Recyclable polymers offer a great opportunity to address the environmental issues of plastics.Herein,functionalization of recyclable polymers,poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),were reported via...Recyclable polymers offer a great opportunity to address the environmental issues of plastics.Herein,functionalization of recyclable polymers,poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),were reported via end-group modifications and block/random copolymerizations.Di-n-butylmagnesium was selected to catalyze ring-opening polymerization(ROP)of(R)-M in the presence of a series of functional alcohols as the initiators.Block/random copolymerizations of(R)-M andε-caprolactone(ε-CL),L-lactide(L-LA)and trimethylene carbonate(TMC)were performed to control the onset decomposition temperature(T_(d)),melting temperature(T_(m))and glass transition temperature(T_(g)).These functionalized recyclable polymers would find broad applications as the sustainable plastics.展开更多
Dimerized small-molecule acceptors (DSMAs)have attracted increasing attention in organic solar cells(OSCs) due to the advantages of long-term morphology stabilityand exceptional repeatability. However, the power conve...Dimerized small-molecule acceptors (DSMAs)have attracted increasing attention in organic solar cells(OSCs) due to the advantages of long-term morphology stabilityand exceptional repeatability. However, the power conversionefficiencies of the DSMA-based OSCs are highlydependent on the dimerization modes and the underlyingstructure-performance relationship remains unclear. Here, wehave revealed the role of end-group (EG) engineering of the AD-A small-molecule acceptors (SMAs) in tuning the electronic,optical, and electron transport properties of vinyl-bridgedDSMAs by multiscale theoretical calculations. The resultspoint out that the EG engineering can effectively modulate thelowest unoccupied molecular orbital (LUMO) electron densityat the linkage atoms of the SMAs, leading to a broad range ofsuper-exchange (SE) couplings for intramolecular electrontransfer between two SMA units among the studied DSMAs.Consequently, the LUMO energy and distribution are greatlychanged, which further change the excited state energy andoscillator strength. In addition, the different EGs have importantinfluences on the intermolecular electronic couplingsand connectivity. Notably, compared to the previously reportedDSMA of BB-V, the new-designed NB-V demonstratessimultaneous improvements in light absorption and electronmobility due to well-balanced intramolecular and intermolecularelectronic couplings. This work provides helpfulinsights into the development of DSMAs for high-efficiencyOSCs.展开更多
A chemically closed-loop-recyclable biodegradable polymer,poly(p-dioxanone)(PPDO),is one of the ideal candidates for single-use plastic products due to its suitability for different application scenarios.Fascinatingly...A chemically closed-loop-recyclable biodegradable polymer,poly(p-dioxanone)(PPDO),is one of the ideal candidates for single-use plastic products due to its suitability for different application scenarios.Fascinatingly,when PPDO wastes can be collected,its monomer p-dioxanone(PDO) will be obtained through chemical recycling of these wastes;when cannot be collected,the wastes are able to be biodegraded into harmless substances.However,unsatisfied thermal stability and low crystallization rate of PPDO restrict its wider applications.Herein,based on end-group regulation,we simultaneously realized the significant enhancement of thermal stability and crystallization of PPDO through the simple melt processing with tributyl phosphite(TBP) or triphenyl phosphite(TPP).The model reactions were conducted to investigate the reaction mechanism and theoretical products during the preparation of PPDO/phosphite compounds.Two kinds of phosphites were proved to act as the end-capped reagent and chain extender in the melt processing,while TBP presented better reactivity.As a result,the activation energy of thermal decomposition was largely elevated,and the unprecedented T_(5%)(the temperature at a weight loss of 5%) and Tmax(the temperature at a maximum rate of weight loss) of PPDO were obtained,i.e.,T_(5%)of ~330 ℃ and Tmaxof ~385 ℃ in N_(2) atmosphere,T_(5%)of ~240 ℃ and Tmaxof ~317 ℃ in air atmosphere,respectively.Furthermore,the increased crystallization rate,crystallinity,crystalline orderliness,and realizable monomer recovery(yield >90%,purity >99.9%) of PPDO/phosphite compounds were confirmed.展开更多
By employing the asymmetric end-group engineering,an asymmetric nonfused-ring electron acceptor(NFREA)was designed and synthesized.Compared with the symmetric analogs(NoCA-17 and NoCA-18),NoCA-19 possesses broader lig...By employing the asymmetric end-group engineering,an asymmetric nonfused-ring electron acceptor(NFREA)was designed and synthesized.Compared with the symmetric analogs(NoCA-17 and NoCA-18),NoCA-19 possesses broader light absorption range,more coplanarπ-conjugated backbone,and appropriate crystallinity according to the experimental and theoretical results.The organic solar cells based on J52:NoCA-19 exhibited a power conversion efficiency as high as 12.26%,which is much higher than those of J52:NoCA-17(9.50%)and J52:NoCA-18(11.77%),mainly due to more efficient exciton dissociation,better and balanced charge mobility,suppressed recombination loss,shorter charge extraction time,longer charge carrier lifetimes,and more favorable blend film morphology.These findings demonstrate the great potential of asymmetric end-group engineering in exploring low-cost and high-performance NFREAs.展开更多
基金supported by The National Natural Science Foundation of China(21504039)。
