Spectroscopic study on variations in illite surface properties after acid-base titration

FT IR, Raman microscopy, XRD, 29 Si and 27 Al MAS NMR, were used to investigate changes in surface properties of a natural illite sample after acid base potentiometric titration. The characteristic XRD lines indicated the presence of surface Al Si complexes, preferable to Al(OH) 3 precipitates. In the microscopic Raman spectra, the vibration peaks of Si O and Al O bonds diminished as a result of treatment with acid, then increased after hydroxide back titration. The varied ratio of signal intensity between IV Al and VI Al species in 27 Al MAS NMR spectra, together with the stable BET surface area after acidimetric titration, suggested that edge faces and basal planes in the layer structure of illite participated in dissolution of structural components. The combined spectroscopic evidence demonstrated that the reactions between illite surfaces and acid leaching silicic acid and aluminum ions should be considered in the model description of surface acid base properties of the aqueous illite.

Deposition of DLC Coating on Biomedical TiNi Alloys by Plasma Based Ion Implantation to Improve Surface Properties

Diamond-like carbon （DLC） films were successfully deposited on Ti- 50.8 at% Ni using plasma based ion implantation （PBII） technique. The influence of the pulsed negative bias voltage applied to the substrate from 12 kV to 40 kV on the microstracture, nano-indentation hardness and Young＇ s modulus, the surface characteristics and corrosion resistant property as well as hemocompatibility were investigated. The experimental resalts showed that C 1 s peak depended heavily on the bias voltage. With the increase of bias voltage, the ratio of sp2 / sp3 first decreased, reaching a minimum value at 20 kV, and then increased. The DLC coating deposited at 20 kV showed the highest hardness and elastic modulus values as a result of lower sp2/sp3 ratio. The RMS values first decreased from 7.202nm（12 kV） to 5.279 nm（20 kV）, and then increased to 11.449 nm（30 kV） and 7.060 nm（ 40 kV）. The uncoated TiNi alloy showed severe pitting corrosion, due to the presence of Cl-ions in the solution. On the contrary, the DLC coated sample showed very little pitting corrosion and behaved better corrosion resistant property especially for the specimens deposited at 20 kV bias voltages. The platelet adhesion test show that the hemocompatibility of DLC coated TiNi alloy is much better than that of bare TiNi alloy, and the hemocompatibility performance of DLC coated TiNi alloy deposited at 20 kV is superior to that of other coated specimens.

Surface Acidity of Amorphous Aluminum Hydroxide

The surface acidity of synthetic amorphous AI hydroxide was determined by acid/base titration with several complementary methods including solution analyses of the reacted solutions and XRD characterization of the reacted solids. The synthetic specimen was characterized to be the amorphous material showing four broad peaks in XRD pattern. XRD analyses of reacted solids after the titration experiments showed that amorphous AI hydroxide rapidly transformed to crystalline bayerite at the alkaline condition （pH〉10）. The solution analyses after and during the titration Ksp=^aAl^3＋/aH^＋^3 ,was 10^10.3. The amount of consumption of added acid or base during the titration experiment was attributed to both the protonation/deprotonation of dissolved AI species and surface hydroxyl group. The surface acidity constants, surface hydroxyl density and specific surface area were estimated by FITEQL 4.0.

Sorption of a triazol derivative by soils: importance of surface acidity

The sorption of a triazol derivative, 1-(4-chlorophenyl)- 4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)penten-3-ol with a common name of S3307D, on fifteen soils and three H_2O_2-treated soils was investigated. The sorption isotherm for each untreated and treated soil was non-linear, and was best fitted to Freundlich sorption equation. Soils containing high amount of clay content or organic matter or both sorbed much higher amounts of the chemical than soils that had low contents of these soil constituents. H_2O_2-treated soils showed considerable sorptive affinity for S3307D. It was concluded that both organic matter and mineral fraction in natural soils contributed to the sorption of the basic compound. Sorption by the H_2O_2 treated soils increased as suspension pH decreased, but all suspension pHs exceeded the pKa of the compound by more than two units. This implies that organic base protonation can occur on surfaces of soil components, and surface acidity (exchangeable acidity ) is important in sorption process of the organic base rather than suspension pH.

