ADSORPTION BEHAVIOR OF AMINO ACIDS ON COPPER SURFACES

The major results of a series of our recent investigations on the adsorption of eight amino acids on Cu(001) and (111) surfaces are reviewed in the present paper. In all studied cases the molecules adsorb onto the surface in their anionic form. With the increase of the coverage three different 2D phases of the adsorbates, that is, the 2D lattice gas, intermediate, and solid phases, appear sequentially, although for few systems one or two of them do not appear. In both the 2D lattice gas and intermediate phases the molecules "stand" with their two oxygen "feet" on the surface and the intermolecular interactions are repulsive, although in the former they can diffuse frequently whereas in the latter they are discommensurate in one direction with the substrate. In the solid phase the molecules "lie" down on the surface to form commensurate superstructures. Adsorption of amino acids may often induce step faceting as well as bunching to form facets. Adsorption of L-lysine on Cu(001) may cause steps bunching to form facets with all the same chirality. Our preliminary results show that it is possible to manipulate individual molecules with the STM tip even at room temperature. These results may have applications in nano-materials, nano-technology, and very likely also in chiral separations or enantioselective heterogeneous catalysis.     

(TiO2)n(n=3—6)团簇吸附水分子的理论研究

给出了优化小分子在团簇表面吸附结构的遗传算法.结合经验势函数,搜寻了水分子在(TiO₂)_n(n=3—6)团簇上可能的吸附方式;利用B3LYP/6-31G^**方法对各种吸附结构进行了优化.结果表明水分子主要通过O原子以非解离方式吸附到团簇中配位数较低或位置比较凸出的Ti原子上.分子轨道分析表明,水分子与团簇之间的成键主要来自吸附位Ti原子3s3p轨道的贡献,水分子的轨道保持了气相水分子中的基本特征,但离域化程度增大 关键词： 2团簇')" href="#">TiO₂团簇 2O吸附')" href="#">H₂O吸附 遗传算法 DFT     

Adsorption-controlled transition of the electrical properties realized in Hematite（alpha-Fe2O3） nanorods ethanol sensing

Alpha-Fe2O3 nanorods are synthesized through a hydrothermal method with no surfactant introduced and ethanol sensors are fabricated from these nanorods.The device can respond to ethanol vapour in a concentration range from 1 to 1500 parts per million and shows both p-type and n-type responding characteristics during the investigation of the ethanol sensing.The sensor displays a p-type characteristic when the ethanol concentration is low and converted into an n-type characteristic as the concentration exceeds a certain value.Such a phenomenon is attributed to the chemisorbed oxygen,which leads to different modifications of the energy band at the surface,namely,depletion layer or inversion layer.     

An Investigation of the Effect of Semi-Acetal Formation on the Properties of Dialdehyde Starch and its Thermoplastic Blend with Glycerol

Dialdehyde sweet potato starch (DASS) with various aldehyde contents was prepared and the properties analyzed in terms of solubility, intrinsic viscosity, scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetric analysis (TGA). The results demonstrated that when the aldehyede content of DASS was increased from 20% to 95%, the solubility, molecular weight, crystallizability, and thermal stability decreased. Thermoplastic DASS (TPDASS) was prepared by adding glycerol as a plasticizer; the thermal, rheological, hydrophobic, and tensile properties of TPDASS were investigated. The results indicated that, for the same glycerol content, with the increase of aldehyde content, the moisture adsorption decreased, while the shear viscosity, glass transition temperature, and tensile properties of TPDASS increased significantly. The effects were attributed to the introduction of aldehyde groups reducing the hydrogen bonds and decreasing the hydrophility of the starch. Moreover, the aldehyde and hydroxyl groups of DASS favored a semi-acetal formation with higher aldehyde content and cross-linking of DASS occurred with the increase of aldehyde content. In summary, compared to starch, the thermoplastic properties and hydrophobicity of DASS was improved. In the presence of water (10 wt%), the tensile strength of TPDASS with 95% aldehyde content (TPDASS95) moderately decreased, from 16.7 MPa to 14.0 MPa, when the glycerol content increased from 10% to 30%. The TPDASS with improved properties will find their applications in preparing biodegradable plastics.     

Rationally Designing Molecularly Imprinted Polymer Toward a High Specific Adsorbent by Using Metal as Assembled Pivot

This article presents an original work aimed at rationally designing molecularly imprinted polymer (MIP) toward a high specific adsorbent. Assembling with cobalt as the pivot, the MIP was prepared by coordinating polymerizable monomers around an inducible template. The use of pivot obviously plays a positive role on increasing the specificity of MIP, so as to adsorb more for the template and less for its analogue. Related studies indicate that these may be a result of increasing specific interaction, which makes the MIP capable of recognizing the imprint species. Further information from thermodynamic analysis reveals that the increasing specific interaction, in logic, can be due to a higher fidelity of imprint, which specifically allures the template to bind.     

