To design high efficiency polymer solar cells(PSCs), it is of great importance to develop suitable polymer donors that work well with the low bandgap acceptors, providing complementary absorption, forming interpenetra...To design high efficiency polymer solar cells(PSCs), it is of great importance to develop suitable polymer donors that work well with the low bandgap acceptors, providing complementary absorption, forming interpenetrating networks in the active layers and minimizing energy loss. Recently, we developed a series of two-dimension-conjugated polymers based on bithienylbenzodithiophene-alt-benzotriazole backbone bearing different conjugated side chains, generally called J-series polymers. They are medium energy bandgap(Eg) polymers(Eg of ca. 1.80 eV)with strong absorptions in the range of 400-650 nm, and exhibit ordered crystalline structures, high hole mobilities, and more interestingly,tunable energy levels depending on the structure variations. In this feature article, we highlight our recent efforts on the design and synthesis of those J-series polymer donors, including an introduction on the polymer design strategy and emphasis on the crucial function of differential conjugated side chain. Finally, the future opportunities and challenges of the J-series polymers in PSCs are discussed.展开更多
In recent years,conjugated polymers have attracted great attention in the application as photovoltaic donor materials in polymer solar cells(PSCs).Broad absorption,lower-energy bandgap,higher hole mobility,relatively ...In recent years,conjugated polymers have attracted great attention in the application as photovoltaic donor materials in polymer solar cells(PSCs).Broad absorption,lower-energy bandgap,higher hole mobility,relatively lower HOMO energy levels,and higher solubility are important for the conjugated polymer donor materials to achieve high photovoltaic performance.Side-chain engineering plays a very important role in optimizing the physicochemical properties of the conjugated polymers.In this article,we review recent progress on the side-chain engineering of conjugated polymer donor materials,including the optimization of flexible side-chains for balancing solubility and intermolecular packing(aggregation),electron-withdrawing substituents for lowering HOMO energy levels,and two-dimension(2D)-conjugated polymers with conjugated side-chains for broadening absorption and enhancing hole mobility.After the molecular structural optimization by side-chain engineering,the2D-conjugated polymers based on benzodithiophene units demonstrated the best photovoltaic performance,with powerconversion efficiency higher than 9%.展开更多
Two-dimensional(2 D) polymers are fascinating as they exhibit unique physical, chemical, mechanical, and electronic properties that are completely different from those of traditional linear or branched polymers. They ...Two-dimensional(2 D) polymers are fascinating as they exhibit unique physical, chemical, mechanical, and electronic properties that are completely different from those of traditional linear or branched polymers. They are very promising for applications in catalysis, separation, optoelectronics, energy storage, and nanomedicine. Recently, ultrathin 2 D conjugated polymers have emerged as advanced materials for converting solar energy into chemical energy. The inherent 2 D planar structure with in-plane periodicity offers many features that are highly desirable for photon-involved catalytic energy conversion processes, including high absorption coefficients,large surface areas, abundant surface active sites, and efficient charge separation. Moreover, the possibility of finely tuning the optoelectronic and structural properties through precise molecular engineering has opened up new opportunities for design and synthesis of novel 2 D polymer nanosheets with unprecedented applications. Herein, we highlight recent advances in developing ultrathin 2 D conjugated polymer nanosheets for solar-to-chemical energy conversion. Specifically, we discuss emerging applications of ultrathin 2 D conjugated polymer nanosheets for solar-driven water splitting and CO2 reduction. Meanwhile, future challenges and prospects for design and synthesis of ultrathin 2 D conjugated polymer nanosheets for solar fuel generation are also included.展开更多
Solvothermal reactions of 3,5-dimethyl-2,6-bis（3-（pyrid-2-yl）-1,2,4-triazolyl） pyridine （L）, 1,4-benzendicarboxylic acid （H2bdc）, and transitional metal cations of M11 （M = Mn, Co, Cd） in the presence of oxa...Solvothermal reactions of 3,5-dimethyl-2,6-bis（3-（pyrid-2-yl）-1,2,4-triazolyl） pyridine （L）, 1,4-benzendicarboxylic acid （H2bdc）, and transitional metal cations of M11 （M = Mn, Co, Cd） in the presence of oxalic acid （H2ox） afford three novel supramolecular polymers （CPs）, namely, {[M2（ox）（L）2][bdc][M2（Hox）2（OH）（H2O）4]·3H2O}n （M = Mn for 1, Co for 2, Cd for 3）. Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2（ox）（L）2]2＋ building block. The bdc2- ligand linked with the unprecedented [M2（Hox）2（OH）2（H2O）4] units through strong O-H...O hydrogen bonds forming a zigzag chain, which are further connected through π-π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.展开更多