Densities and surface tensions of ionic liquids/sulfuric acid binary mixtures

The densities and surface tensions of [Bmim][TFO]/H2SO4, [Hmim][TFO]/H2SO4 and [Omim][TFO]/H2SO4 binary mixtures were measured by pycnometer and Wilhelmy plate method respectively. The results show that densities and surface tensions of the mixtures decreased monotonously with increasing temperatures and increasing ionic liquid （IL） molar fraction. IL with longer alkyl side-chain length brings a lower density and a smaller surface tension to the ILs/H2SO4 binary mixtures. The densities and surface tensions of the mixtures are fitted well by Jouyban-Acree （JAM） model and LWW model respectively. Redlich-Kister （R-K）equation and modified Redlich-Kister （R-K） equation describe the excess molar volumes and excess surface tensions of the mixtures well respectively. Adding a small amount of ILs （XIL 〈 0.1 ） into sulfuric acid brings an obvious decrease to the density and the surface tension. The results imply that the densities and surface tensions of IL5/H2SO4 binary mixtures can be modulated by changing the IL dosage or tailoring the IL structure.

Study on the Surface Photovoltage and Fluorescence Properties of N, N-Bis(4-aminopheny)-1, 4 quinonenediimine Doped with H_4SiW_(12)O_(40)

Aniline oligomer composite materials using heteropolyacid H4SiW12O40 as dopant was synthesized, and the effect of the doping concentration on the photoluminescence and surface photovoltaic properties were investigated.

Two Dehydroabietic Acid-based Arylamines: Synthesis, Crystal Structure and Fluorescent Properties

Two dehydroabietic acid-based arylamines have been synthesized and characterized by FTIR, 1H NMR, 13C NMR, MS spectra and elemental analysis. Their spatial structures were determined by X-ray diffraction analysis. UV-Vis absorption and fluorescence spectral characteristics of these compounds in methanol were investigated. Their fluorescence emission spectra in different polarity solvents were further evaluated. Fluorescent properties and structural relationship of the compounds showed that fluorescence intensity and quantum yield inversely increase with the non-coplanar degree. In addition, the solvent polarity has different effects on the fluorescence emission spectra of two compounds.

A Novel Dinuclear Copper(Ⅱ)Complex:Synthesis,Crystal Structure,Properties and Hirshfeld Surface Analysis

A novel copper complex [Cu2（L）（DMF）2]（1, H4L =（1 Z,N？Z）-3,5-dibromo-N？-（（3,5-dibromo-2-hydroxyphenyl）（hydroxy）methylene）-2-hydroxybenzohydrazonic acid which was synthesized by in-situ oxidation reaction derived from H2hdb（H2hdb = 6,6′-（（1 E,1？E）-hydrazine-1,2-diylidenebis（methanylylidene）） bis（2,4-dibromophenol）） has been synthesized and characterized by IR, elemental analysis（CHN）, TG and single-crystal X-ray diffraction. The single crystal belongs to monoclinic system, space group P21/c with a = 13.538（1）, b = 3.912（1）, c = 23.778（1）A°, β = 105.232（5）o, Mr = 857.08, V = 1214.9（1） A°^3, Z = 2, Dc = 2.343 g/cm^3, F（000） = 824, μ = 8.375 mm^–1, R = 0.0566, and w R = 0.1610. Compound 1 displays weak anti-ferromagnetic interactions through a η^1：η^1：η^1：η^1：η^1：η^1：μ2-L^4- bridging mode. Hirshfeld surface analysis revealed that complex 1 was supported mainly by Br···H and H···H intermolecular interactions.

