From the standpoint of chemical structures,the organic backbones of energetic materials can be classified into aromatic rings,nonaromatic rings,and open chains.Although the category of aromatic energetic compounds exh...From the standpoint of chemical structures,the organic backbones of energetic materials can be classified into aromatic rings,nonaromatic rings,and open chains.Although the category of aromatic energetic compounds exhibits several advantages in the regulation of energetic properties,the nonaromatic heterocycles,assembling nitramino explosophores with simple alkyl bridges,still have prevailed in benchmark materials.The methylene bridge plays a pivotal role in the constructions of the classic nonaromatic heterocycle-based energetic compounds,e.g.,hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX)and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX),whereas ethylene bridge is the core moiety of state-of-the-art explosive 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20).In this context,it is of great interest to employ simple and practical bridges to assemble aromatic and nonaromatic nitrogen-rich heterocycles,thereby expanding the structural diversity of energetic materials,e.g.,bridged and fused nitrogen-rich poly-heterocycles.Furthermore,alkyl-bridged poly-heterocycles highlight the potential for the open chain type of energetic materials.In this review,the development of alkyl bridges in linking nitrogen-rich heterocycles is presented,and the perspective of the newly constructed energetic backbones is summarized for the future design of advanced energetic materials.展开更多
In recent years,the introduction of fused rings own high density and low sensitivity has promoted the development of energetic materials.However,the development of energetic compounds containing fused and bridged ring...In recent years,the introduction of fused rings own high density and low sensitivity has promoted the development of energetic materials.However,the development of energetic compounds containing fused and bridged rings by introducing multiple nitrogen heterocycles at different sites of fused rings is still difficult to progress,which seriously limits the emergence of advanced energetic compounds.In this study,a series of energetic materials choosing different nitrogen rich heterocycles at the vacancies of the fused ring,i.e.,neutral compound 5,6 and their ionic derivatives(compounds 7-12)were designed and synthesized.Compounds 5 and 6 were further confirmed by single crystal X-ray diffraction,while the crystal analysis and theoretical calculations were carried out to explore the relationship between crystal structure and physicochemical properties.All of the newly synthesized compounds(5-12)are insensitive to mechanical stimulation(IS>40 J;FS≥342 N)and they own the high detonation velocity(D:8322-9075 m/s).Notably,hydrazine salt 11 own the higher detonation velocity(9075 m/s)and powder density(1.83 g/cm^(3)),but exhibits lower sensitivity(IS>40 J)than the classical energetic compound RDX(8795 m/s,1.80 g/cm^(3),7.5 J).It is obvious that the combination of 5,6-fused triazolo-triazine and nitropyrazole-tetrazole may be a new energetic skeleton for synthesising the heterocyclic compounds with balanced energy-stability.展开更多
