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61.
Pingli Lv Rongxiu Zhu Tongxiang Lu Steven E. Wheeler Dongju Zhang Ruoxi Wang Chengbu Liu 《Tetrahedron: Asymmetry》2013,24(24):1598-1604
Computational studies to determine the origin of enantioselectivity in the (1R,2R)-1,2-diphenylethane-1,2-diamine (DEPN)–Brønsted acid catalyzed epoxidation of 2-cyclohexen-1-one have been performed using density functional theory. Transition states for conjugate addition and ring closure steps of the epoxidations catalyzed by three different catalyst systems were characterized. Our calculations show that the Csp2H?O H-bond interaction between the benzene ring of the catalyst and H2O is mainly responsible for the chiral discrimination observed. The Brønsted acid counterion plays a very important role in ensuring high enantioselectivity by improving the rigidity of the transition state structures to allow the efficient formation of the Csp2H?O H-bond. Moreover, we explain why these two diamine catalysts (1S,2S)-DACH and (1R,2R)-DPEN display consistent enantioselectivities in the catalytic epoxidation of 2-cyclohexen-1-one when combining with three different cocatalysts; achiral TFA, and chiral (R)- and (S)-TRIP. 相似文献
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64.
Dr. Yukun Zhu Chunxiao Lv Zhuocheng Yin Prof. Jun Ren Prof. Xianfeng Yang Prof. Chung-Li Dong Prof. Hongwei Liu Dr. Rongsheng Cai Yu-Cheng Huang Prof. Wolfgang Theis Prof. Shaohua Shen Prof. Dongjiang Yang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(2):878-883
Red phosphorus is a promising photocatalyst with wide visible-light absorption up to 700 nm, but the fast charge recombination limits its photocatalytic hydrogen evolution reaction (HER) activity. Now, [001]-oriented Hittorf's phosphorus (HP) nanorods were successfully grown on polymeric carbon nitride (PCN) by a chemical vapor deposition strategy. Compared with the bare PCN and HP, the optimized PCN@HP hybrid exhibited a significantly enhanced photocatalytic activity, with HER rates reaching 33.2 and 17.5 μmol h−1 from pure water under simulated solar light and visible light irradiation, respectively. It was theoretically and experimentally indicated that the strong electronic coupling between PCN and [001]-oriented HP nanorods gave rise to the enhanced visible light absorption and the greatly accelerated photoinduced electron–hole separation and transfer, which benefited the photocatalytic HER performance. 相似文献
65.
Regulating PdC3/PtC3···thiophene interaction by small molecule doping (AgOTf,CuBr, CuI,CuBr2, PdCl2)
Structural Chemistry - The influences of small molecule doping on PdC3/PtC3···thiophene interaction have been investigated by atoms in molecules (AIM) theory, electron location... 相似文献
66.
Huaizhi Gao Runnan Yu Zongwen Ma Yongshuai Gong Biao Zhao Qianglong Lv Zhan'ao Tan 《Journal of polymer science. Part A, Polymer chemistry》2022,60(6):865-916
Organometallic complexes (OMCs) consisting of organic and metal active moieties have shown immense potential for application in solar cells. The diverse structure, rich porosity, and unique charge centers of OMCs enable them to be functional in solar cells. In this review, we introduced four types of OMCs, such as crown organometallic complexes, β-diketone metal complexes, cyclometallic complexes, and main chain metal-containing polymers, providing an in-depth analysis of the structure-performance relationship. OMCs could serve as active or interlayer materials in a variety of solar cell systems such as organic solar cells, perovskite solar cells, and dye-sensitized solar cells, especially some metals to improve the photoelectric performance of the device as dopants. In the end, perspectives on the opportunities and challenges of OMCs are given. 相似文献
67.
Hydrogenation of acetophenone over nano‐Cu/SiO2 catalysts was investigated. The catalysts, prepared by a liquid precipitation method using various precipitating agents, were characterized using low‐temperature nitrogen adsorption, X‐ray diffraction, temperature‐programmed desorption of ammonia, hydrogen temperature‐programmed reduction, transmission electron microscopy and X‐ray photoelectron spectroscopy. It was found that the catalysts prepared by a homogeneous precipitation method had better activity and stability than those prepared by a co‐precipitation method. The catalyst prepared using urea as precipitating agent had well‐dispersed copper species, high surface area and abundant pore structure. The catalytic performance and mechanism of the Cu/SiO2 catalysts were further studied. It was found that the activity and stability of the catalysts could be improved by adjusting the proportion of Cu+/(Cu+ + Cu0). The sample prepared using urea as precipitating agent presented higher activity and selectivity. Also, the catalyst prepared using urea maintained a high catalytic performance while being continuously used for 150 h under the optimal reaction conditions. 相似文献
68.
