Herein,we developed for the first time two carboxylic acid based intrinsic proton conductors(COOHCOF-1 and COOH-COF-2)via pre-assembly approach.The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical...Herein,we developed for the first time two carboxylic acid based intrinsic proton conductors(COOHCOF-1 and COOH-COF-2)via pre-assembly approach.The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical and thermal stabilities,but also exhibit superhigh intrinsic proton conductive behaviors.Especially,the intrinsic proton conductivity of COOH-COF-2 is up to 2.6×10^(−3) S/cm at 353 K and 98%RH,which is the highest value among all the reported acid functionalized COFs.This work lights up the way for the rational design of functional COFs with remarkably intrinsic proton conducting performance and related practical applications.展开更多
Ammonia(NH_(3))is one of the most important industrial feedstocks in the fields of fertilizers,drugs,explosives,ordnance,commercial cleanings,and so on.However,the features of ammonia such as high toxicity and corrosi...Ammonia(NH_(3))is one of the most important industrial feedstocks in the fields of fertilizers,drugs,explosives,ordnance,commercial cleanings,and so on.However,the features of ammonia such as high toxicity and corrosivity,and difficulty in handling would inevitably increase the risk of environmental damage and the deterioration of natural/public lands.Although sorts of solid adsorbents such as metal oxides,zeolites,organic polymers,activated carbons,and metal organic frameworks have been applied in NH_(3) capture,they still show low uptake capacity,low affinities,and instability.Herein,we developed the first case of a highly stable sulfuric acid covalent organic framework(COF),namely TpBD-(SO_(3)H)_(2),as NH_(3) capturer,in which sulfonic acid sites can strongly interact with NH_(3) molecules,and enhance the performance of NH_(3) sorption.As a result,TpBD-(SO_(3)H)_(2) shows high chemical stability under strong acid and water conditions,an important merit for the potential application in harsh environment.And it also exhibits high ammonia capacity of 11.5 mmol·g^(−1) at 298 K and 1.0 bar,making it one of the best in all chemically stable NH_(3) adsorbents up to date.This work thus develops sulfuric acid COF materials as a new platform for ammonia capture and storage.展开更多
Second harmonic generation(SHG) is one of the most extensively applied nonlinear optical phenomena. Compared to traditional inorganic SHG materials, organic SHG materials, including non-centrosymmetric small molecular...Second harmonic generation(SHG) is one of the most extensively applied nonlinear optical phenomena. Compared to traditional inorganic SHG materials, organic SHG materials, including non-centrosymmetric small molecular crystals and organic polymers, have been extensively explored for SHG optics due to their advantageous properties, including high light-induced damage threshold, ultrafast response speed, high polarization ratio, wide transparency range, and elevated dielectric constant. However,in organic SHG materials, most small molecular crystals often show poor thermal stability(<200 ℃) due to their low molecular weight, which is an important obstacle for practical application under high temperatures. On the other hand, the difficulty in the growth of large-size crystals as well as the disorderly array of chromospheres on polymer chains associated with organic polymers have hindered their widespread application in SHG due to the requirements of processability and homogeneity.Therefore, it is significantly necessary to develop novel organic SHG material with high thermal stability, large-size crystals,excellent processability, high homogeneity, and a well SHG effect. In the contribution, we developed herein porous organic cages(POCs) as a novel platform for SHG optics. Thanks to its inherent macromolecular composition and zero-dimensional discrete structures, POCs can not only solve the instability problem of small molecule crystals but also overcome the drawbacks in growing large-size crystals for organic polymer. The obtained two POCs with chiral asymmetric centers(CPOC-R-5 and CPOCS-7) display advantageous features for SHG optics including well SHG performance, large-size crystal(5 mm×3 mm×1 mm),high thermal stability(≥250 ℃), wide transparency window(750–2,000 nm) and high polarization ratio(up to 94.5%). This work thus develops POCs as a new platform toward the construction of organic NLO materials with the potential application in sorts of SHG optics.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21978138 and 22035003)the Fundamental Research Funds for the Central Universities(Nankai University)the Haihe Laboratory of Sustainable Chemical Transformations(No.YYJC202101).