Small molecule ladder-type heteroarenes IHBT-2F is designed and synthesized with strong electrondonating and molecular packing properties, where the central unit, fused thienobenzene-thienothiphene (IHBT), is attached...Small molecule ladder-type heteroarenes IHBT-2F is designed and synthesized with strong electrondonating and molecular packing properties, where the central unit, fused thienobenzene-thienothiphene (IHBT), is attached with the strong electron-deficient 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2FIC) as the end group. The counterpart IDBT-2F with indancenodibenzothiophene (IDBT) mainchain is sythesized for comparison, in which thieno[3,2-b]thiophene (TT) core of IHBT is replaced by benzene core. Relative to benzene-core IDBT-2F, TT-core IHBT-2F shows a much higher highest occupied molecular orbital energy level (IHBT-2F:-5.46 eV;IDBT-2F:-5.72 eV) and significantly redshifted absorption, due to the π-donor capability of the sulfur atom, the larger π-conjugation and stronger intermolecular π-π stacking. The as-cast organic solar cells (OSCs) based on blends of PTB7-Th donor and IHBT-2F acceptor without additional treatments exhibit power conversion efficiencies (PCEs) as high as 8.74%, which is much higher than that of PTB7-Th:IDBT-2F (6.73%).展开更多
A new remedy is proposed in this study to increase the ductility of cross-braced frames to a level comparable with ductile moment frames.The suggested system consists of one or two concentric steel rings installed in ...A new remedy is proposed in this study to increase the ductility of cross-braced frames to a level comparable with ductile moment frames.The suggested system consists of one or two concentric steel rings installed in the cross-braced bay vertically.The steel rings are designed such that they fail in bending sooner than failure of the braces in compression.Then the rings act as seismic fuses with multiple bending plastic hinges.Using nonlinear static analysis,it is shown that the proposed system can be designed to behave like cross-braced frames with regard to stiffness and strength,and like special moment frames with regard to ductility.Seismic design factors for the proposed system are recommended based on nonlinear pushover and cyclic analysis studies.展开更多
In this paper, bendloss characteristics of an optical fibre are investigated in detail, and the results show that the resonator with a smaller ring radius, wider free spectrum range （FSR）, higher fineness （f） and ...In this paper, bendloss characteristics of an optical fibre are investigated in detail, and the results show that the resonator with a smaller ring radius, wider free spectrum range （FSR）, higher fineness （f） and quality-factor （Q） can be achieved by using microfibres. Based on the improved fused taper technique, a high-quality microfibre with 5 ttm radius has been fabricated, and an all-fibre micro-ring resonator with a radius of only 500μm is realized using self-coiling coupling method. The good-resonant characteristic makes the all-fibre device be expected to avoid bendloss and connection loss associated with planar waveguide integration.展开更多
半导体光催化剂是一种极具前景的绿色催化剂,广泛用于污染物降解、水解制氢和有机合成等领域,有望利用太阳能来解决能源和环境问题,是当前的研究前沿和热点.然而,单组分半导体光催化剂的光生电子和空穴容易复合,导致量子效率差和光催化...半导体光催化剂是一种极具前景的绿色催化剂,广泛用于污染物降解、水解制氢和有机合成等领域,有望利用太阳能来解决能源和环境问题,是当前的研究前沿和热点.然而,单组分半导体光催化剂的光生电子和空穴容易复合,导致量子效率差和光催化效率低.近年人们发现,将两种或多种催化材料结合,构建异质结光催化体系可有效促进光生电子-空穴分离.但传统的异质结体系中光生电子的还原性和光生空穴的氧化性通常在电荷转移后变弱,因此,很难同时具备高电荷转移效率和强氧化还原能力.研究发现,构建Z型异质结光催化体系不仅可以减少本体电子-空穴的复合,使其在不同半导体材料上实现空间分离,具有光谱响应宽、电荷分离效率高和稳定性高等优势,而且能保持良好的氧化还原能力.在半导体材料领域,石墨相氮化碳(g-C_(3)N_(4))作为一种无金属聚合物半导体,具有良好的热化学稳定性、电学和光学特性,但存在量子效率低和适用范围窄等局限性.而五氧化二钒(V_(2)O_(5))是一种重要的过渡金属氧化物半导体,由于具有良好的电学和光学性能被广泛用于锂离子电池、气敏传感器和光电器件.V_(2)O_(5)能带间隙(~2.19 e V)窄,具有合适的能量频带边缘(ECB=0.81 e V,EVB=3.0 e V),可以与g-C_(3)N_(4)(ECB=1.14 e V,EVB=1.59 e V)很好地匹配,形成稳定状态的Z型光催化体系,并提高光催化有机合成反应的效率.本文以三聚氰胺和偏钒酸铵为原料,采用热处理法分别制备g-C_(3)N_(4)和V_(2)O_(5),采用水热法制备Z型V_(2)O_(5)/g-C_(3)N_(4)二元复合材料.X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和紫外-可见光吸收光谱(UV-Vis)等结果表明,成功制备了Z型V_(2)O_(5)/g-C_(3)N_(4).UV-Vis结果表明,V_(2)O_(5)/g-C_(3)N_(4)具有较宽的光吸收范围,从而提高了复合半导体材料的光学性能.