Calculating the Climatology and Anomalies of Surface Cloud Radiative Effect Using Cloud Property Histograms and Cloud Radiative Kernels

Cloud radiative kernels(CRK)built with radiative transfer models have been widely used to analyze the cloud radiative effect on top of atmosphere(TOA)fluxes,and it is expected that the CRKs would also be useful in the analyses of surface radiative fluxes,which determines the regional surface temperature change and variability.In this study,CRKs at the surface and TOA were built using the Rapid Radiative Transfer Model(RRTM).Longwave cloud radiative effect(CRE)at the surface is primarily driven by cloud base properties,while TOA CRE is primarily decided by cloud top properties.For this reason,the standard version of surface CRK is a function of latitude,longitude,month,cloud optical thickness(τ)and cloud base pressure(CBP),and the TOA CRK is a function of latitude,longitude,month,τand cloud top pressure(CTP).Considering that the cloud property histograms provided by climate models are functions of CTP instead of CBP at present,the surface CRKs on CBP-τhistograms were converted to CTP-τfields using the statistical relationship between CTP,CBP andτobtained from collocated CloudSat and MODIS observations.For both climate model outputs and satellites observations,the climatology of surface CRE and cloud-induced surface radiative anomalies calculated with the surface CRKs and cloud property histograms are well correlated with those calculated from surface radiative fluxes.The cloud-induced surface radiative anomalies reproduced by surface CRKs and MODIS cloud property histograms are not affected by spurious trends that appear in Clouds and the Earth's Radiant Energy System(CERES)surface irradiances products.

Surface Modification of Natural Fibrous Brucite with Stearic Acid

Fibrous brucite,a kind of brucite with unique structure and physical properties,was modified with stearic acid as a surface modifier.In order to investigate the mechanism of surface modification,the fixation of stearic acid on fibrous brucite and the induced changes in surface properties were studied by using X-ray diffraction（XRD）,scanning electron microscopy（SEM）,infrared spectroscopy（IR）,Raman spectroscopy and thermo-gravimetric analysis（TGA）.XRD analysis indicates that the modification of fibrous brucite with stearic acid does not cause any changes in the structure of fibrous brucite mineral.Spectroscopy and thermal analysis show that the surfactant molecules are not only directly adsorbed on the surface of the mineral,but also chemisorbed on mineral surface by forming chemical bonds between the modifier and magnesium hydroxide.

A New 3D Pb(Ⅱ) Coordination Polymer [Pb(L)]_n Based on a Long Flexible Octane-1,8-dicarboxylic Acid:Crystal Structure and Physical Properties

A new Pb（II）-based coordination polymer, [Pb（L）]n （1）, was hydrothermally synthesized and its structure was determined by single-crystal X-ray diffraction （H2L = octane- 1,8-dicarboxylic acid）. Compound 1 crystallizes in orthorhombic, space group Pnma with a = 32.061（4）, b = 7.2597（8）, c = 4.8084（5） A, V= 1119.2（2） A3, Z = 4, C10H1604Pb, Mr = 407.42, Dc = 2.418 g/cm3, F（000） = 760, μ（MoKa） = 15.066 mm-1, R = 0.0270 and wR = 0.0666. In 1, each Pb（II） cation is coordinated by six carboxylate oxygen atoms from four L2- anions. Each L2- anion bridges three Pb（ll） atoms in a μ3：η2：η1：η1 mode to form a 3D framework. The structure of 1 was characterized by IR spectrum and thermogravimetric analysis. Moreover, solid state luminescent property of 1 was also investigated.

