SO5 SU2 SU2 U1 U1及SO5 U1 U1的矢量相干态表示

本文讨论了SO₅ SU₂ SU₂ U₁ U₁及SO₅ U₁ U₁的VCS表示.计算了SO₅ U₂ U₂的约化矩阵元,并利用K矩阵技术确定了SO₅权的多重度.     

Li2K(IO3)3与Li2NH4(IO3)3的晶体结构

本文用X射线粉末法测定了Li₂K(IO₃)₃与Li₂NH₄(IO₃)₃的晶体结构和原子参数。发现Li₃K(IO₃)₃,Li₂NH₄(IO₃)₃与Li₂Rb(IO₃)₃同晶型,属单斜晶系,空间群为P2₁/α,每个单胞含有四个化合式量。室温的点阵常数分别为α=11.198?,b=11.046?,c=8.254?,β=111.53°,及α=11.327?,b=11.078?,c=8.341?,β=111.87°。讨论了二元化合物的形成与离子半径的关系。 关键词：     

Mg2(BH4)2(NH2)2脱氢机理的理论研究

对Mg₂(BH₄)₂(NH₂)₂的脱氢机理展开系统的理论研究发现相对于分子内的脱氢过程,分子间的脱氢过程在热力学和动力学方面都是比较有利的. Mg₂(BH₄)₂(NH₂)₂脱氢过程的第一步是BH₄^-中的B-H^δ-和NH2-中     

合成反铁磁Ni81Fe19/Co90Fe10/Ru/Co90Fe10/Ni81Fe19的研究

采用直流磁控溅射方法制备了一系列的合成反铁磁及以其为自由层的自旋阀.研究发现,在Ni₈₁Fe₁₉与Ru层之间插入适当厚度的Co₉₀Fe₁₀层后,可有效地提高合成反铁磁两磁性层间的反铁磁耦合强度,得到具有饱和场H_s更高、饱和磁化强度M_s更低、热稳定性更好的合成反铁磁.另外,以这种合成反铁磁作自旋阀的自由层时,可有效提高自旋阀的稳定性. 关键词： 合成反铁磁 退火 自旋阀     

正磷酸盐晶体Ba3(PO4)2和Sr3(PO4)2高温拉曼光谱研究

测量了碱土金属正磷酸盐Ba₃(PO₄)₂和Sr₃(PO₄)₂常温及高温拉曼光谱, 对拉曼振动模式进行指认, 并分析了晶体拉曼振动光谱及晶体结构在高温下的变化. 在温度升高的过程中, 拉曼振动频率向低频移动且振动峰宽度展宽, 晶体中的P-O平均键长随温度升高而变长, 但O-P-O的键角并未发生变化. 晶体在900 ℃以下无结构相变发生. 关键词： 3(PO₄)₂和Sr₃(PO₄)₂')" href="#">Ba₃(PO₄)₂和Sr₃(PO₄)₂ 高温拉曼光谱 振动模式 高温结构     

CH4/H2和CH4/He体系等离子体发射光谱分析

 在CH₄/H₂和CH₄/He和CH₄/He两种系统中,利用光学发射谱技术对螺旋波放电产生低压甲烷等离子体内活性粒子的光学发射特征进行了原位诊断。在实验中,两种体系下同时都测得的主要荷电粒子为CH,Ha,Hb,Hg以及H2等。研究了各实验参数对这些活性粒子CH, Ha,Hb以及Hg的发射光谱强度的影响。结果表明：在CH₄/H₂体系下,随着射频功率的增大,Ha,Hb,Hg以及CH基团的相对强度都随着增加,而当放电气压变化时它们都呈现先增大而后减小的趋势。在CH₄/He体系下,随射频功率的增加,Ha,Hb,Hg以及CH相对强度变化的总体趋势也都是先增加而后减小,当工作气压增加时,Ha,Hb以及Hg的相对强度变化也是呈现先增大而后减小,但CH基团的相对强度却是逐渐减小的;这些结果为等离子体沉积各种薄膜过程的理解及制备工艺参数的调整提供了参考。     

