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141.
Houfu Lv Dr. Tianfu Liu Dr. Xiaomin Zhang Dr. Yuefeng Song Hiroaki Matsumoto Prof. Dr. Na Ta Chaobin Zeng Prof. Dr. Guoxiong Wang Prof. Dr. Xinhe Bao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16102-16107
In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal–oxide interface for CO2 electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La0.4Sr0.6Co0.2Fe0.7Mo0.1O3−δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal–oxide interface improves CO2 adsorption and activation, showing a higher CO2 electrolysis performance than the LSCFM counterparts. 相似文献
142.
Xiangyu Ma Yuyuan Bai Yongbo Song Qinzhen Li Ying Lv Hui Zhang Prof. Haizhu Yu Prof. Manzhou Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17387-17391
Precise atomic structure of metal nanoclusters (NCs) is fundamental for elucidating the structure–property relationships and the inherent size-evolution principles. Reported here is the largest known FCC-based (FCC=face centered cubic) silver nanocluster, [Ag100(SC6H33,4F2)48(PPh3)8]−: the first all-octahedral symmetric nesting Ag nanocluster with a four-layered Ag6@Ag38@Ag48S24@Ag8S24P8 structure, consistent symmetry elements, and a unique rhombicuboctahedral morphology distinct from theoretical predictions and previously reported FCC-based Ag clusters. DFT studies revealed extensive interlayer interactions and degenerate frontier orbitals. The FCC-based Russian nesting doll model constitutes a new platform for the study of the size-evolution principles of Ag NCs. 相似文献
143.
Meng Lv Yang Yu María E. Sandoval-Salinas Prof. Jianhua Xu Dr. Zuhai Lei Prof. David Casanova Prof. Youjun Yang Prof. Jinquan Chen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22363-22368
Spiro conjugation has been proposed to dictate the efficiency of charge transfer, which could directly affect the spin–orbit charge transfer intersystem crossing (SOCT-ISC) process. However, this process has yet to be exemplified. Herein, we prepared three spirobis[anthracene]diones, in which two benzophenone moieties are locked in close proximity and differentially functionalized to fine-tune the charge transfer state. Its feasibility for SOCT-ISC was theoretically predicted, then experimentally evaluated. Through fine-tuning the spiro conjugation coupling and varying the solvent dielectric constants, ISC rate constants were engineered to vary in a dynamic range of three orders of magnitude, from 7.8×108 s−1 to 1.0×1011 s−1, which is the highest ISC rate reported for SOCT-ISC system to our knowledge. Our findings substantiate the key factors for effective SOCT-ISC and offer a new avenue for the rational design of heavy atom free triplet sensitizers. 相似文献
144.
Yang Lv Dr. Miaomiao Han Dr. Wanbing Gong Dongdong Wang Dr. Chun Chen Prof. Guozhong Wang Prof. Haimin Zhang Prof. Huijun Zhao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23727-23732
Selective hydrogenation of C=O against the conjugated C=C in cinnamaldehyde (CAL) is indispensable to produce cinnamyl alcohol (COL). Nonetheless, it is challenged by the low selectivity and the need to use organic solvents. Herein, for the first time, we report the use of Fe-Co alloy nanoparticles (NPs) on N-doped carbon support as a selective hydrogenation catalyst to efficiently convert CAL to COL. The resultant catalyst with the optimized Fe/Co ratio of 0.5 can achieve an exceptional COL selectivity of 91.7 % at a CAL conversion of 95.1 % in pure water medium under mild reaction conditions, ranking it the best performed catalyst reported to date. The experimental results confirm that the COL selectivity and CAL conversion efficiency are, respectively promoted by the presence of Fe and Co, while the synergism of the alloyed Fe-Co is the key to concurrently achieve high COL selectivity and CAL conversion efficiency. 相似文献
145.
Hypochlorous acid (HOCl), one of the reactive oxygen species (ROS), is a key microbicidal agent which is used for natural defense. However, it is also linked to varieties of human diseases owing to the overproduction of HOCl. Much effort has been made to exploit selective fluorescent sensors for the detection of HOCl, but most of them have some disadvantages such as short excitation wavelength, low selectivity, and slow response and so on. These restrict the biological application of the probes. In this work, BR-O was designed and synthesized on the base of phenoxazine for the detection of HOCl. BR-O exhibited a violent fluorescence enhancement in the presence of HOCl, showing excellent selectivity and high sensitivity. More importantly, the probe BR-O was capable of detecting exogenous and endogenous HOCl in living cells. 相似文献
146.