Zemin Sun Mengwei Yuan Kefan Shi Yuhui Liu Di Wang Dr. Caiyun Nan Dr. Huifeng Li Prof. Genban Sun Prof. Xiaojing Yang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7244-7249
NiFe layered double hydroxides (LDHs) have been denoted as benchmark non-noble-metal electrocatalysts for the oxygen evolution reaction (OER). However, for laminates of NiFe LDHs, the edge sites are active, but the basal plane is inert, leading to underutilization as catalysts for the OER. Herein, for the first time, light and electron-deficient Li ions are intercalated into the basal plane of NiFe LDHs. The results of theoretical calculations and experiments both showed that electrons would be transferred from near Ni2+ to the surroundings of Li+, resulting in electron-deficient properties of the Ni sites, which would function as “electron-hungry” sites, to enhance surface adsorption of electron-rich oxygen-containing groups, which would enhance the effective activity for the OER. As demonstrated by the catalytic performance, the Li−NiFe LDH electrodes showed an ultralow overpotential of only 298 mV at 50 mA cm−2, which was lower than that of 347 mV for initial NiFe LDHs and lower than that of 373 mV for RuO2. Reasonable intercalation adjustment effectively activates laminated Ni2+ sites and constructs the electron-deficient structure to enhance its electrocatalytic activity, which sheds light on the functional treatment of catalytic materials. 相似文献
69.
Hao Zhang Dr. Xu Liu Ting-Ting Lu Peng Lv Prof. Wen-Yong Lai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3909-3917
A series of monodisperse six-armed conjugated starbursts ( Tr1F , Tr2F , and Tr3F ) containing a truxene core and multibranched oligofluorene bridges capped with diphenylamine (DPA) units has been designed, synthesized, and investigated as robust gain media for organic semiconductor lasers (OSLs). The influence of electron-rich DPA end groups on their optoelectronic characteristics has been discussed at length. DPA cappers effectively raise HOMO levels of the starbursts, thus enhancing the hole injection and transport ability. Solution-processed electroluminescence devices based on the resulting six-armed starbursts exhibited efficient deep-blue electroluminescence with clear reduced turn-on voltages (3.2–3.5 V). Moreover, the resulting six-armed molecules showed stabilized electroluminescence and amplified spontaneous emission with low thresholds (27.4–63.9 nJ pulse−1), high net gain coefficients (80.1–101.3 cm−1), and small optical loss (2.6–4.4 cm−1). Distributed feedback OSLs made from Tr3F exhibited a low lasing threshold of 0.31 kW cm−2 (at 465 nm). The results suggest that the construction of truxene-centered six-armed conjugated starbursts with the incorporation of DPA units can effectively enhance EL properties by precisely regulating the HOMO energy levels, and further optimizing their optical gain properties. 相似文献
70.
Chenyang Fan Chonglin Song Gang Lv Jiangjun Wei Xuyang Zhang Yuehan Qiao Ye Liu 《Proceedings of the Combustion Institute》2019,37(4):4821-4829
Post injection has significant benefit in the reduction of diesel soot emissions. Therefore, there is a need to understand the effect of post-injection strategy on soot physicochemical properties and reactivity because they play an important role in soot oxidation process that governs the final soot emissions. This work focuses on the impact of post injection on the physicochemical properties and reactivity of diesel in-cylinder soot using a main plus post injection (M*P) and a single injection (M) strategy. The soot was sampled by a developed total cylinder sampling system, and the dividing points of soot formation-dominant and oxidation-dominant phases were used for studying the impacts of post injection on the characteristics of in-cylinder soot. The physicochemical properties of the soot samples, including primary particle size, nanostructure, carbon chemical state and surface functional groups, were characterized. The soot reactivity was evaluated in terms of peak temperature, burnout temperature and apparent activation energy. In the oxidation-dominant phase, the M*P soot initially possesses smaller primary particle size, shorter fringe length, larger tortuosity, lower sp2/sp3 hybridization ratio of carbon atoms and higher content of aliphatic CH groups than the M soot. The beneficial influence of physicochemical properties on soot reactivity when using post injection is validated by the thermogravimetric data, which shows that the M*P soot is more reactive than the M soot at the onset of the oxidation-dominant phase. In the M*P case, the soot generated from the main-injection combustion has lower reactivity than the soot from the post-injection combustion after they experience the soot formation-dominant phase. The results indicate that the use of post injection leads to in-cylinder soot with physicochemical properties that favor reactivity. The enhancement of reactivity means that the soot will be more readily oxidized in the subsequent combustion process, and consequently contributes to a reduction in final soot emissions. 相似文献