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排序方式: 共有75条查询结果,搜索用时 15 毫秒
1.
Carbene‐metal‐amides (CMAs) are a promising family of donor–bridge–acceptor molecular charge‐transfer (CT) emitters for organic light‐emitting diodes. A universal approach is demonstrated to tune the energy of their CT emission. A blueshift of up to 210 meV is achievable in solid state via dilution in a polar host matrix. The origin of this shift has two components: constraint of thermally‐activated triplet diffusion, and electrostatic interactions between guest and polar host. This allows the emission of mid‐green CMA archetypes to be tuned to sky blue without chemical modifications. Monte‐Carlo simulations based on a Marcus‐type transfer integral successfully reproduce the concentration‐ and temperature‐dependent triplet diffusion process, revealing a substantial shift in the ensemble density of states in polar hosts. In gold‐bridged CMAs, this shift does not lead to a significant change in luminescence lifetime, thermal activation energy, reorganization energy, or intersystem crossing rate. These discoveries offer new insight into coupling between the singlet and triplet manifolds in CMA materials, revealing a dominant interaction between states of CT character. The same approach is employed using materials which have been chemically modified to alter the energy of their CT state directly, shifting the emission of sky‐blue chromophores into the practical blue range.  相似文献   
2.
Hydrogen gas generation with an effective response to changing application demands was achieved with the use of a hydrogen storage battery based on aqueous cesium bicarbonate hydrogenation/formate dehydrogenation, homogeneously catalyzed by an Ir(I)N-heterocyclic carbene complex. In this device, the storage solution was circulated through a small volume tubular reactor heated to the required high temperature to allow fast hydrogen evolution while the high volume reservoir was kept at ambient temperature at which no H2 was generated. Merely by the control of the reactor temperature, it was possible to regulate the rate of hydrogen evolution as required. The results also demonstrate the feasibility of homogeneous catalysis for the purpose of hydrogen generation in flow systems.  相似文献   
3.
郭杰  张帆  谢世玉  由立新  孙亚光 《化工学报》2022,73(8):3608-3614
1,3-二(1-羧乙基)咪唑盐(HL)和Zn(NO3)2·6H2O反应合成二维配位聚合物[Zn(L)2] n (Zn-L),产物再与K2PdCl4在四氢呋喃溶液中反应引入氮杂环卡宾-钯(NHC-Pd)催化位点,制得催化剂NHC-Pd@Zn-L,并通过PXRD、TGA、ICP、SEM、EDS和XPS进行表征。结果表明,NHC-Pd@Zn-L具有良好的热稳定性且修饰后晶体的框架结构没有发生变化,Pd以NHC-Pd的形式结合在Zn-L中,并均匀分散在配位聚合物中。将NHC-Pd@Zn-L用于催化Suzuki-Miyaura交叉偶联反应,当以苯硼酸和溴苯为底物,催化剂用量为15 mg,乙醇为溶剂,碳酸钾为碱的条件下60℃反应6 h,产率达到>99%,而且催化剂易于回收并可循环使用3次。  相似文献   
4.
范凤兰  刘少冕  昌健 《工业催化》2017,25(11):69-72
通过一种由二氧化硅或聚苯乙烯树脂固载化的卡宾催化剂催化甲醛缩合制备1,3-二羟基丙酮(DHA),在合成过程中不使用含有卤素的溴化3-乙基苯并噻唑盐和有毒有害的三乙胺,同时催化剂能够分离回收重复使用。在N2保护下,考察了反应温度、反应时间和不同溶剂对产物1,3-二羟基丙酮收率的影响。采用HLPC分析方法对DHA定量分析,在反应温度140℃,反应时间3 h和以二氧六环为溶剂的体系中,甲醛转化率可达100%,1,3-二羟基丙酮选择性为92.37%,并通过~1HNMR,~(13)CNMR及IR光谱分析确证了化合物的结构。  相似文献   
5.
Ionic liquid-functionalized mesoporous polymeric networks with specific surface area up to 935 m2/g have been successfully synthesized one pot by solvothermal copolymerization of divinylbenzene and monomeric ionic liquids. The as-obtained polymers exhibit a monolithic structure featuring large pore volumes, an abundant mesoporosity and an adjustable content of ionic liquids. The effect of the reaction conditions on the pore structure has been studied in detail. These poly(ionic liquid)-based porous networks (PILPNs) have then been employed as precursors in two distinct applications, namely organocatalysis and production of microporous carbon monoliths. Selected organocatalyzed reactions, including carbonatation of propylene oxide by cycloaddition with carbon dioxide, benzoin condensation, and cyanosilylation of benzaldehyde have been readily triggered by PILPNs acting as crosslinked polymer-supported (pre)catalysts. The two latter reactions required the prior deprotonation of the imidazolium salt units with a strong base to successfully generate polymer-supported N-heterocyclic carbenes, referred to as poly(NHC)s. Facile recycling and reuse of polymer-supported (pre)catalysts was achieved by simple filtration owing to the heterogeneous reaction conditions. Furthermore, PILPNs could be easily converted into microporous carbon monoliths via CO2 activation.  相似文献   
6.
