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161.
162.
The transition states of intramolecular 1,4 and 1,5 H-atom transfers, from/to primary (p), secondary (s) or tertiary alkyl (t) and primary (p
a), secondary (s
a) or tertiary (t
a) allyl carbon atoms, have been studied at the level of the semiempirical quantum-chemical method AM1 with the UHF approximation. The activation and reaction enthalpies were calculated and compared with experimental data available in the literature and the calculated data obtained for analogous reactions in alkyl radicals. Correlations were found between the activation enthalpies and the dissociation enthalpies of the bonds broken and formed. 相似文献
163.
《中国化学快报》2021,32(10):3221-3225
Electrochemical heterogeneous catalytic ozonation (E-catazone) is a promising and advanced oxidation technology that uses a titanium dioxide nanoflower (TiO2-NF)-coated porous Ti gas diffuser as an anode material. Our previous study has highlighted that the importance of the TiO2-NF coating layer in enhancing OH production and rapidly degrading O3-resistant drugs. It is well known that the properties of TiO2-NF are closely related to its sintering temperature. However, to date, related research has not been conducted in E-catazone systems. Thus, this study evaluated the effect of the sintering temperature on the degradation of the O3-resistant drug para-chlorobenzoic acid (p-CBA) using both experimental and kinetic modeling and revealed its influence mechanism. The results indicated that the TiO2-NF sintering temperature could influence p-CBA degradation and OH production. TiO2-NF prepared at 450 °C showcased the highest p-CBA removal efficiency (98.5% in 5 min) at a rate of 0.82 min−1, and an OH exposure of 8.41 × 10−10 mol L−1 s. Kinetic modeling results and interface characterization data revealed that the sintering temperature could alter the TiO2 crystallized phase and the content of surface-adsorbed oxygen, thus affecting the two key limiting reactions in the E-catazone process. That is, ≡TiO2 surface reacted with H2O to form TiO2-(OH)2, which then heterogeneously catalyzed O3 to form OH. Consequently, E-catazone with a TiO2-NF anode prepared at 450 °C generated the highest surface reaction rate (5.00 × 10−1 s−1 and 4.00 × 10-3 L mol-1 s−1, respectively), owing to its higher anatase content and adsorbed oxygen. Thus, a rapid O3-TiO2 reaction was achieved, resulting in an enhanced OH formation and a highly effective p-CBA degradation. Overall, this study provides novel baseline data to improve the application of E-catazone technology. 相似文献
164.
Prof. Dr. Muhammet Erkan Köse 《Chemphyschem》2021,22(20):2078-2092
Excited state geometries of molecules can be calculated with highly reliable wavefunction schemes. Most of such schemes, however, are applicable to small molecules and can hardly be viewed as error-free for excited state geometries. In this study, a theoretical approach is presented in which the excited state geometries of molecules can be predicted by using vibrationally resolved experimental absorption spectrum in combination with the theoretical modelling of vibrational pattern based on Franck-Condon approximation. Huang-Rhys factors have been empirically determined and used as input for revealing the structural changes occurring between the ground and the excited state geometries upon photoexcitation. Naphthalene molecule has been chosen as a test case to show the robustness of the proposed theoretical approach. Predicted 1B2u excited state geometry of the naphthalene has similar but slightly different bond length alternation pattern when compared with the geometries calculated with CIS, B3LYP, and CC2 methods. Excited state geometries of perylene and pyrene molecules are also determined with the presented theoretical approach. This powerful method can be applied to other molecules and specifically to relatively large molecules rather easily as long as vibrationally resolved experimental spectra are available to use. 相似文献
165.
SiO2/α-FeOOH和SiO2/γ-Fe2O3微粒的界面研究 总被引:1,自引:0,他引:1
α-FeOOH微粒由于其表面高活性,在转变成γ-Fe2O3的热处理过程中容易烧结,一旦这种烧结现象发生,得到的γ-Fe2O3磁粉磁性能大大下降[1].为了克服这一困难,目前采用在α-FeOOH微粒表面包敷有机物[2]和无机物[3]来隔离颗粒,阻止其聚集.其中SiO2表面包敷处理是最令人感兴趣的研究课题之一[4,5].SiO2是一种难烙性的非磁性材料,它包敷在α-FeOOH微粒表面外,不仅可提高α-FeOOH转变成γ-Fe2O3的热处理温度,有利于得到外形完好、晶格完整的γ-Fe2O3磁粉,而且由包效层与内核之间的界面相互作用引起的表面各向异性常… 相似文献
166.
借助定量金相、扫描电子显微镜、透射电子显微镜等微观分析手段对钨质量分数为93%的钨合金在15~50GPa冲击压力下微观结构响应性态进行了考察,发现了一些钨合金所特有的现象,即钨颗粒与粘结相交界处出现成分迁移,新相析出;并结合断口分析,探讨了钨合金在冲击作用下发生断裂的微观特征与韧脆转化间的关系及其物理本质。 相似文献
167.
