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71.
Haicun Yang Shuipi Cai Yu Jiang Zheng Cao Wenzhong Ma Fanghong Gong Guoliang Tao Chunlin Liu 《Journal of polymer science. Part A, Polymer chemistry》2022,60(10):1571-1587
The commonly used multi-center initiation methods always lead to the formation of quantities of homopolymer in the surface tailoring based on reverse atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. In this study, a monocenter redox pair constructed of silica bearing tert-butyl hydroperoxide groups and ascorbic acid (SiO2-TBHP/AsAc) was applied to substitute the commonly used initiation method of R-supported RAFT grafting polymerization. All the propagating radicals were restricted on the surface of solid particles during the whole procedure theoretically, resulting in a higher grafting efficiency of 95.1% combined with the “controllable” feature at 10 h. This redox pair was also used to initiate the reverse ATRP in miniemulsion successfully with a grafting efficiency of 86.3% at 10 h. The grafting efficiency obtained under this monocenter initiation method was significantly higher than that of the frequently reported surface modification by reverse ATRP and RAFT polymerization. In addition, the high-efficient surface tailoring was traced and confirmed by nuclear magnetic resonance, Fourier transform infrared, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, and other analysis tests. The advantage of this monocenter redox pair will open a new avenue for the potential “high-efficient” surface tailoring of various materials. 相似文献
72.
Nucleic acids dye Goldview is widely used in agarose gel electrophoresis (AGE). However, in this study, a sample of multiplasmid DNA (multi-pDNA) stained with Goldview analyzed by AGE showed its instability at low temperature. Three types of DNA samples were analyzed, including linear DNA (ladder), single-plasmid DNA (single-pDNA), and multi-pDNA, electrophoretic conditions were optimized by adjusting the dye, the buffer, and the temperature (1–50°C). The results showed that the light intensity of Gelred is 2.2-times higher than that of Goldview in staining multi-pDNA. Compared with the single-pDNA and the linear DNA, the multi-pDNA stained with Goldview was greatly affected by temperature. This short communication indicated that Gelred is a highly applicable dye for analyzing multiplasmid samples. The degree and the way of binding of Goldview to multi-pDNA are greatly affected by temperature. 相似文献
73.
Qiuyu He Lirong Cao Yiran Wei Prof. Gregory R. Dake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(42):e202201328
The utility of 2-diphenylphosphoryloxy-1,3-dienes for the construction of substituted six-membered nitrogen heterocycles is presented. These dienes undergo boron trifluoride-promoted aza-Diels–Alder reactions when reacted with imines or related species formed in situ using aldehydes and amine derivatives. The stability of the dienes allows this three-component reaction to be carried out with no special precautions to eliminate water or air. Thirty-one examples of this process are presented. The usefulness of the enol phosphate functional group is highlighted in further reactions after the cycloaddition step to generate functionalized piperidenes or pyridines. 相似文献
74.
天然气、油田伴生气、高炉煤气等化工生产过程中伴生COS气体,不仅会腐蚀管道和毒害催化剂,还会严重污染环境并危害人类健康。COS催化水解反应可在温和条件下高效的将COS脱除,是最具应用前景的COS脱除技术之一。碱金属元素因其具有独特的电子供体性质、表面碱性和静电吸附等特性,常被用作助催化剂以提高Al2O3的COS催化水解性能。近年来,以钾为助剂改性的Al2O3催化剂(K2CO3/Al2O3)在COS催化水解反应中得到广泛的应用,但由于负载在Al2O3上的K物种的组成复杂,目前研究者对K2CO3/Al2O3催化剂上COS水解机理的理解仍存在一定的困惑和争议。本论文通过湿法浸渍法合成出一系列钾盐和钠盐改性的Al2O3催化剂,并利用各类先进的表征技术对这些催化剂进行分析。活性测试表明,以K2CO3、K2C2O4、NaHCO3、Na2CO3和NaC2O4改性Al2O3催化剂均有助于COS的水解。其中K2CO3/Al2O3拥有最佳的COS水解性能,连续运行20 h后其COS转化率仍高于~93%,远远优于未改性的Al2O3 (~58%)。我们利用原位红外光谱和X射线光电子能谱探明了反应过程中催化剂的化学结构特征,阐明了H2O分子在K2CO3/Al2O3上的水解作用机制。原位红外表明COS在K2CO3/Al2O3上的水解过程中形成了硫代碳酸氢盐中间产物。X射线光电子能谱表征证明催化剂的失活主要是因为催化剂表面积累了硫酸盐和单质硫。此外,我们还研究了水蒸气含量对COS水解性能的影响,研究发现,由于H2O和COS分子在催化剂表面存在竞争吸附,过量的H2O会引起催化活性的下降。上述研究表明,K2CO3/Al2O3催化剂上COS水解性能的提高主要是形成了HO-Al-O-K界面活性位。更为重要的是,所制备的催化剂都是在模拟工业工况条件下进行的,这为后续的工业应用提供了宝贵理论指导。本工作为理解助剂钾在Al2O3催化剂上COS水解活性的增强提供了新的见解,这为未来设计稳定高效的COS水解催化剂打开了新的发展方向。 相似文献
75.
