Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition ⁻O₂C---C_n---CO₂⁻; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles.     

Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid-fluid molecular parameters for the system amorphous silica-Ar and amorphous silica-N₂, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.     

Nonequilibrium Statistical Thermodynamics of Two Dissipative Processes in Solids: Energy Losses of Channeled Particles at Low Velocities and Ultrasound Absorption by Conduction Electrons

We use methods of nonequilibrium statistical thermodynamics to investigate two dissipative processes in solids. We find the electron energy losses of a particle moving in a planar channeling regime and the sound absorption coefficient in metals under electron impurity scattering. The oscillator model is used to analyze the contribution from the effect of electron entrainment by a moving scattering center to the total dissipated energy. We investigate the frequency and temperature dependence of energy losses and also the dependence of the absorption coefficient on the sound wave vector.     

Quantum Phase Transition in Quasi-two-dimensional Heisenberg Antiferromagnet with Single-Ion Anisotropy

In the present paper, we investigate the quantum phase transition in a spatially anisotropic antiferrornagnetic Heisenberg model of S =1 with single-ion energy anisotropy. By using the Schwinger boson representation, we calculate the Gaussian correction to the critical value J⊥^c caused by quantum spin fluctuations. We find that, for the positive single-ion energy, a nonzero value of J⊥^c is always needed to stabilize the antiferromagnetic long-range order in this model. It resolves a difference among literature and shows clearly that the effect of quantum fluctuations may qualitatively change a result obtained by the mean-field theories on lower-dimensional systems.     

Spectral Analysis of Powers of the Operator (Vf)(x)=q(x)∫0 xw(t)f(t),dt

Mathematical Notes -     

On the Similarity between Volterra Operators and Transformation Operators for Integro-Differential Operators of Fractional Order

We establish the similarity between certain Volterra integral operators and the Riemann--Liouville fractional integration operator as well as the existence of a triangular transformation operator for integro-differential equations of fractional order. The results obtained are consistent with similar results for the case of integer order.     

Triple differential cross sections for ionization of hydrogen atoms by positrons in a Schwinger variational calculation

Schwinger variational principle has been used to calculate triple differential cross-sections for ionization of hydrogen atoms by positrons at intermediate and high energies for Ehrhardt type asymmetric geometry. The results agree in general with the calculations of Brauneret al [8] and with the second Born calculation.     

Interpolatory integration rules and orthogonal polynomials with varying weights

We investigate which types of asymptotic distributions can be generated by the knots of convergent sequences of interpolatory integration rules. It will turn out that the class of all possible distributions can be described exactly, and it will be shown that the zeros of polynomials that are orthogonal with respect to varying weight functions are good candidates for knots of integration rules with a prescribed asymptotic distribution.Research supported by the Deutsche Forschungsgemeinschaft (AZ: Sta 299/4-2).     

超大规模集成电路波导光互连技术的现状与前景

介绍超大规模集成电路(VLSI)波导(?)互连技术的最新进展,并预测其发展方向,以及如阿解决存在的实际问题。     

鸟嘌呤和次黄嘌呤的铜络合物的吸附作用和伏安特性研究

本文研究了鸟瞟呤(Gua)和次黄嘌呤(Hxa)铜络合物在悬汞电极(HMDE)上的吸附作用和电极反应机理,溶液中形成的1:1络合物有强烈吸附性,通过分子结构的比较,推断出Cu~(2+)与Gua和Hxa的咪唑环N(7)和外环氧O(6)原子结合形成封闭的五元环。嘌呤环的π-电子有使分子呈平面吸附的趋势,但是Gua络合物分子优先取“倾斜”定向;随着表面吸附浓度增加,Hxa络合物分子存在从“平面”向“垂直”的再定向作用。本文测定了单层吸附浓度、包含的电量和每个分子占据的面积。络合物吸附得到S形等温线,它与Frumkin吸附等温线接近。本文还列出有关吸附参数B、a、△G_A~O和θ~*的计算结果。