Extraction of seed oil from Diospyros lotus optimized using response surface methodology

Oil from seeds of Diospyros lotus was extracted using a conventional method with two different solvents:hexane and petroleum ether. A central composite design with response surface methodology were used to optimize the process. A second-order polynomial equation was employed, and ANOVA was applied to evaluate the impact of various operating parameters including extraction temperature(x_1; 44.9–70.1 °C), extraction time(x_2;5.0–10.0 h) and solvent to solid ratio(x_3;11.6–28.4 mL g^(-1)), on oil yield. Experiments to validate the model showed decent conformity between predicted and actual values. Extraction conditions for optimal oil yield were 61 °C, 8.75 h extraction duration and 19.25 mL g^(-1) solvent to solid ratio. Under these conditions, the oil yield was predicted to be 5.1340%. Oil samples obtained were then analyzed using gas chromatography. The fatty acid composition revealed the major fatty acids to be oleic acid(C18:1) and linoleic acid(C18:2). The analysis of oil also demonstrated a decent ratio between omega-3 and omega-6 fatty acids. The structure of seeds was imaged using scanning electron microscopy. Oil quality was analyzed thermogravimetrically and by Fourier transform infrared spectroscopy. The assigned nutritional features of the D. lotus oil suggested that it can be used as an edible oil in pharmaceutical and food industry in the future.

Controllably tailoring external surface sites of nanosheet HZSM-5 for maximizing light olefins in catalytic cracking of n-decane

A series of triphenylethoxysilane(TPEOS)-modified nanosheet HZSM-5 catalysts(ZN-x,x=4%,8%and16%,mass)were synthesized by chemical liquid deposition to selectively change external acidity distributions.TPEOS modification was found to passivate some external Br?nsted and Lewis acid sites by37.8%,in which Br?nsted acid sites(BAS)were found more easily sacrificed by breaking the surface Al AO bond of bridging hydroxyl groups and forming Si AOASi bonds.The selectivity of ZN-8 catalyst for light olefins(ethylene,propylene and butene)in n-decane catalytic cracking is up to 26%(450℃,WHSV=10.95 h^(-1)),which is ca.78%higher than that of parent one.The better performance was attributed to the appropriate external acid density in ZN-8,which inhibits bimolecular hydrogen transfer reaction of light olefins on the adjacent acid sites,resulting in more olefins,few coke precursors and thus an excellent catalytic stability.

Synthesis, Acid and Base Resistance of Various Copper Phosphate Pigments by the Substitution with Lanthanum

Transition metal phosphates are used as inorganic pigments, however these materials have a weak point for acid or base resistance. Because lanthanum phosphate is insoluble in acidic or basic solution, the addition of lanthanum was tried to improve the acid or base resistance of copper phosphate pigment. Various cooper – lanthanum phosphates were synthesized in wet (H3PO4, Cu(NO3)2, La(NO3)3) or dry (H3PO4, CuCO3●Cu(OH)2●H2O, La2O3) processes. The additional effects of lanthanum were studied on the chemical composition, particle shape and size distribution, specific surface area, color, acid and base resistance of the precipitates and their thermal products.

Surface Characterization of Glass Fiber by Inverse Gas Chromatography

The surface properties of glass fiber were quantificationally analyzed by inverse gas chromatography （IGC）. Five n-alkanes （C6, C7, C8, C9, and C10） were chosen as apolar probes to characterize the dispersive component of surface free energy. Trichloromethane （CHCl3）, acetone, and tetrahydrofuran （THF） were chosen as polar probes to detect the Lewis acid-base parameters. It is found that the dispersive components of free energy are 32.3, 30.5, 27.5, and 26.9 mJ/m^2 at 70, 80, 90, and 100 ℃. respectively. The Lewis acidic number Ka of the glass fiber is 0.512 4, and the basic number Kb is 2.862. The results mean the glass fiber is a Lewis basic material.

Surface Graft Polymerization of PET and PE Fibers by UV Irradiation and Their Characteristics

Polyethylene terephthalate(PET)and polyethylene(PE)fibers were surface photo-grafted with acrylic acid(AA)by using UV irradiation photochemical initiationduring a continuous winding process within 1-2 min-utes.The grafted fibers were characterized by measure-ments of dye uptaking,moisture regain,pull-out forcesof monofilament from cured matrix,as well as by analy-sis of ESCA and ATR-FTIR spectra.All these resultsconfirm that the surface behavior of the UV-irradiationgrafted fibers was greatly improved.It was also provedthat the original excellent mechanical properties of the fi-bers were well-retained after the surface grafting treat-ment.