Observation of simultaneous ν1(SF6) + ν3(NF3) and ν2(SF6) + ν3(NF3) transitions enhanced by the resonance dipole-dipole interaction with the ν1 + ν3 and ν2 + ν3 states of the SF6 molecule

IR spectra of the solution of SF₆ molecules in liquid NF₃ at 84 K have been recorded. In a solvent transmission window of 1500–1750 cm⁻¹, two wide absorption bands with pronounced peaks in the high-frequency part are observed. The profile of these bands is explained by the influence of the resonance dipole-dipole (RDD) interaction of the states of the simultaneous transition ν₁(SF₆) + ν₃(NF₃) and ν₂(SF₆) + ν₃(NF₃) with the states (ν₁ + ν₃) and (ν₂ + ν₃) of the SF₆ molecules, respectively. The use of three isotopic modifications ³²SF₆, ³³SF₆, and ³⁴SF₆ has allowed us to vary the resonance detuning and thus to change the strength of the RDD interaction. With the liquid near the melting point being represented as a close-packed cubic crystal, the profile was calculated and its spectral characteristics were determined. The frequencies of the main peaks coincide with the experimental values accurate to the error.     

SU3 U1 U1的矢量相干态表示

本文讨论了U₃的矢量相干态表示.利用K矩阵技术得到了SU₃ U₁ U₁的正交基矢,从而确定了权的多重度.     

High-resolution study of the ν1/ν5 and 2ν1/ν1+ν5 P-H stretching bands of PH2D

The P-H stretching bands ν₁/ν₅ and 2ν₁/ν₁+ν₅ were recorded using a Bruker 120 HR interferometer with a resolution of 0.0042 and 0.0088 cm⁻¹, respectively, and analyzed. From the fits 33 and 50, respectively, vibrational, rotational, centrifugal distortion, and resonance interaction parameters were obtained. These reproduce 668 and 497 rovibrational energies of the pairs of states ν₁/ν₅ and 2ν₁/ν₁+ν₅ with experimental accuracies, rms=0.00016 and , respectively. “Local mode” behavior of the PH₂ fragment is established and discussed in detail.     

(NH4)2SO4，NH4NO3和(NH4)2SO4/NH4NO3混合气溶胶吸湿质量增长因子的快速测量方法

气溶胶颗粒的吸湿性决定了其尺寸、浓度、化学组成以及相态,从而显著影响着全球气候、大气异相化学以及人类健康。运用在线、原位、连续扫描衰减全反射傅里叶变换红外光谱（ATR-FTIR）技术, 结合线性湿度（RH）控制系统,实现了RH连续变化条件下气溶胶FTIR-ATR光谱的快速测量。根据水弯曲振动谱带（~1 640 cm-1）峰面积随RH的变化,得到了(NH₄)₂SO₄,NH₄NO₃和(NH₄)₂SO₄/NH₄NO₃混合气溶胶的质量增长因子（MGFs）、潮解点（DRH）和风化点（ERH）。与气溶胶的E-AIM模型预测值相比较,实验结果表现出良好的一致性,证实该方法是一种测量大气气溶胶MGFs,ERH和DRH的快速测量方法。     

不同含能取代基和桥基对碳桥联四唑-2-氮氧化物的性能影响密度泛函理论研究

Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N-oxides with different energetic substituent groups (-NH₂, -N₃, -NO₂, NF₂, -NHNO₂) and energetic bridge groups (-CH₂-, -CH₂-CH₂-, -NH-, -N=N-, -NH-NH-) were designed. The overall performance and the effects of different energetic substituent groups and energetic bridge groups on the performance were investigated by density functional theory and electrostatic potential methods. The results showed that most of designed compounds have oxygen balance around zero, high heats of formation, high density, high energy, and acceptable sensitivity, indicating that tetrazole N-oxide is a useful parent energetic compound employed for obtaining high energy compounds, even only combined with some very common energetic substituent groups and bridge groups. Comprehensively considering the effects on energy and sensitivity, the -NO₂, -NF₂, -NH-and -NH-NH-are appropriate substituent groups for combining tetrozale N-oxide to design new energetic compounds, while -NH₂, -N₃, -CH₂-CH₂-, and -N=N-are inappropriate.     