在温和条件下,以未活化烯烃修饰的喹唑啉酮和芳基氧膦为反应物,V_(2)O_(5)/g-C_(3)N_(4)为多相光催化剂,进行膦酰化自由基偶联反应,制得一系列环合的膦酰化喹唑啉酮,收率为63%-83%.该反应具有原料易得、条件温和、底物范围广、产品收率及区域选择性良好等优点,同时催化剂循环使用性能良好.值得注意的是,不同吸电子取代基、供电子取代基修饰的喹唑啉酮和非对称结构的芳基氧膦均能兼容于该反应体系,并以中等至良好的收率得到了各种膦酰化喹唑啉酮化合物.本文采用的合成策略同样适用于三氟甲基化、二氟烷基化和芳基磺酰化等自由基串联环化反应,且具有良好的催化性能.机理研究结果表明,V_(2)O_(5)/g-C_(3)N_(4)被光激发后,V_(2)O_(5)导带(CB)上的光生电子与g-C_(3)N_(4)价带(VB)上的光生空穴迅速复合,导致g-C_(3)N_(4)的导带上无法与本体空穴复合的电子发生单电子转移(SET)过程,且与分子氧(空气中)反应生成超氧阴离子自由基(O_(2)·^(-)).V_(2)O_(5)价带上的空穴氧化芳基氧膦产生自由基阳离子,去质子化产生氧膦自由基,随后加成到未活化烯烃生成新的自由基物种,最后发生分子内环化反应,得到目标产物.V_(2)O_(5)/g-C_(3)N_(4)成本较低,且该光催化反应策略可实现克级制备,循环使用5次后催化活性保持不变.综上,本文可为光催化自由基串联环化反应,杂环化合物合成研究和Z型异质结的光催化应用提供参考.展开更多
In this work, four fused ring electron acceptors(FREAs), 2F-C5, 2F-C6, 2F-C8 and 2F-C10, are developed to investigate the effect of side-chain size on the molecular properties and photovoltaic performance of FREA syst...In this work, four fused ring electron acceptors(FREAs), 2F-C5, 2F-C6, 2F-C8 and 2F-C10, are developed to investigate the effect of side-chain size on the molecular properties and photovoltaic performance of FREA systematically. The elongation of side-chains in the FREAs not only improves their solubility in the processing solvent, but also enhances their miscibility with the donor PBDB-T. It helps the FREA diffuse into the donor PBDB-T during film-formation, thus leading to the decrease in domain size and domain purity from PBDB-T:2F-C5 to PBDB-T:2F-C10 blend films in sequence. The smaller domain size affords more D/A interfaces to benefit exciton dissociation and inhibit monomolecular recombination. However, severe bimolecular recombination occurs when the domain purity decreases to a critical point. Due to the dual function of the increment of side-chain length, both short-circuit current density(J_(SC)) and fill factor(FF) of devices exhibit an evolution of first increasing then decreasing from 2F-C5, 2F-C6, 2F-C8 to 2F-C10 based OSCs. The PBDB-T:2F-C8 based OSCs get a fine balance in morphology with moderate domain size as well as high domain purity simultaneously for the least charge carrier recombination, thus achieving the highest power conversion efficiency of 12.28% with the best J_(SC)(21.27 mA cm^(-2)) and FF(71.96%).展开更多
A series of new organic semiconductors based on s-indaceno[1,2-b：5,6-b＇]dithiophene-4,9-dione was success fully synthesized and characterized. The electron withdrawing carbonyl group lowers the LUMO energy levels, l...A series of new organic semiconductors based on s-indaceno[1,2-b：5,6-b＇]dithiophene-4,9-dione was success fully synthesized and characterized. The electron withdrawing carbonyl group lowers the LUMO energy levels, leading to increased electronegativities, which is beneficial for high photo-stability in air. The n-alkyl substituted compounds, lc and ld, crystallize with the rigid coplanar systems packed into slipped face-to-face n-stacks. Inter- estingly, lc and ld also show liquid crystalline behaviors, which give highly ordered molecular packing over large area.展开更多
基金National Natural Science Foundation of China(Grant Nos.22075023,22205022,and 22235003)to provide fund for conducting experiments。
文摘From the standpoint of chemical structures,the organic backbones of energetic materials can be classified into aromatic rings,nonaromatic rings,and open chains.Although the category of aromatic energetic compounds exhibits several advantages in the regulation of energetic properties,the nonaromatic heterocycles,assembling nitramino explosophores with simple alkyl bridges,still have prevailed in benchmark materials.The methylene bridge plays a pivotal role in the constructions of the classic nonaromatic heterocycle-based energetic