Two-dimensional (2D) materials and ultrathin nanosheets have attracted tremendous research interests [1-4]. Exfoliation of porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) with 2D coordination st...Two-dimensional (2D) materials and ultrathin nanosheets have attracted tremendous research interests [1-4]. Exfoliation of porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) with 2D coordination structures is emerging as a viable strategy for preparation of new types of 2D materials [5-8]. The relatively weak bonding within and strong interactions between 2D coordination networks are the main problems for successful exfoliation [9]. Pretreatments of the layered MOFs to expand the interlayer distances can be helpful [10-12]. Capturing the exfoliation intermediates and visualizing their structures are valuable for understanding the exfoliation mechanism and confirming the structures of the final 2D materials [11,12].展开更多
2D polymers(2DPs)have attracted increasing interests in sensors,catalysis,and gas storage applications.Furthermore,2DPs with unique band structure and tunable photophysical properties also have immense potential for a...2D polymers(2DPs)have attracted increasing interests in sensors,catalysis,and gas storage applications.Furthermore,2DPs with unique band structure and tunable photophysical properties also have immense potential for application in photonic neuromorphic computing.Here,photonic synaptic transistors based on 2DPs as the light-tunable charge-trapping medium are developed for the first time.The resulted organic transistors can successfully emulate common synaptic functions,including excitatory postsynaptic current,pair-pulse facilitation,the transition of short-term memory to long-term memory,and dynamic filtering.Benefitting from the high photosensitivity of the 2DP,the devices can be operated under a low operating voltage of0.1 V,and achieve an ultralow energy consumption of~0.29 pJ per event.In addition,the heterostructure formed between the 2DP and organic semiconductor enables spectrum-dependent synaptic responses,which facilitates the simulation of visual learning and memory processes in distinct emotional states.The underlying mechanism of spectrum-dependent synaptic-like behaviors is systematically validated with in situ atomic force microscopy based electrical techniques.The spectrum-enabled tunability of synaptic behaviors further promotes the realization of optical logic functions and associative learning.This work inspires the new application of 2DPs in photonic synapses for future neuromorphic computing.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.51722308,51673200,21734008,and 51820105003)Guangdong Major Project of Basic and Applied Basic Research(No.2019B030302007)Fundamental Research Funds for the Central Universities(No.Buctrc201822,XK1802-2)。
文摘To design high efficiency polymer solar cells(PSCs), it is of great importance to develop suitable polymer donors that work well with the low bandgap acceptors, providing complementary absorption, forming interpenetrating networks in the active layers and minimizing energy loss. Recently, we developed a series of two-dimension-conjugated polymers based on bithienylbenzodithiophene-alt-benzotriazole backbone bearing different conjugated side chains, generally called J-series polymers. They are medium energy bandgap(Eg) polymers(Eg of ca. 1.80 eV)with strong absorptions in the range of 400-650 nm, and exhibit ordered crystalline structures, high hole mobilities, and more interestingly,tunable energy levels depending on the structure variations. In this feature article, we highlight our recent efforts on the design and synthesis of those J-series polymer donors, including an introduction on the polymer design strategy and emphasis on the crucial function of differential conjugated side chain. Finally, the future opportunities and challenges of the J-series polymers in PSCs are discussed.
基金supported by the National Basic Research Program of China(2014CB643501)the National Natural Science Foundation of China(91433117,91333204 and 21374124)
文摘In recent years,conjugated polymers have attracted great attention in the application as photovoltaic donor materials in polymer solar cells(PSCs).Broad absorption,lower-energy bandgap,higher hole mobility,relatively lower HOMO energy levels,and higher solubility are important for the conjugated polymer donor materials to achieve high photovoltaic performance.Side-chain engineering plays a very important role in optimizing the physicochemical properties of the conjugated polymers.In this article,we review recent progress on the side-chain engineering of conjugated polymer donor materials,including the optimization of flexible side-chains for balancing solubility and intermolecular packing(aggregation),electron-withdrawing substituents for lowering HOMO energy levels,and two-dimension(2D)-conjugated polymers with conjugated side-chains for broadening absorption and enhancing hole mobility.After the molecular structural optimization by side-chain engineering,the2D-conjugated polymers based on benzodithiophene units demonstrated the best photovoltaic performance,with powerconversion efficiency higher than 9%.
文摘利用基于萘[1,2-c:5,6-c]二[1,2,5]噻二唑共轭聚合物(NTOD)为给体,富勒烯衍生物PC71BM为受体,制备本体异质结聚合物光探测器.NTOD与PC71BM的共混薄膜吸收范围为300~830 nm.通过对NTOD:PC71BM活性层厚度的调控实现器件暗电流密度的显著降低,增强了探测器的二极管性能,同时保持较高的外量子转化效率.当活性层厚度为385 nm时,聚合物光探测器在-0.1 V偏压下的暗电流为6.69×10–10A cm^(-2).在–0.1 V偏压下器件在440~800 nm的工作波段的比探测率均超过1013 cm Hz^(1/2)W^(-1),处于750 nm的工作波长下达到最大比探测率为1.50×1013 cm Hz^(1/2) W^(-1),光响应率为0.22 A W^(-1),这些结果表明基于NTOD:PC71BM的有机光探测器具有广阔的应用前景.