Improvement of amine-modification with piperazine for the adsorption of CO2

Both selectivity and capacity of CO₂ adsorption were considerably increased when PZ (piperazine) was added in MDEA (methyldiethylamine) that used to modify the surface of silica gels. The adsorbent saturated with CO₂ was regenerated at ambient temperature through nitrogen purge. A set of PSA (pressure swing adsorption) operation with 200 cycles was carried out and applicability of the modified adsorbent was thus illustrated. The CO₂ content in the column-top stream decreased from 13% to below 0.05% at steady state.     

Density functional theory study into the adsorption of CO2, H and CHx (x = 0-3) as well as C2H4 on α-Mo2C(0 0 0 1)

The structures and energetics of the chemisorbed CO₂, CH_x species and H as well as C₂H₄ on the α-Mo₂C(0 0 0 1) surface have been computed at the GGA-RPBE level of density functional theory. It is found that CO₂ adsorbs dissociately into CO and O, in agreement with the experimental finding. The adsorbed O, CH_x and H species prefer the site of three surface molybdenum atoms over a second layer carbon atom (V_C site). On the basis of the calculated adsorption energies of CH_x and H, the sequential dehydrogenation of CH₄ and the C/C coupling reaction of CH_x have been discussed.     

Computational investigation of the performance of ZIF-8 with encapsulated ionic liquids towards CO2 capture*

The effect of Ionic Liquid (IL) encapsulation in Metal Organic Frameworks (MOFs) is extensively studied towards the enhancement of the MOFs as CO₂-selective materials. The influence of the IL anion-cation pair type is investigated through the combination of two different cations, namely 1-butyl-3-methylimidazolium [bmim⁺] and 1-octyl-3-methylimidazolium [omim⁺] and three distinct anions, namely bis-trifluoromethylsulfonyl-imide [Tf₂N^?], tricyanomethanide [TCM^?], and tertracyanoborate [B(CN)₄^?], that can be encapsulated in ZIF-8, resulting in a series of ZIF hybrids (IL@ZIF-8). The study investigates the impact of the anion and the cation on the separation of CO₂ from mixtures with CH₄ and N₂. Monte Carlo simulations of adsorption of the three gases in both the pristine ZIF-8 and in ILs@ZIF-8 reveal that CO₂ capacity increases dramatically for the case of ILs@ZIF-8. Moreover, analysis of the simulations and additional density functional theory calculations show that CO₂/CH₄ (related to natural gas purification) and CO₂/N₂ (related to post-combustion CO₂ capture) mixture selectivity is affected by the distribution, composition and type of the IL pair. Moreover, the sorbent selection parameter, S, and the regenerability factor, R, are used to evaluate the performance of all IL@ZIF-8 analogues along with other known CO₂-selective materials.     

Pd修饰Cu电极的电化学CO2还原

利用微分电化学质谱和电化学原位衰减全反射红外光谱技术探究了Cu和CuPd催化剂上CO₂和CO的电化学还原行为. 红外光谱观察到了生成甲醇、甲烷与乙烯的CH_x中间物种. 在CuPd电极CO₂还原过程中，红外光谱的CO吸附峰起始电位比Cu正移大约300 mV，说明CuPd能够有效促进CO₂还原；CO饱和溶液中，Cu和CuPd电极CO起始吸附电位基本相同；两电极上CO谱带出现的电位与CO₃^2-的谱带降低的电位基本相同，说明CO的吸附需要CO₃^2-的脱附. 利用电化学在线质谱发现在CuPd电极上CO还原产生CH₄和CH₃OH的起始电位比Cu电极正移约200 mV. 推测催化活性的提升可能是由于Pd的引入改变了Cu的d能带，且Pd吸附更多的H，从而促进CO₂还原，使CO能够与H结合并被深度还原.     

Carbon molecular sieves from PET for separations involving CH4, CO2, O2 and N2

Carbon molecular sieves (CMS) have been made for the first time from PET textile fibres by carbonisation and pore mouth narrowing using CVD of benzene. The diffusion of O₂, N₂, CO₂ and CH₄ in these materials, and also in the commercial CMS Takeda 3A, was studied. It was found that the best PET based CMS was obtained after 10 min CVD time and had adsorption capacities and rates of diffusion similar to those of the Takeda 3A.     