Adsorption of Polycyclic Aromatic Hydrocarbons on Graphene Oxides and Reduced Graphene Oxides

Graphene has attracted increasing attention in multidisciplinary studies because of its unique physical and chemical properties. Herein, the adsorption of polycyclic aromatic hydrocarbons (PAHs), such as naphthalene (NAP), anthracene (ANT), and pyrene (PYR), on reduced graphene oxides (rGOs) and graphene oxides (GOs) as a function of pH, humic acid (HA), and temperature were elucidated by means of a batch technique. For comparison, nonpolar and nonporous graphite were also employed in this study. The increasing of pH from 2 to 11 did not influence the adsorption of PAHs on rGOs, whereas the suppressed adsorption of NAP on rGOs was observed both in the presence of HA and under high‐temperature conditions. Adsorption isotherms of PAHs on rGOs were in accordance with the Polanyi–Dubinin–Ashtahhov (PDA) model, providing evidence that pore filling and flat surface adsorption were involved. The saturated adsorbed capacities (in mmol g^?1) of rGOs for PAHs calculated from the PDA model significantly decreased in the order of NAP>PYR>ANT, which was comparable to the results of theoretical calculations. The pore‐filling mechanism dominates the adsorption of NAP on rGOs, but the adsorption mechanisms of ANT and PYR on rGOs are flat surface adsorption.     

First-principles characterization of formate and carboxyl adsorption on stoichiometric CeO2(111) and CeO2(110) surfaces

Molecular adsorption of formate and carboxyl on stoichiometric CeO₂(111) and CeO₂(110) surfaces was studied using periodic density functional theory (DFT+U) calculations. Two distinguishable adsorption modes (strong and weak) of formate are identified. The bidentate configuration is more stable than the monodentate adsorption configuration. Both formate and carboxyl bind at the more open CeO₂(110) surface are stronger. The calculated vibrational frequencies of two adsorbed species are consistent with the experimental measurements. Finally, the effects of U parameters on the adsorption of formate and carboxyl over both CeO₂ surfaces were investigated. We found that the geometrical configurations of two adsorbed species are not affected by different U parameters (U = 0, 5, and 7). However, the calculated adsorption energy of carboxyl pronouncedly increases with the U value while the adsorption energy of formate only slightly changes (<0.2 eV). The Bader charge analysis shows the opposite charge transfer occurs for formate and carboxyl adsorption where the adsorbed formate is negatively charge while the adsorbed carboxyl is positively charged. Interestingly, with the increasing U parameter, the amount of charge is also increased.     

Adsorption of Nonionic Surfactant from Its Aqueous Solution onto Commercial Rubber

Adsorption of Ethoxylated Nonyl Phenol (ENP) surfactant from its aqueous solution onto a commercial tire cutting from different sites. Outer Peristalitic (O.P.), Outer Smouth (O.S.), and Internal Tire (I.T.) is studied after different immersion times, 24, 48, 72, and 144 hrs at 30° C. The adsorption isotherms are determined by a surface tension method. A two stepped L-type isotherm is characteristic below the CMC of ENP; above this concentration the isotherm deviates from the L-type and the slope of the isotherm increases sharply. A Langmuir fit has been found below the CMC of ENP. From the maximum amounts adsorbed at pseudo-plateau (T_max of the tested samples it was found that the efficiency of adsorption onto the rubber surface decreases in the order, O.P. > O.S. > I.T.     

Dried Biomass of Activated Sludge for Cu2+ Adsorption: Behaviors and Mechanisms

Activated sludge was tested for its ability to remove Cu²⁺ from aqueous solution. The effects of various experimental parameters (initial pH, initial Cu²⁺ concentration, adsorbent dosage, and temperature) on Cu²⁺ adsorption were evaluated. The Langmuir isotherm model well described the adsorption of Cu²⁺ onto activated sludge. The pseudo-second-order kinetic equation was appropriate for describing the kinetic performance of the sorption. Furthermore, Webber–Morris models indicated that the sorption of Cu²⁺ was generally found to involve with the intraparticle diffusion process. Parameters of adsorption thermodynamic suggested that the interaction of Cu²⁺ adsorbed by sludge was spontaneous and exothermic. Activated sludge was characterized by Fourier transform infrared spectroscopy analysis and results showed that active groups such as –OH, –COOH, –NH₂ were involved in Cu²⁺ adsorption. Zeta potential analysis demonstrated inner-sphere adsorption for Cu²⁺ adsorption on sludge.     

Development of Complex Mathematical Model of Light Naphtha Isomerization and Rectification Processes

The technique of developing a mathematical model of catalytic isomerization of light naphtha is stated Using experimental data from an industrial isomerization unit shows adequacy of the mathematical model to the real process. The paper presents a method for optimizing the operation of the plant together with catalytic isomerization unit and separation columns. Selection of optimal modes of separation columns allows achieving the desired flow separation between units, as well as extension of the life of the catalyst SI-2.