Dehydrogenation is a sustainable form of oxidation catalysis, as it avoids any primary oxidant and the waste that would accompany it. Homogeneous catalyst design for this reaction is delicate: the catalyst must have a sufficient H2 affinity to abstract two hydrogen atoms from the substrate but not so much affinity as to fail to release them as free H2. N-Heterocyclic carbene (NHC) ligands achieve this balancing act in a series of iridium catalysts based on the Ir(IMe)2 motif (IMe=N,N′-dimethylimidazol-2-ylidene). Catalyst design also needs to account for mechanistic points outside of the catalytic cycle itself. To enter the cycle, there is often an initial precatalyst activation process, and elucidating this can lead to optimization of both precatalyst and reaction conditions. To leave the cycle, we can have reversible formation of off-cycle species as well as an irreversible catalyst deactivation step. In our Cp*Ir(IMe)2Cl precatalyst for dehydrogenative oxidation, Cp* is lost in the activation step. This suggested moving to a catalyst precursor lacking the Cp*, [Ir(IMe)2(CO)2]+. Catalyst deactivation produces a series of unusual cluster cations such as [Ir6(IMe)8(CO)2H14]2+. Among applications, dehydrogenative oxidation can be useful in upgrading of biomass glycerol by conversion to lactate, as a part of hydrogen borrowing chemistry and in reversible hydrogenation/dehydrogenation for H2 storage.   相似文献   
7.
8.
新颖、独特的聚烯烃合成方法新进展(下)   总被引:1,自引:1,他引:0  
吕立新 《石油化工》2012,41(10):1105-1112
目前聚烯烃产品的全球产量已占热塑性塑料全球总产量的一半。但由于聚烯烃产品的结构中缺乏功能性基团,且用传统的配位聚合方法又难于引入极性基团,因此拓宽聚烯烃的应用领域就受到一定限制。回顾并阐述近年来出现的全新的烯烃聚合物的合成方法,包括:非环二烯易位聚合、碳烯聚合、催化链增长反应、点击反应和不用烷基铝的配位聚合的聚合方法及其反应原理。  相似文献   
9.
以3,5-二三氟甲基苯胺、乙二醛、甲醛、氯化铵和氯化苄或1-溴癸烷为原料,经缩合、亲核取代反应得到氯化1-苄基-3-(3,5-二三氟甲基)苯基咪唑盐和溴化1-癸基-3-(3,5-二三氟甲基)苯基咪唑盐,收率分别达59.0%和76.6%;通过氯化1-苄基-3-(3,5-二三氟甲基)苯基咪唑盐和溴化1-癸基-3-(3,5-二三氟甲基)苯基咪唑盐的阴离子交换反应得到4种目标产物:1-苄基-3-(3,5-二三氟甲基)苯基咪唑四氟硼酸盐、1-癸基-3-(3,5-二三氟甲基)苯基咪唑四氟硼酸盐、1-苄基-3-(3,5-二三氟甲基)苯基咪唑六氟磷酸盐和1-癸基-3-(3,5-二三氟甲基)苯基咪唑六氟磷酸盐,产物结构通过1HNMR、13CNMR得以确认。考察了溶剂对亲核取代反应的影响,得出最佳反应溶剂为甲苯。  相似文献   
10.
A metal Fischer carbene [(CO)5WC(φ)OCH2CH3] was covalently linked for the first time to the silanol groups of the mesoporous channels of SBA15 by following two different synthetic anchoring routes. The first one goes through the reaction of the SBA15 mesoporous silica walls functionalized by aminopropyltriethoxysilane (APTES) with a tungsten carbene Wφ, while in the second approach a precursor synthesized by reacting APTES with the carbene Wφ is then anchored via a direct bond to the silanol groups in the interior pore channels of SBA-15.

This tethering is helpful to prevent the decomposition of the metallic complex. XRD, N2 adsorption–desorption, and TEM analysis provide strong evidence that the mesoporous support structure retains its long-range ordering after the grafting process, despite a significant reduction of its specific surface area, pore-volume and pore-size. The chemical bonding of the tungsten carbene to the silanol groups of SBA-15 materials was studied with solid-state NMR spectroscopy. Both 13C MAS NMR and 29Si CP MAS NMR spectra confirm the covalent linking of the carbene to the silica-pore system.  相似文献   

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