compounds,e.g.,hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX)and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX),whereas ethylene bridge is the core moiety of state-of-the-art explosive 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20).In this context,it is of great interest to employ simple and practical bridges to assemble aromatic and nonaromatic nitrogen-rich heterocycles,thereby expanding the structural diversity of energetic materials,e.g.,bridged and fused nitrogen-rich poly-heterocycles.Furthermore,alkyl-bridged poly-heterocycles highlight the potential for the open chain type of energetic materials.In this review,the development of alkyl bridges in linking nitrogen-rich heterocycles is presented,and the perspective of the newly constructed energetic backbones is summarized for the future design of advanced energetic materials.
基金supported by the National Natural Science Foundation of China(Grant No.21875110,22075143)the Science Challenge Projectthe Qing Lan Project for the grant。
文摘In recent years,the introduction of fused rings own high density and low sensitivity has promoted the development of energetic materials.However,the development of energetic compounds containing fused and bridged rings by introducing multiple nitrogen heterocycles at different sites of fused rings is still difficult to progress,which seriously limits the emergence of advanced energetic compounds.In this study,a series of energetic materials choosing different nitrogen rich heterocycles at the vacancies of the fused ring,i.e.,neutral compound 5,6 and their ionic derivatives(compounds 7-12)were designed and synthesized.Compounds 5 and 6 were further confirmed by single crystal X-ray diffraction,while the crystal analysis and theoretical calculations were carried out to explore the relationship between crystal structure and physicochemical properties.All of the newly synthesized compounds(5-12)are insensitive to mechanical stimulation(IS>40 J;FS≥342 N)and they own the high detonation velocity(D:8322-9075 m/s).Notably,hydrazine salt 11 own the higher detonation velocity(9075 m/s)and powder density(1.83 g/cm^(3)),but exhibits lower sensitivity(IS>40 J)than the classical energetic compound RDX(8795 m/s,1.80 g/cm^(3),7.5 J).It is obvious that the combination of 5,6-fused triazolo-triazine and nitropyrazole-tetrazole may be a new energetic skeleton for synthesising the heterocyclic compounds with balanced energy-stability.
基金NSFC (21504058)NSFC/RGC Joint Research Scheme No. N_CUHK418/17+1 种基金Research Grant Council of Hong Kong (General Research Fund No. 14314216)the beam time and technical supports provided by 19U2 beamline at SSRF, Shanghai
文摘Small molecule ladder-type heteroarenes IHBT-2F is designed and synthesized with strong electrondonating and molecular packing properties, where the central unit, fused thienobenzene-thienothiphene (IHBT), is attached with the strong electron-deficient 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2FIC) as the end group. The counterpart IDBT-2F with indancenodibenzothiophene (IDBT) mainchain is sythesized for comparison, in which thieno[3,2-b]thiophene (TT) core of IHBT is replaced by benzene core. Relative to benzene-core IDBT-2F, TT-core IHBT-2F shows a much higher highest occupied molecular orbital energy level (IHBT-2F:-5.46 eV;IDBT-2F:-5.72 eV) and significantly redshifted absorption, due to the π-donor capability of the sulfur atom, the larger π-conjugation and stronger intermolecular π-π stacking. The as-cast organic solar cells (OSCs) based on blends of PTB7-Th donor and IHBT-2F acceptor without additional treatments exhibit power conversion efficiencies (PCEs) as high as 8.74%, which is much higher than that of PTB7-Th:IDBT-2F (6.73%).