J. Mayer T. Szreder M. Szadkowska-Nicze A. Faucitano 《Journal of polymer science. Part A, Polymer chemistry》1998,36(8):1217-1226
A pulse radiolysis study of isotactic polypropylene (PP) film has been carried out with the main aims of investigating charge trapping in an undoped system and solute radical ion generation in an pyrene (Py) doped matrix. In PP, pulse radiolysis gives electron–positive hole pairs. The electron can be stabilized in the undoped system as a trapped electron, e. The transient absorption spectrum of e in the near-IR (up to 1800 nm) was observed in the temperature range 30–100 K. This IR absorption was not detected in the case of oxidized PP. In such a matrix electrons can be scavenged by oxidation products generating respective radical-anions (absorption in the UV RANGE, λ < 350 nm). In a doped matrix transient absorption bands centered at 450 and 500 nm were observed which can be assigned to the Py radical cation and anion, respectively. The recombination of these ionic species leads to monomer excited-state formation observed during and after the 17 ns pulse. Contrary to the Py-doped polyethylene no excimer emission was detected at room temperature even if Py content in PP was close to 0.02 mol dm−3. The rate of Py radical-ion decay was found to be temperature dependent. Two linear parts of the Arrhenius plot were observed which intersected at ca. 240 K, the glass transition temperature, Tg, for PP. The activation energies calculated for two parts of Arrhenius plot were equal to 111 and ca. 0.78 kJ mol−1 for T > Tg and T < Tg, respectively. Some preliminary results concerning the ionic processes in PP containing two solutes (Py, 3,3′-dimethyldiphenyl) were presented. The mechanism of ionic recombination in PP will be proposed and discussed. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1217–1226, 1998 相似文献
168.
The concept of nanoarchitectonics has been proposed as an extensional development of nanotechnology through fusions with material science and the other fields. In nanoarchitectonics, nano-units of atoms, molecules, and nanomaterials are architected into construction of functional material systems. In order to assemble intended structures or hierarchical structures from nano-units, it is more useful to confine nano-units at the interface. In addition, nanoarchitectonics is expected to output functions by harmonizing many units in dynamic environments. However, the liquid interfaces still have lots of unexplored matters in nanoscale because supports by advanced apparatus and techniques in nanotechnology are not always available. Specifically, this review paper summarizes examples of research on molecular manipulation, molecular arrangement and assembly, materials synthesis, and life manipulation at the liquid interface. These examples demonstrate that the liquid interface enables the control of dynamic functions of various size regions, from molecular-level phenomena such as the control of molecular machines to techniques of living creature size such as the control of stem cell differentiation. Liquid interfaces are very useful environments for controlling dynamic functions for a wide range of targets and would have tremendous potential in terms of functional exploration. The great potential of nanoarchitectonics at the liquid interface and the challenges to be solved in the future are also discussed. 相似文献
169.
Hong-Jun Liu Cheng-Ye Yang Mei-Chen Han Chun-Yu Yu Prof. Xiaofeng Li Prof. Zhong-Zhen Yu Prof. Jin Qu 《Angewandte Chemie (International ed. in English)》2023,62(11):e202217458
Constructing efficient artificial solid electrolyte interface (SEI) film is extremely vital for the practical application of lithium metal batteries. Herein, a dense artificial SEI film, in which lithiophilic Zn/LixZny are uniformly but nonconsecutively dispersed in the consecutive Li+-conductors of LixSiOy, Li2O and LiOH, is constructed via the in situ reaction of layered zinc silicate nanosheets and Li. The consecutive Li+-conductors can promote the desolvation process of solvated-Li+ and regulate the transfer of lithium ions. The nonconsecutive lithiophilic metals are polarized by the internal electric field to boost the transfer of lithium ions, and lower the nucleation barrier. Therefore, a low polarization of ≈50 mV for 750 h at 2.0 mA cm−2 in symmetric cells, and a high capacity retention of 99.2 % in full cells with a high lithium iron phosphate areal loading of ≈13 mg cm−2 are achieved. This work offers new sights to develop advanced alkali metal anodes for efficient energy storage. 相似文献
170.
电催化二氧化碳还原反应(E-CO2RR)可在温和条件下将CO2转化成高附加值燃料或化学品,近年来受到广泛关注,其在实际反应中涉及到气体扩散和多电子转移等复杂过程,构筑高效、稳定的催化电极是其发展的核心之一。然而,传统涂敷电极制备时,需要将催化剂与粘结剂混合涂覆于集流体表面,此过程会造成活性位点包埋和传质过程受限,致使催化剂活性位利用率下降,同时在反应过程中电极表面容易粉化,造成稳定性下降,难以重复利用。因此,如何调控电极反应界面,提升催化剂活性位的利用率仍面临挑战。将催化剂原位生长于集流体上得到的一体化电极可直接应用于电催化反应,不仅有利于提升活性位利用率以及电荷传输能力,还能有效调控三相界面处的微观反应环境(如pH、反应物及反应中间体的浓度等),从而实现电催化性能强化。本文综述了一体化电极用于E-CO2RR的最新进展,分析了结构和表界面调控对E-CO2RR性能的影响规律,并对该领域仍然存在的挑战和未来一体化E-CO2RR电极的发展进行了评述与展望。 相似文献