微量生物炭表面酸性官能团质量摩尔浓度定量分析方法

表面官能团是生物炭的重要组成部分,其种类与数量对生物炭的性质、性能和应用有很大影响。现有碳材料表面官能团定量分析主要方法为Boehm滴定法,该方法耗炭量大、操作步骤多、耗时长。为此,通过构建质子消耗模型、编写Python程序、进行酸碱滴定实验、调试模型参数,建立一种微量生物炭表面官能团质量摩尔质量摩尔浓度定量分析方法,能够快速测量微量生物炭的表面官能团质量摩尔浓度与对应的酸解离常数p K_(a)。通过调整参数、训练模型,分析此方法适用的生物炭质量范围,发现测试样品质量为50 mg时模型的均方误差E_(MS)<0.002,迭代次数设置为20000时模型的E_(MS)<0.001,表明测量结果准确度较高。该方法测定的生物炭表面官能团总量与Boehm滴定法的相对误差在2%以内,且生物炭用量缩减95%、测量时间缩短10 h以上、实验操作步骤大幅简化,满足生物炭表面官能团定量分析微量、快速的技术需求。

植酸基阻燃剂对泡桐木材燃烧性能和热稳定性的影响

以植酸为主要原料,分别通过层层组装法、两步法、溶胶-凝胶法3种方式,合成植酸基阻燃剂(植酸-壳聚糖全生物质阻燃剂、植酸铵-环糊精膨胀型阻燃剂、植酸铵-硅溶胶环保阻燃剂);通过表面涂覆的方式在泡桐(Paulownia)木材表面构建阻燃涂层,研究3种阻燃剂对试件点燃时间、热释放速率、总热释放量、总烟释放量、一氧化碳和二氧化碳产量、残余物质量和热稳定性的影响。结果表明:与天然木材相比,植酸铵-环糊精阻燃木材、植酸铵-硅溶胶阻燃木材的点燃时间均延长一倍以上,3种阻燃剂对降低木材的热释放速率、总热释放量、二氧化碳产量均具有促进作用,残余物质量增加量的提高超过6.89%,但总烟释放量、一氧化碳产量有所增加;阻燃木材的热分解速率明显下降,植酸-壳聚糖阻燃木材、植酸铵-环糊精阻燃木材、植酸铵-硅溶胶阻燃木材的残炭量分别提高163.24%、58.04%、121.77%,热稳定性显著提高。

Support effect of the supported ceria-based catalysts during NH_3-SCR reaction

To investigate how the physicochemical properties and NH3‐selective catalytic reduction(NH3‐SCR)performance of supported ceria‐based catalysts are influenced as a function of support type,a series of CeO2/SiO2,CeO2/γ‐Al2O3,CeO2/ZrO2,and CeO2/TiO2catalysts were prepared.The physicochemical properties were probed by means of X‐ray diffraction,Raman spectroscopy,Brunauer‐Emmett‐Teller surface area measurements,X‐ray photoelectron spectroscopy,H2‐temperature programmed reduction,and NH3‐temperature programmed desorption.Furthermore,the supported ceria‐based catalysts'catalytic performance and H2O+SO2tolerance were evaluated by the NH3‐SCR model reaction.The results indicate that out of the supported ceria‐based catalysts studied,the CeO2/γ‐Al2O3catalyst exhibits the highest catalytic activity as a result of having a high relative Ce3+/Ce4+ratio,optimum reduction behavior,and the largest total acid site concentration.Finally,the CeO2/γ‐Al2O3catalyst also presents excellent H2O+SO2tolerance during the NH3‐SCR process.