文摘A new remedy is proposed in this study to increase the ductility of cross-braced frames to a level comparable with ductile moment frames.The suggested system consists of one or two concentric steel rings installed in the cross-braced bay vertically.The steel rings are designed such that they fail in bending sooner than failure of the braces in compression.Then the rings act as seismic fuses with multiple bending plastic hinges.Using nonlinear static analysis,it is shown that the proposed system can be designed to behave like cross-braced frames with regard to stiffness and strength,and like special moment frames with regard to ductility.Seismic design factors for the proposed system are recommended based on nonlinear pushover and cyclic analysis studies.
基金Project supported by the National Natural Science Foundation of China(Grant No60607001)the Natural Science Foundation of Beijing,China(Grant No4052023)the Talents of Beijing Jiaotong University,Beijing,China(Grant No2007RC015)
文摘In this paper, bendloss characteristics of an optical fibre are investigated in detail, and the results show that the resonator with a smaller ring radius, wider free spectrum range （FSR）, higher fineness （f） and quality-factor （Q） can be achieved by using microfibres. Based on the improved fused taper technique, a high-quality microfibre with 5 ttm radius has been fabricated, and an all-fibre micro-ring resonator with a radius of only 500μm is realized using self-coiling coupling method. The good-resonant characteristic makes the all-fibre device be expected to avoid bendloss and connection loss associated with planar waveguide integration.
文摘半导体光催化剂是一种极具前景的绿色催化剂,广泛用于污染物降解、水解制氢和有机合成等领域,有望利用太阳能来解决能源和环境问题,是当前的研究前沿和热点.然而,单组分半导体光催化剂的光生电子和空穴容易复合,导致量子效率差和光催化效率低.近年人们发现,将两种或多种催化材料结合,构建异质结光催化体系可有效促进光生电子-空穴分离.但传统的异质结体系中光生电子的还原性和光生空穴的氧化性通常在电荷转移后变弱,因此,很难同时具备高电荷转移效率和强氧化还原能力.研究发现,构建Z型异质结光催化体系不仅可以减少本体电子-空穴的复合,使其在不同半导体材料上实现空间分离,具有光谱响应宽、电荷分离效率高和稳定性高等优势,而且能保持良好的氧化还原能力.在半导体材料领域,石墨相氮化碳(g-C_(3)N_(4))作为一种无金属聚合物半导体,具有良好的热化学稳定性、电学和光学特性,但存在量子效率低和适用范围窄等局限性.而五氧化二钒(V_(2)O_(5))是一种重要的过渡金属氧化物半导体,由于具有良好的电学和光学性能被广泛用于锂离子电池、气敏传感器和光电器件.V_(2)O_(5)能带间隙(~2.19 e V)窄,具有合适的能量频带边缘(ECB=0.81 e V,EVB=3.0 e V),可以与g-C_(3)N_(4)(ECB=1.14 e V,EVB=1.59 e V)很好地匹配,形成稳定状态的Z型光催化体系,并提高光催化有机合成反应的效率.本文以三聚氰胺和偏钒酸铵为原料,采用热处理法分别制备g-C_(3)N_(4)和V_(2)O_(5),采用水热法制备Z型V_(2)O_(5)/g-C_(3)N_(4)二元复合材料.X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和紫外-可见光吸收光谱(UV-Vis)等结果表明,成功制备了Z型V_(2)O_(5)/g-C_(3)N_(4).UV-Vis结果表明,V_(2)O_(5)/g-C_(3)N_(4)具有较宽的光吸收范围,从而提高了复合半导体材料的光学性能.在温和条件下,以未活化烯烃修饰的喹唑啉酮和芳基氧膦为反应物,V_(2)O_(5)/g-C_(3)N_(4)为多相光催化剂,进行膦酰化自由基偶联反应,制得一系列环合的膦酰化喹唑啉酮,收率为63%-83%.该反应具有原料易得、条件温和、底物范围广、产品收率及区域选择性良好等优点,同时催化剂循环使用性能良好.