文摘Recyclable polymers offer a great opportunity to address the environmental issues of plastics.Herein,functionalization of recyclable polymers,poly((R)-3,4-trans six-membered ring-fused GBL)(P((R)-M)),were reported via end-group modifications and block/random copolymerizations.Di-n-butylmagnesium was selected to catalyze ring-opening polymerization(ROP)of(R)-M in the presence of a series of functional alcohols as the initiators.Block/random copolymerizations of(R)-M andε-caprolactone(ε-CL),L-lactide(L-LA)and trimethylene carbonate(TMC)were performed to control the onset decomposition temperature(T_(d)),melting temperature(T_(m))and glass transition temperature(T_(g)).These functionalized recyclable polymers would find broad applications as the sustainable plastics.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0520102)the National Natural Science Foundation of China (22173108)the Youth Innovation Promotion Association CAS (2023037)。
文摘Dimerized small-molecule acceptors (DSMAs)have attracted increasing attention in organic solar cells(OSCs) due to the advantages of long-term morphology stabilityand exceptional repeatability. However, the power conversionefficiencies of the DSMA-based OSCs are highlydependent on the dimerization modes and the underlyingstructure-performance relationship remains unclear. Here, wehave revealed the role of end-group (EG) engineering of the AD-A small-molecule acceptors (SMAs) in tuning the electronic,optical, and electron transport properties of vinyl-bridgedDSMAs by multiscale theoretical calculations. The resultspoint out that the EG engineering can effectively modulate thelowest unoccupied molecular orbital (LUMO) electron densityat the linkage atoms of the SMAs, leading to a broad range ofsuper-exchange (SE) couplings for intramolecular electrontransfer between two SMA units among the studied DSMAs.Consequently, the LUMO energy and distribution are greatlychanged, which further change the excited state energy andoscillator strength. In addition, the different EGs have importantinfluences on the intermolecular electronic couplingsand connectivity. Notably, compared to the previously reportedDSMA of BB-V, the new-designed NB-V demonstratessimultaneous improvements in light absorption and electronmobility due to well-balanced intramolecular and intermolecularelectronic couplings. This work provides helpfulinsights into the development of DSMAs for high-efficiencyOSCs.
基金supported by the National Key R&D Program of China (2021YFB3801904)the National Natural Science Foundation of China (U19A2095)+2 种基金the Institutional Research Fund from Sichuan University (2020SCUNL205)the Fundamental Research Funds for the Central Universitiesthe 111 Project (B20001)。
文摘A chemically closed-loop-recyclable biodegradable polymer,poly(p-dioxanone)(PPDO),is one of the ideal candidates for single-use plastic products due to its suitability for different application scenarios.Fascinatingly,when PPDO wastes can be collected,its monomer p-dioxanone(PDO) will be obtained through chemical recycling of these wastes;when cannot be collected,the wastes are able to be biodegraded into harmless substances.However,unsatisfied thermal stability and low crystallization rate of PPDO restrict its wider applications.Herein,based on end-group regulation,we simultaneously realized the significant enhancement of thermal stability and crystallization of PPDO through the simple melt processing with tributyl phosphite(TBP) or triphenyl phosphite(TPP).The model reactions were conducted to investigate the reaction mechanism and theoretical products during the preparation of PPDO/phosphite compounds.Two kinds of phosphites were proved to act as the end-capped reagent and chain extender in the melt processing,while TBP presented better reactivity.As a result,the activation energy of thermal decomposition was largely elevated,and the unprecedented T_(5%)(the temperature at a weight loss of 5%) and Tmax(the temperature at a maximum rate of weight loss) of PPDO were obtained,i.e.,T_(5%)of ~330 ℃ and Tmaxof ~385 ℃ in N_(2) atmosphere,T_(5%)of ~240 ℃ and Tmaxof ~317 ℃ in air atmosphere,respectively.Furthermore,the increased crystallization rate,crystallinity,crystalline orderliness,and realizable monomer recovery(yield >90%,purity >99.9%) of PPDO/phosphite compounds were confirmed.
基金the financial support fromtheNSFC(21975055,U2001222,52103352,52120105006,and 51925306)National Key R&D Program of China(2018FYA 0305800)+2 种基金Key Research Program of Chinese Academy of Sciences(XDPB08-2)the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022165)the Fundamental Research Funds for the Central Universities.DFT results described in this article were obtained from the National Supercomputing Centre in Shenzhen(Shenzhen Cloud Computing Centre).
文摘By employing the asymmetric end-group engineering,an asymmetric nonfused-ring electron acceptor(NFREA)was designed and synthesized.Compared with the symmetric analogs(NoCA-17 and NoCA-18),NoCA-19 possesses broader light absorption range,more coplanarπ-conjugated backbone,and appropriate crystallinity according to the experimental and theoretical results.The organic solar cells based on J52:NoCA-19 exhibited a power conversion efficiency as high as 12.26%,which is much higher than those of J52:NoCA-17(9.50%)and J52:NoCA-18(11.77%),mainly due to more efficient exciton dissociation,better and balanced charge mobility,suppressed recombination loss,shorter charge extraction time,longer charge carrier lifetimes,and more favorable blend film morphology.These findings demonstrate the great potential of asymmetric end-group engineering in exploring low-cost and high-performance NFREAs.