文摘Herein,we developed for the first time two carboxylic acid based intrinsic proton conductors(COOHCOF-1 and COOH-COF-2)via pre-assembly approach.The obtained COOH-COF-1 and COOH-COF-2 not only show outstanding chemical and thermal stabilities,but also exhibit superhigh intrinsic proton conductive behaviors.Especially,the intrinsic proton conductivity of COOH-COF-2 is up to 2.6×10^(−3) S/cm at 353 K and 98%RH,which is the highest value among all the reported acid functionalized COFs.This work lights up the way for the rational design of functional COFs with remarkably intrinsic proton conducting performance and related practical applications.
基金supported by the National Natural Science Foundation of China(Nos.21978138 and 22035003)the Funda-mental Research Funds for the Central Universities(Nankai University)the Haihe Laboratory of Sustainable Chemical Trans-formations(No.YYJC202101).
文摘Ammonia(NH_(3))is one of the most important industrial feedstocks in the fields of fertilizers,drugs,explosives,ordnance,commercial cleanings,and so on.However,the features of ammonia such as high toxicity and corrosivity,and difficulty in handling would inevitably increase the risk of environmental damage and the deterioration of natural/public lands.Although sorts of solid adsorbents such as metal oxides,zeolites,organic polymers,activated carbons,and metal organic frameworks have been applied in NH_(3) capture,they still show low uptake capacity,low affinities,and instability.Herein,we developed the first case of a highly stable sulfuric acid covalent organic framework(COF),namely TpBD-(SO_(3)H)_(2),as NH_(3) capturer,in which sulfonic acid sites can strongly interact with NH_(3) molecules,and enhance the performance of NH_(3) sorption.As a result,TpBD-(SO_(3)H)_(2) shows high chemical stability under strong acid and water conditions,an important merit for the potential application in harsh environment.And it also exhibits high ammonia capacity of 11.5 mmol·g^(−1) at 298 K and 1.0 bar,making it one of the best in all chemically stable NH_(3) adsorbents up to date.This work thus develops sulfuric acid COF materials as a new platform for ammonia capture and storage.
基金supported by the National Key R&D Program of China (2022YFA1503301)the National Natural Science Foundation of China (21978138, 22035003)+3 种基金the Fundamental Research Funds for the Central Universities (Nankai University)the Haihe Laboratory of Sustainable Chemical Transformations (YYJC202101)the China Postdoctoral Science Foundation (2022TQ0162)the Science Foundation of National Key Laboratory of Science and Technology on Advanced Composites in Special Environments (JCKYS2022603C023)。
文摘Second harmonic generation(SHG) is one of the most extensively applied nonlinear optical phenomena. Compared to traditional inorganic SHG materials, organic SHG materials, including non-centrosymmetric small molecular crystals and organic polymers, have been extensively explored for SHG optics due to their advantageous properties, including high light-induced damage threshold, ultrafast response speed, high polarization ratio, wide transparency range, and elevated dielectric constant. However,in organic SHG materials, most small molecular crystals often show poor thermal stability(<200 ℃) due to their low molecular weight, which is an important obstacle for practical application under high temperatures. On the other hand, the difficulty in the growth of large-size crystals as well as the disorderly array of chromospheres on polymer chains associated with organic polymers have hindered their widespread application in SHG due to the requirements of processability and homogeneity.Therefore, it is significantly necessary to develop novel organic SHG material with high thermal stability, large-size crystals,excellent processability, high homogeneity, and a well SHG effect. In the contribution, we developed herein porous organic cages(POCs) as a novel platform for SHG optics. Thanks to its inherent macromolecular composition and zero-dimensional discrete structures, POCs can not only solve the instability problem of small molecule crystals but also overcome the drawbacks in growing large-size crystals for organic polymer. The obtained two POCs with chiral asymmetric centers(CPOC-R-5 and CPOCS-7) display advantageous features for SHG optics including well SHG performance, large-size crystal(5 mm×3 mm×1 mm),high thermal stability(≥250 ℃), wide transparency window(750–2,000 nm) and high polarization ratio(up to 94.5%). This work thus develops POCs as a new platform toward the construction of organic NLO materials with the potential application in sorts of SHG optics.