值得注意的是,不同吸电子取代基、供电子取代基修饰的喹唑啉酮和非对称结构的芳基氧膦均能兼容于该反应体系,并以中等至良好的收率得到了各种膦酰化喹唑啉酮化合物.本文采用的合成策略同样适用于三氟甲基化、二氟烷基化和芳基磺酰化等自由基串联环化反应,且具有良好的催化性能.机理研究结果表明,V_(2)O_(5)/g-C_(3)N_(4)被光激发后,V_(2)O_(5)导带(CB)上的光生电子与g-C_(3)N_(4)价带(VB)上的光生空穴迅速复合,导致g-C_(3)N_(4)的导带上无法与本体空穴复合的电子发生单电子转移(SET)过程,且与分子氧(空气中)反应生成超氧阴离子自由基(O_(2)·^(-)).V_(2)O_(5)价带上的空穴氧化芳基氧膦产生自由基阳离子,去质子化产生氧膦自由基,随后加成到未活化烯烃生成新的自由基物种,最后发生分子内环化反应,得到目标产物.V_(2)O_(5)/g-C_(3)N_(4)成本较低,且该光催化反应策略可实现克级制备,循环使用5次后催化活性保持不变.综上,本文可为光催化自由基串联环化反应,杂环化合物合成研究和Z型异质结的光催化应用提供参考.
基金supported by the National Postdoctoral Program for Innovative Talents (BX201700253)the China Postdoctoral Science Foundation (2017M620068, 2018M630208)+1 种基金the National Natural Science Foundation of China (21673257, 21805288)the Ministry of Science and Technology (2016YFA0200700)
文摘In this work, four fused ring electron acceptors(FREAs), 2F-C5, 2F-C6, 2F-C8 and 2F-C10, are developed to investigate the effect of side-chain size on the molecular properties and photovoltaic performance of FREA systematically. The elongation of side-chains in the FREAs not only improves their solubility in the processing solvent, but also enhances their miscibility with the donor PBDB-T. It helps the FREA diffuse into the donor PBDB-T during film-formation, thus leading to the decrease in domain size and domain purity from PBDB-T:2F-C5 to PBDB-T:2F-C10 blend films in sequence. The smaller domain size affords more D/A interfaces to benefit exciton dissociation and inhibit monomolecular recombination. However, severe bimolecular recombination occurs when the domain purity decreases to a critical point. Due to the dual function of the increment of side-chain length, both short-circuit current density(J_(SC)) and fill factor(FF) of devices exhibit an evolution of first increasing then decreasing from 2F-C5, 2F-C6, 2F-C8 to 2F-C10 based OSCs. The PBDB-T:2F-C8 based OSCs get a fine balance in morphology with moderate domain size as well as high domain purity simultaneously for the least charge carrier recombination, thus achieving the highest power conversion efficiency of 12.28% with the best J_(SC)(21.27 mA cm^(-2)) and FF(71.96%).
文摘A series of new organic semiconductors based on s-indaceno[1,2-b：5,6-b＇]dithiophene-4,9-dione was success fully synthesized and characterized. The electron withdrawing carbonyl group lowers the LUMO energy levels, leading to increased electronegativities, which is beneficial for high photo-stability in air. The n-alkyl substituted compounds, lc and ld, crystallize with the rigid coplanar systems packed into slipped face-to-face n-stacks. Inter- estingly, lc and ld also show liquid crystalline behaviors, which give highly ordered molecular packing over large area.
