(4)TBAPy was better than that of the complex 1. In addition,it is found that 1@H_(4)TBAPy has high selectivity and sensitivity to aromatic aldehyde SA,5-Mesal and HMBA. Such strategy to enhance the emission of NDI based Ln-BINDI MOFs,will open up an avenue to obtain more fluorescent MOFs for sensing.
基金supported by the National Natural Science Foundation of China (grant nos.22375070 and 22288101)the Jilin Province Science and Technology Development Plan (grant nos.20220101048JC and 20210101112JC)the 111 Project the Ministry of Education of China (grant no.B17020).
文摘Donor-Acceptor(D-A)alignment is considered a productive strategy to improve the charge separation efficiency of covalent organic frameworks(COFs)and enhance the charge-transfer yield(CTY)of COFs.Moreover,organic molecules containing heteroatoms can produce coordination interaction with PbI2 of perovskite precursor to affect the crystallization process,thereby impeding the decomposition and improving the stability of perovskite materials.Herein,a thiazolo[5,4-d]thiazole(TZ)-based D-A type COF_(TPDA-TZDA) was designed and synthesized from N,N,N′,N′-tetrakis(4-aminophenyl)-1,4-benzenediamine(TPDA)and 4,4′-(thiazolo[5,4-d]thiazole-2,5-diyl)dibenzaldehyde(TZDA).Upon incorporation into the FAPbI3 layer,COF_(TPDA-TZDA) not only restrained the perovskite defects and enhanced the grain size of perovskite films through the coordination effect of the N atoms of TZDA but also ameliorated the charge transport within the perovskite film,which was the benefit of the D-A structure of COF_(TPDA-TZDA).As a result,incorporation of COF_(TPDA-TZDA) into the perovskite solar cells(PSCs)led to a remarkable power conversion efficiency(PCE)of up to 23.51%.Furthermore,even after being stored in high relative humidity(RH≈60%)for 480 h,these PSCs maintained over 90.55%of their original PCE.This work sets the foundation for the development of highly efficient and stable PSCs by utilizing TZ-based D-A type COFs.