Man Zheng Bohan Cao Jiaxian Liu Kun Shi Yufan Zhang Huan Wang 《Electroanalysis》2023,35(7):e202200519
In this study, a simple method was designed to prepare ordered mesoporous carbons embedded with molybdenum without any extreme conditions. We prepared three different ordered molybdenum carbide materials with mesoporous structures to explore the influence of the structure of molybdenum-based materials on the HER catalytic efficiency. The ordered mesoporous molybdenum carbide catalysts (CMK-3-MoCx, fCMK-3-MoCx, CMK-8-MoCx) were characterized by SEM, TEM, XRD, nitrogen adsorption-desorption and XPS. The HER is catalyzed efficiently on the three electrocatalysts, fCMK-3-MoCx shows the best HER electro-catalytic performance with a small onset potential of −0.06 V vs. RHE, a low tafel slope of 66 mV dec−1 and a small over-potential value of 89 mV at 10 mA cm−2. This excellent performance on HER is due to its high specific surface area and highly ordered mesoporous structure that resulted in excellent proton transport efficiency and high electron transfer rate. Our results provide a new research direction for the application of flat ordered mesoporous structures in catalysis. 相似文献
76.
Dr. Songlin Xue Dr. W. Ryan Osterloh Xiaojuan Lv Ningchao Liu Yimei Gao Dr. Haitao Lei Dr. Yuanyuan Fang Dr. Zhongti Sun Dr. Peifeng Mei Dr. Daiki Kuzuhara Dr. Naoki Aratani Dr. Hiroko Yamada Dr. Rui Cao Dr. Karl M. Kadish Dr. Fengxian Qiu 《Angewandte Chemie (International ed. in English)》2023,62(17):e202218567
The molecular structure, electrochemistry, spectroelectrochemistry and electrocatalytic oxygen reduction reaction (ORR) features of two CoII porphyrin(2.1.2.1) complexes bearing Ph or F5Ph groups at the two meso-positions of the macrocycle are examined. Single crystal X-ray analysis reveal a highly bent, nonplanar macrocyclic conformation of the complex resulting in clamp-shaped molecular structures. Cyclic voltammetry paired with UV/Vis spectroelectrochemistry in PhCN/0.1 M TBAP suggest that the first electron addition corresponds to a macrocyclic-centered reduction while spectral changes observed during the first oxidation are consistent with a metal-centered CoII/CoIII process. The activity of the clamp-shaped complexes towards heterogeneous ORR in 0.1 M KOH show selectivity towards the 4e− ORR pathway giving H2O. DFT first-principle calculations on the porphyrin catalyst indicates a lower overpotential for 4e− ORR as compared to the 2e− pathway, consistent with experimental data. 相似文献
77.
Dr. Pengwei Li Linfang Yan Qingli Cao Prof. Chao Liang He Zhu Sihui Peng Yongpeng Yang Yuncai Liang Rudai Zhao Prof. Shuangquan Zang Prof. Yiqiang Zhang Prof. Yanlin Song 《Angewandte Chemie (International ed. in English)》2023,62(13):e202217910
Low-dimensional Ruddlesden-Popper (LDRP) perovskites still suffer from inferior carrier transport properties. Here, we demonstrate that efficient exciton dissociation and charge transfer can be achieved in LDRP perovskite by introducing γ-aminobutyric acid (GABA) as a spacer. The hydrogen bonding links adjacent spacing sheets in (GABA)2MA3Pb4I13 (MA=CH3NH3+), leading to the charges localized in the van der Waals gap, thereby constructing “charged-bridge” for charge transfer through the spacing region. Additionally, the polarized GABA weakens dielectric confinement, decreasing the (GABA)2MA3Pb4I13 exciton binding energy as low as ≈73 meV. Benefiting from these merits, the resultant GABA-based solar cell yields a champion power conversion efficiency (PCE) of 18.73 % with enhanced carrier transport properties. Furthermore, the unencapsulated device maintains 92.8 % of its initial PCE under continuous illumination after 1000 h and only lost 3 % of its initial PCE under 65 °C for 500 h. 相似文献
78.
