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1.
利用旋转式金刚石对顶砧压机(RDAC)结合显微激光拉曼光谱和微区X射线衍射,研究了三水铝石(γ-Al(OH)3)在高压剪切作用下的结构稳定性。常温加压至1.5 GPa,旋转180°后,γ-Al(OH)3的结构开始转变。初始样品在高波数段的4个羟基伸缩振动峰(3363、3434、3524和3618 cm-1)相继消失,出现3303和3560 cm-12个新峰。低波数段拉曼谱强度明显减弱,无非晶态宽峰;Al-O-Al变形振动双峰(568、539 cm-1)和Al-O伸缩振动肩峰(321和307cm-1)分别融合为一个振动峰;4个羟基变形振动峰(1052、1018、981和922 cm-1)仍然可见。继续加压至3.5 GPa,旋转360°后卸至常压,高波数段新出现的两个羟基伸缩振动峰、原Al-O-Al变形振动峰和Al-O伸缩振动峰仍然可见。对比准静水压条件下γ-Al(OH)3高压相的拉曼谱和相转变压力(约2.7 GPa),认为常温高压剪切作用下γ-Al(OH)3脱羟基生成了H2O和H3O-2。卸压样品微区的X射线衍射谱进一步揭示,在高压剪切作用下,γ-Al(OH)3的(OH)-Al-(OH)配位八面体骨架被破坏,沿c轴方向原子叠加的层间距缩小,对称性增强。这种不同于准静水压实验的结构改变来自腔体内压力的不均匀分布(0.5~4.5 GPa)。高压剪切作用下,三水铝石的结构稳定性研究对查明板块冷俯冲带中含水矿物的稳定性,推演俯冲板片的物理化学性质以及板块俯冲的速率具有重要意义。 相似文献
2.
Dr. Shanyu Han Prof. Antonio G. S. de Oliveira-Filho Dr. Yinan Shu Prof. Donald G. Truhlar Prof. Hua Guo 《Chemphyschem》2022,23(8):e202200039
We present a new full-dimensional diabatic potential energy matrix (DPEM) for electronically nonadiabatic collisions of OH(A 2Σ+) with H2, and we calculate the probabilities of electronically adiabatic inelastic collisions, nonreactive quenching, and reactive quenching to form H2O+H. The DPEM was fitted using a many-body expansion with permutationally invariant polynomials in bond-order functions to represent the many-body part. The dynamics calculations were carried out with the fewest-switches with time uncertainty and stochastic decoherence (FSTU/SD) semiclassical trajectory method. We present results both for head-on collisions (impact parameter b equal to zero) and for a full range of impact parameters. The results are compared to experiment and to earlier FSTU/SD and quantum dynamics calculations with a previously published DPEM. The various theoretical results all agree that nonreactive quenching dominates reactive quenching, but there are quantitative differences between the two DPEMs and between the b=0 results and the all-b results, especially for the probability of reactive quenching. 相似文献
3.
The new transition metal oxo‐thiostannate {[Ni(cyclen)]6[Sn6S12O2(OH)6]} · 2(ClO4) · 19H2O ( 1 ) was prepared under hydrothermal conditions using Na4SnS4 · 14H2O and [Ni(cyclen)](ClO4)2 as reactants. In the crystal structure the rare [Sn6S12O2(OH)6]10– anion is observed, which is composed of SnS2O(OH)3 and SnS4O2 octahedra, and SnS4 tetrahedra sharing edges and corners. The anion is expanded by six Ni2+ centered complexes via Ni–S and Ni–OH bonds. The photocatalytic properties for the visible light driven hydrogen evolution reaction shows that 26.6 mmol · g–1 H2 were evolved after 3 h. 相似文献
4.
Iron Oxide Nanoparticles: Facile Synthesis of Gd(OH)3‐Doped Fe3O4 Nanoparticles for Dual‐Mode T1‐ and T2‐Weighted Magnetic Resonance Imaging Applications (Part. Part. Syst. Charact. 10/2015) 下载免费PDF全文
5.
Shuang-Shuang Yang Ming-Jiang Xie Yu Shen Yong-Zheng Wang Xue-Feng Guo Bin Shen 《中国化学快报》2016,27(4):507-510
Chemical doping of nickel hydroxide with other cations(e.g. Al~(3+)) is an efficient way to enhance its electrochemical capacitive performances. Herein, a simple cation–anion(Ni~(2+)and AlO_2) double hydrolysis method was developed toward the synthesis of nickel–aluminum(Ni–Al) composite hydroxides. The obtained composite hydroxides possesses a porous structure, large surface area(121 m~2/g) and homogeneous element distribution. The electrochemical test shows that the obtained composite hydroxides exhibits a superior supercapacitive performances(specific capacitance of 1670F/g and rate capability of 87% from 0.5 A/g to 20 A/g) to doping-free nickel hydroxide(specific capacitance of 1227 F/g and rate capability of 47% from 0.5 A/g to 20 A/g). Moreover, the galvanostatic charge/discharge test displays that after 2000 cycles at large current density of 10 A/g, the composite hydroxides achieves a high capacitance retention of 98%, indicative of an excellent electrochemical cycleability. 相似文献
6.