Dr. Jinqiao Dong Yutong Pan Dr. Heng Wang Dr. Kuiwei Yang Dr. Lingmei Liu Prof. Zhiwei Qiao Yi Di Yuan Shing Bo Peh Dr. Jian Zhang Dr. Leilei Shi Prof. Hong Liang Prof. Yu Han Prof. Xiaopeng Li Prof. Jianwen Jiang Prof. Bin Liu Prof. Dan Zhao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(25):10237-10245
The self-assembly of highly stable zirconium(IV)-based coordination cages with aggregation induced emission (AIE) molecular rotors for in vitro bio-imaging is reported. The two coordination cages, NUS-100 and NUS-101, are assembled from the highly stable trinuclear zirconium vertices and two flexible carboxyl-decorated tetraphenylethylene (TPE) spacers. Extensive experimental and theoretical results show that the emissive intensity of the coordination cages can be controlled by restricting the dynamics of AIE-active molecular rotors though multiple external stimuli. Because the two coordination cages have excellent chemical stability in aqueous solutions (pH stability: 2–10) and impressive AIE characteristics contributed by the molecular rotors, they can be employed as novel biological fluorescent probes for in vitro live-cell imaging. 相似文献
147.
受限条件下水的介电性质因测量极具挑战,其在诸多电化学过程与反应输运过程中如何扮演关键角色从未被定量地澄清.本工作利用平衡态分子动力学模拟和受限体系介电性质计算方法,系统性地探索了0.65 nm限域尺寸、5×108 Pa限域压强、不同温度条件下单分子受限冰和受限水的介电性质.详细比较了恒定偶极矩SPC/E水分子模型和可极化的SWM4-NDP水分子模型在描述受限冰、水结构与介电性质上的优劣势,包括统计分析SWM4-NDP模型模拟的单分子层受限水和受限冰的瞬时分子偶极矩概率密度分布,计算每个模拟体系的静态结构因子、静态偶极空间关联函数、静态介电常数、体系偶极时间关联函数和德拜弛豫时间.首次发现了极化水分子模型描述的低维度受限水和受限冰的奇异分子极性变化,并观察到两种模型描述静态结构性质的效果相当,SWM4-NDP模型对于静态介电常数描述的优势会因受限条件的增强而被大幅削减.但在受限水介电极化弛豫动力学性质描述上SWM4-NDP模型明显优于SPC/E模型.我们推断SWM4-NDP模型在探索受限水结构相变动力学以及受限体系离子输运和溶剂化动力学等过程的模拟研究中是比SPC/E模型更好的选择.本工作将在进一步开展基于受限水系统储能、传感、输运的设计工作中提供一定的理论指导意义. 相似文献
148.
苝二酰亚胺类小分子由于其固有的强分子聚集特性,导致活性层形貌难于调控,器件效率相对于近年来报道的受体-给体-受体型稠环小分子受体一直处于劣势.针对这一关键问题,我们设计并合成了三个以吡咯并吡咯二酮为中心核的双臂型和四臂型苝二酰亚胺类小分子受体.其中,c-PDI2和nc-PDI2两个双臂型分子分别将两个苝二酰亚胺臂置于吡咯并吡咯二酮核心骨架的碳取代位和氮取代位;四臂型PDI4是将四个苝二酰亚胺臂置于吡咯并吡咯二酮核心骨架的四个取代位.通过对三个受体小分子的光谱吸收、能级水平、薄膜形貌以及光伏性能的详细研究,发现三个受体小分子都拥有扭曲的分子结构并由此带来无定形薄膜形貌,表明其分子聚集趋势得到了有效的抑制.相对于双臂型受体分子,四臂型PDI4具有更强的光吸收能力和电子传输性能,从而获得了8.45%的最高光电转换效率,是c-PDI2器件效率的2倍和nc-PDI2器件效率的1.5倍. 相似文献
149.
Fluorescence switch plays a vital role in bioelectronics and bioimaging.Herein,we presented a new kind of facile electrostatic complex nanoparticles(ECNs)for fluorescence switching in cells and marking of individual cell.The ECNs were prepared by mixing positively charged poly(6-(2-(thiophen-3-yl)ethoxy)hexyl trimethylammonium bromide)(PT)and negatively charged diarylethene sodium salt(DAECOONa).DAE-COONa is a photoswitchable molecule which can be transformed between the ring-closed fo rm and ring-open form under the irradiation of UV or visible light.The closed-form of DAE-COONa can efficie ntly quench the fluorescence of PT through intermolecular energy transfer,while the open form of DAE-COONa does not influence the emission of PT.Thus,the fluorescence of ECNs can be modulated by light irradiation,and the ECNs with good fluorescence switching performance have been employed for fluorescence imaging and individual cell lighting up process successfully.We demonstrate that the electrostatic complex strategy provides a facile method to construct fluorescence switch fo r selective cell marking and imaging applications. 相似文献
150.
Structural Chemistry - A first-principle study of dehydrogenation mechanism from Sr(NH2BH3)2 was performed. Three different pathways were explored for Sr(NH2BH3)2 monomer, and the most favorable... 相似文献