Dr. Yuxuan Hu Dr. Jingsheng Miao Dr. Cheng Zhong Yang Zeng Prof. Shaolong Gong Dr. Xiaosong Cao Xue Zhou Dr. Yu Gu Prof. Chuluo Yang 《Angewandte Chemie (International ed. in English)》2023,62(19):e202302478
Heavy-atom integration into thermally activated delayed fluorescence (TADF) molecule could significantly promote the reverse intersystem crossing (RISC) process. However, simultaneously achieving high efficiency, small roll-off, narrowband emission and good operational lifetime remains a big challenge for the corresponding organic light-emitting diodes (OLEDs). Herein, we report a pure green multi-resonance TADF molecule BN-STO by introducing a peripheral heavy atom selenium onto the parent BN-Cz molecule. The organic light-emitting diode device based on BN-STO exhibited state-of-the-art performance with a maximum external quantum efficiency (EQE) of 40.1 %, power efficiency (PE) of 176.9 lm W−1, well-suppressed efficiency roll-off and pure green gamut. This work reveals a feasible strategy to reach a balance between fast RISC process and narrow full width at half maximum (FWHM) of MR-TADF by heavy atom effect. 相似文献
79.
Zhiguo Sun Huijuan Zhang Linlin Cao Xiaokang Liu Dan Wu Xinyi Shen Xue Zhang Zihang Chen Sen Ru Xiangyu Zhu Zhiyuan Xia Qiquan Luo Faqiang Xu Prof. Tao Yao 《Angewandte Chemie (International ed. in English)》2023,62(13):e202217719
The construction and understanding of synergy in well-defined dual-atom active sites is an available avenue to promote multistep tandem catalytic reactions. Herein, we construct a dual-hetero-atom catalyst that comprises adjacent Cu-N4 and Se-C3 active sites for efficient oxygen reduction reaction (ORR) activity. Operando X-ray absorption spectroscopy coupled with theoretical calculations provide in-depth insights into this dual-atom synergy mechanism for ORR under realistic device operation conditions. The heteroatom Se modulator can efficiently polarize the charge distribution around symmetrical Cu-N4 moieties, and serve as synergistic site to facilitate the second oxygen reduction step simultaneously, in which the key OOH*-(Cu1-N4) transforms to O*-(Se1-C2) intermediate on the dual-atom sites. Therefore, this designed catalyst achieves satisfied alkaline ORR activity with a half-wave potential of 0.905 V vs. RHE and a maximum power density of 206.5 mW cm−2 in Zn-air battery. 相似文献
80.
Shubo Geng Hang Xu Chun-Shuai Cao Prof. Tony Pham Prof. Bin Zhao Prof. Zhenjie Zhang 《Angewandte Chemie (International ed. in English)》2023,62(32):e202305390
Adsorption-based removal of carbon dioxide (CO2) from gas mixtures has demonstrated great potential for solving energy security and environmental sustainability challenges. However, due to similar physicochemical properties between CO2 and other gases as well as the co-adsorption behavior, the selectivity of CO2 is severely limited in currently reported CO2-selective sorbents. To address the challenge, we create a bioinspired design strategy and report a robust, microporous metal–organic framework (MOF) with unprecedented [Mn86] nanocages. Attributed to the existence of unique enzyme-like confined pockets, strong coordination interactions and dipole-dipole interactions are generated for CO2 molecules, resulting in only CO2 molecules fitting in the pocket while other gas molecules are prohibited. Thus, this MOF can selectively remove CO2 from various gas mixtures and show record-high selectivities of CO2/CH4 and CO2/N2 mixtures. Highly efficient CO2/C2H2, CO2/CH4, and CO2/N2 separations are achieved, as verified by experimental breakthrough tests. This work paves a new avenue for the fabrication of adsorbents with high CO2 selectivity and provides important guidance for designing highly effective adsorbents for gas separation. 相似文献