Adsorption of CO2 on PbO at ambient temperature

The adsorption of CO₂ on metal oxides at ambient temperature received less study largely due to the small adsorption amount. However, the adsorption is of interest in refreshing the atmosphere of isolated spaces. It was shown in the present work that P_bO was sensitive to low concentration CO₂ in the presence of water. An XPS examination indicated that P_bO changed to P_bCO₃ after the adsorption of CO₂; therefore, the adsorption is chemical in nature. In order to enlarge the CO₂ capacity, P_bO was dispersed on the surface of a silica gel with large surface area (710 m²/g). Both CO₂ capacity and adsorption rate indicated that the optimal dispersion manner of P_bO is the mono-molecular layer surface coverage. Breakthrough experiments showed that the prepared adsorbent could effectively capture low-concentration CO₂ at ambient temperature and pressure yielding a CO₂ capacity of 59.1 mg g⁻¹. The saturated adsorbent was regenerated on heating at 380 °C and the CO₂ capability was recovered.     

Holey Graphitic Carbon Derived from Covalent Organic Polymers Impregnated with Nonprecious Metals for CO2 Capture from Natural Gas

Natural gas (NG), as a renewable and clean energy gas, is considered to be one of the most attractive energy carriers owing to its high calorific value, low price, and less pollution. Efficiently capturing CO₂ from NG is a very important issue since CO₂ reduces energy density of natural gas and corrodes equipment in the presence of water. In this study, the authors use holey graphene‐like carbon derived from covalent organic polymers (COP) impregnated with nonprecious metals, i.e., COP graphene, as highly efficient separation materials. The dual‐site Langmuir–Freundlich adsorption model based ideal absorbed solution theory is applied to explore the adsorption selectivity. The experimental results along with first principles calculations show Mn‐impregnated COP graphene exhibits greater CO₂/CH₄ selectivity than Fe and Co impregnated materials. Particularly, the selectivity of C–COP–P–Mn reaches 11.4 at 298 K and 12 bars, which are much higher than those in many reported conventional porous materials and can be compared to the highest separation performance under similar condition. Importantly, all the three COP graphene show remarkably high regenerability (R > 77%), which are much better than many reported promising zeolites, active carbon, and metal organic frameworks. Accordingly, COP graphene are promising cyclic adsorbents with high selectivity for separation and purification of CO₂ from natural gas.     

Kinetic aspect of CO2 reforming of CH4 on Ni(1 1 1): A density functional theory calculation

Reaction pathways of CO₂ reforming of CH₄ on Ni(1 1 1) were investigated by using density functional theory calculation. The computed kinetic parameters agree with the available experimental data, and a new and simplified mechanism was proposed on the basis of computed energy barriers. The first step is CO₂ dissociation into surface CO and O (CO₂ → CO + O) and CH₄ sequentially dissociation into surface CH and H (CH₄ → CH₃ → CH₂ → CH). The second step is CH oxygenation into CHO (CH + O → CHO), which is more favored than its dissociation into C and hydrogen (CH → C + H). The third step is the dissociation of CHO into surface CO and H (CHO → CO + H). Finally, H₂ and CO desorb from Ni(1 1 1) and form free H₂ and CO. The rate-determining step is the CH₄ dissociative adsorption, and the key intermediate is surface adsorbed CHO. Parameters, which might modify the proposed mechanism, have been analyzed. In addition, the formation, deposition and elimination of surface carbon have been discussed accordingly.     

CO2 dissociation on Ni(2 1 1)

The direct and H-mediated dissociation of CO₂ on Ni(2 1 1) were investigated at the level of density functional theory. Although formate (HCOO) formation via CO₂ hydrogenation was widely reported for CO₂ adsorption on metal surfaces, it is found that on Ni(2 1 1) HCOO dissociation into CHO and O is much difficult, while direct dissociation of adsorbed CO₂ into CO and O is more favorable. It is also found that the degree of electron transfer from surface to adsorbed CO₂ correlates with the elongation of C-O bond lengths and the reduction of the CO₂ dissociation barrier.