Theoretical investigations on the insertion reaction mechanisms of three- membered-ring silylenoid H2 Si Li F with GeH 3R(R = F, OH, NH2) have been systematically carried out by combined density functional theory(DFT) and ab initio quantum chemical calculations. The geometries of all stationary points for these reactions were optimized using the B3 LYP method and then the QCISD method was used to calculate the single-point energies. The calculated results indicate that, there are one precursor complex(Q), one transition state(TS), and one intermediate(IM) which connect the reactants and the products along the potential energy surface. The insertion reactions of three-membered-ring silylenoid with Ge H3 R proceed in a concerted manner, forming H2RSi-Ge H3 and Li F. The calculated potential energy barriers of the three reactions are 29.17, 30.90, and 54.07 k J/mol, and the reaction energies for the three reactions are –127.05, –116.91, and –103.31 k J/mol, respectively. The insertion reactions in solvents are similar to those in vacuum. Under the same situation, the insertion reactions should occur easily in the following order: GeH 3-F GeH 3-OH GeH 3-NH2. The elucidations of the mechanism of these insertion reactions provided a new mode of silicon-germanium bond formation. 相似文献
7.
Glucose detection plays very important roles in diagnostics and management of diabetes. The search for novel catalytic materials with appropriate architectures is the key step in the fabrication of highly sensitive glucose sensors. In this work, α-Ni(OH)2 roselike structures (Ni(OH)2-RS) assembled from nanosheet building blocks were successfully synthesized by a hydrothermal method through the hydrolysis of nickel chloride in the mixed solvents of water and ethanol with the assistance of polyethylene glycol (PEG). The structure and morphology of the roselike α-Ni(OH)2 were characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD) and N2 adsorption–desorption isotherm measurement. TEM and FE-SEM images showed that the synthesized Ni(OH)2 was roselike and the size of the leaf-shaped nanosheet was about 5 nm in thickness, which leads to larger active surface areas and faster electron transfer for the detection of glucose. Compared with the bare GCE and bulk Ni(OH)2/GCE, the Ni(OH)2-RS/GCE had higher catalytic activity toward the oxidation of glucose. Under the optimal conditions, the Ni(OH)2-RS/GCE offers a variety of merits, such as a wide linear response window for glucose concentrations ranging from 0.87 μM to 10.53 mM, short response time (3 s), a lower detection limit of 0.08 μM (S/N = 3), as well as long term stability and repeatability. 相似文献
8.
Hydroxylation of the silica in microfabricated thin layer chromatography plates as probed by time‐of‐flight secondary ion mass spectrometry and diffuse reflectance infrared Fourier transform spectroscopy 下载免费PDF全文
Supriya S. Kanyal Bhupinder Singh Cody V. Cushman Daniel T. Jankowski Matthew R. Linford 《Surface and interface analysis : SIA》2015,47(3):340-344
Microfabricated silica thin layer chromatography (TLC) plates have previously been prepared on patterned carbon nanotube forests. The high temperatures used in their fabrication reduce the number of hydroxyl groups on their surfaces. Fortunately, silica can be rehydroxylated. In diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), a silanol peak below 3740 cm?1 indicates a well‐hydroxylated silica surface that is fit for chromatography. Hydroxylations of our materials with HF are so effective that it is not possible to discern the position of this peak. In contrast, this signal is discernable when the plates are treated with NH4OH. To find a more convenient method for studying the surfaces of TLC plates, time‐of‐flight secondary ion mass spectroscopy (ToF‐SIMS) was considered. ToF‐SIMS is advantageous because multiple microfabricated TLC plates must be scraped to obtain enough silica for one DRIFT analysis, while static SIMS can be performed on very small regions (500 × 500 µm2 or less) of individual plates. Ratios of the SiOH+ and Si+ ToF‐SIMS signals for microfabricated TLC plates correlated well with ~3740 cm?1 silanol peaks from DRIFT. Thus, SIMS allows direct analysis of all of our treated and untreated plates, including those hydroxylated with HF. The best hydroxylation condition for HF, which was better than any studied for NH4OH, was around 150 ppm at room temperature. The best hydroxylation condition for NH4OH was 50 °C for 72 h. ToF‐SIMS versus DRIFT results of commercial TLC plates were also obtained and evaluated. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
9.
采用UωB97X-D/6-311+G**方法, 研究了气相、 甲苯和水中OH自由基(·OH)引发CH3SSCH3自由基阳离子(CH3SSC +, DMDS?+)裂解的反应机理, 并讨论了溶剂效应对反应的影响. 结果表明, ·OH和DMDS·+首先形成自由基耦合产物CH3S(OH)SCH3+(R1)和氢提取产物复合物[CH2=SSCH3+H2O]+(R2); 随后R1裂解直接发生 S—S键断裂协同质子转移, 而R2裂解依次发生构象变化、 C=S键亲碳加成和S—S键断裂协同质子转移. 去质子化的裂解产物为CH3SOH, CH2=S和HSCH2OH. 甲苯略微降低了裂解反应速控步骤的自由能垒. 水溶剂有利于R1裂解, 但不利于R2裂解, 尤其是单个水分子参与反应. 在气相、 甲苯和水中, 以·OH和DMDS·+为初始反应物, 虽然速控步骤的自由能垒为167.6~202.8 kJ/mol, 但裂解反应均是放热反应(?154.3~?31.4 kJ/mol). 相似文献
10.
本文使用波长为2.8 μm的分布式反馈激光器来测量水汽辉光放电产生的物种. 使用浓度调制光谱仅观察到OH自由基和瞬态H2O分子的吸收光谱. 吸收峰的强度和方向随解调相位而变化,但是H2O的一个吸收峰的方向始终与其它峰相反. OH和H2O的不同光谱取向反映了能级中粒子数量的增加或减少. 如果在放电过程中可以检测到更多的瞬态物种,则可以更好地研究H2O的激发、电离和分解动力学. 研究表明,浓度调制光谱的解调相位关系可以用来研究分子能级的布居数变化. 相似文献