基金financially supported by National Key R&D Program of China(Nos.2017YFA0207301 and 2015CB351903)the National Natural Science Foundation of China(Nos.21474095and 21875235)the Fundamental Research Funds for the Central Universities
文摘Two-dimensional(2 D) polymers are fascinating as they exhibit unique physical, chemical, mechanical, and electronic properties that are completely different from those of traditional linear or branched polymers. They are very promising for applications in catalysis, separation, optoelectronics, energy storage, and nanomedicine. Recently, ultrathin 2 D conjugated polymers have emerged as advanced materials for converting solar energy into chemical energy. The inherent 2 D planar structure with in-plane periodicity offers many features that are highly desirable for photon-involved catalytic energy conversion processes, including high absorption coefficients,large surface areas, abundant surface active sites, and efficient charge separation. Moreover, the possibility of finely tuning the optoelectronic and structural properties through precise molecular engineering has opened up new opportunities for design and synthesis of novel 2 D polymer nanosheets with unprecedented applications. Herein, we highlight recent advances in developing ultrathin 2 D conjugated polymer nanosheets for solar-to-chemical energy conversion. Specifically, we discuss emerging applications of ultrathin 2 D conjugated polymer nanosheets for solar-driven water splitting and CO2 reduction. Meanwhile, future challenges and prospects for design and synthesis of ultrathin 2 D conjugated polymer nanosheets for solar fuel generation are also included.
基金supported by the National Natural Science Foundation of China (No. 21101097)Natural Science Foundation of Shandong Province (ZR2010BQ023)the State Key Laboratory of Solid Lubrication (No. 0701)
文摘Solvothermal reactions of 3,5-dimethyl-2,6-bis（3-（pyrid-2-yl）-1,2,4-triazolyl） pyridine （L）, 1,4-benzendicarboxylic acid （H2bdc）, and transitional metal cations of M11 （M = Mn, Co, Cd） in the presence of oxalic acid （H2ox） afford three novel supramolecular polymers （CPs）, namely, {[M2（ox）（L）2][bdc][M2（Hox）2（OH）（H2O）4]·3H2O}n （M = Mn for 1, Co for 2, Cd for 3）. Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2（ox）（L）2]2＋ building block. The bdc2- ligand linked with the unprecedented [M2（Hox）2（OH）2（H2O）4] units through strong O-H...O hydrogen bonds forming a zigzag chain, which are further connected through π-π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.
基金supported by the National Natural Science Foundation of China (21731007, 21701191, and 21821003)the Guangdong Pearl River Talents Program (2017BT01C161)the Fundamental Research Funds for the Central Universities (18lgpy42)
文摘Two-dimensional (2D) materials and ultrathin nanosheets have attracted tremendous research interests [1-4]. Exfoliation of porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) with 2D coordination structures is emerging as a viable strategy for preparation of new types of 2D materials [5-8]. The relatively weak bonding within and strong interactions between 2D coordination networks are the main problems for successful exfoliation [9]. Pretreatments of the layered MOFs to expand the interlayer distances can be helpful [10-12]. Capturing the exfoliation intermediates and visualizing their structures are valuable for understanding the exfoliation mechanism and confirming the structures of the final 2D materials [11,12].
基金Beijing National Laboratory for Molecular Sciences,Grant/Award Number:BNLMS201904Fundamental Research Funds for the Central Universities+4 种基金Large Scale Instrument Test Funds of Tongji University,Grant/Award Number:2021GX002National Key Research and Development Program of China,Grant/Award Number:2017YFA0103904National Natural Science Foundation of China,Grant/Award Numbers:61822405,62074111Science and Technology Foundation of Shanghai,Grant/Award Numbers:19JC1412402,20JC1415600Shuguang Program supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission,Grant/Award Number:18SG20。
文摘2D polymers(2DPs)have attracted increasing interests in sensors,catalysis,and gas storage applications.Furthermore,2DPs with unique band structure and tunable photophysical properties also have immense potential for application in photonic neuromorphic computing.Here,photonic synaptic transistors based on 2DPs as the light-tunable charge-trapping medium are developed for the first time.The resulted organic transistors can successfully emulate common synaptic functions,including excitatory postsynaptic current,pair-pulse facilitation,the transition of short-term memory to long-term memory,and dynamic filtering.Benefitting from the high photosensitivity of the 2DP,the devices can be operated under a low operating voltage of0.1 V,and achieve an ultralow energy consumption of~0.29 pJ per event.In addition,the heterostructure formed between the 2DP and organic semiconductor enables spectrum-dependent synaptic responses,which facilitates the simulation of visual learning and memory processes in distinct emotional states.The underlying mechanism of spectrum-dependent synaptic-like behaviors is systematically validated with in situ atomic force microscopy based electrical techniques.The spectrum-enabled tunability of synaptic behaviors further promotes the realization of optical logic functions and associative learning.This work inspires the new application of 2DPs in photonic synapses for future neuromorphic computing.
