Intensification of delignification of Tectona grandis saw dust as sustainable biomass using acoustic cavitational devices

Delignification of sawdust was studied using ultrasound assisted alkali peroxide approach using longitudinal horn for the first time and the efficacy compared with more commonly used configurations of ultrasonic reactors. Comparison with the conventional approach based on stirring has also been presented to establish the process intensification benefits. Effect of different operating parameters such as sodium carbonate concentration (0.1, 0.15, 0.2, 0.25 M), hydrogen peroxide concentration (0.2, 0.4, 0.6, 0.8, 1 M) and biomass loading (2, 4, 6, 8, 10 wt%), on the efficacy of lignin extraction has been investigated for different ultrasonic reactors. The optimum conditions for probe type ultrasonic horn were established as 150 W, 50% duty cycle and 80% amplitude with optimum process conditions as Na₂CO₃ concentration as 0.2 M, H₂O₂ concentration as 1 M, biomass loading of 10 wt% and operating time of 70 min. Longitudinal horn resulted in best efficacy (both in terms of yield and energy requirements) followed by ultrasonic horn and ultrasonic bath whereas the conventional approach was least effective. The obtained lignin was also analyzed using different characterization techniques. The presence of peaks at wavelength range of 875–817, 1123–1110, and at 1599 cm⁻¹ for the extracted sample confirmed the presence of lignin. Increase in the crystallinity index of the processed sample (maximum for longitudinal horn) also confirmed the lignin removal as lignin is amorphous in nature. Overall it has been concluded that ultrasound can be effectively used for delignification with longitudinal horn as best configuration.     

TiO~2修饰的介孔分子筛MCM-41的合成、表征及光 催化性研究

首次以三种不同的含钛有机物为氧化钛的前驱体,合成了三种TiO~2呈单层分散状态的TiO~2修饰的介孔分子筛MCM-41,并以XRD,FT-IR,液氮温度下N~2吸附-脱附曲线,固体UV-vis漫反射等表征手段对其结构特征和氧化钛分散状态进行了研究。TiO~2在介孔分子筛MCM-41孔道中分散,MCM-41仍能保持骨架结构,没有晶相TiO~2生成;TiO~2与MCM-41孔道表面的≡Si－OH以化学键连接,生成Si－O－Ti键;TiO~2在MCM-41内孔壁呈均匀单层分散状态;TiO~2粒子的减小使其对紫外光的吸收发生明显的蓝移现象。并以苯酚降解反应为模型检验合成的具有光催化性的TiO~2修饰的MCM-41的光催化活性。     

微波消解-电感耦合等离子体发射光谱(ICP-OES)法测生物质中的碱金属和碱土金属

为研究并解决测试生物质样品中碱金属和碱土金属含量的干扰,采用微波消解-电感耦合等离子体发射光谱(ICP-OES)法对生物质中的碱金属和碱土金属钾、钙、钠、镁元素进行测定,考察了样品消解后不同的酸体系,共存元素干扰对钾、钠、钙、镁含量测定的干扰研究。经过研究表明,接近分析标准曲线酸浓度的样品干扰小,铅、铟、钛、锰元素对钠元素测定造成干扰,砷、铜、镉对钙元素测定干扰,铝对钾元素测定有干扰,镁测定不受共存元素干扰影响,运用干扰系数法可以减少共存元素对测定元素的误差。各待测元素标准曲线相关系数大于0.9996,检出限为0.0014~0.023 mg/L,玉米芯各元素的相对标准偏差为0.98%~1.9%,加标回收率为80.2%~106%;西瓜皮的各元素相对标准偏差为0.91%~2.3%,加标回收率为85.3%~106%。方法用于测定国家标准物质GBW07603,各元素结果均在标准值参考范围内。方法用于测定生物质中碱金属和碱土金属的结果,用t检验法与离子色谱测定值进行比对,结果无显著性差异。     

Evaluation of defect induced surface heterogeneity in Metal-Organic Framework materials with alkali dopants employing adsorption isotherm modelling

In this article, an assessment of surface structural heterogeneity in porous metal organic framework (MOF) structure has been demonstrated by employing the methane and carbon-dioxide adsorption isotherms data. The virgin MIL-101-(Cr) MOF was synthesized by the hydrothermal method and defects were induced in the MOF structure by doping with various alkali (K, Na, Li) cations. The synthesized MOFs were characterized by XRD, SEM, EDX and BET measurement techniques. In order to understand the defect induced surface heterogeneity by alkali cation dopants, the surface energy distributions for CH₄ and CO₂ adsorptions on MOFs were measured by Dubinin – Astakhov model equation. The surface heterogeneity is mainly controlled by the limiting uptakes of adsorbates, the polarizability of adsorbates and the adsorbate-adsorbent interaction energy.     

Ni/C催化剂上山梨醇氢解反应中碱对乳酸形成的影响

山梨醇是重要的生物基平台化合物,其选择加氢裂解制备乙二醇和1,2-丙二醇等低碳二元醇,是一个具有重要科学意义和应用前景的催化过程.山梨醇氢解反应涉及C-C键和C-O键等化学键的裂解,裂解选择性尤为关键.通常情况下,添加NaOH,KOH,Ca(OH)2,CaO和Ba(OH)2等碱性物质可增加糖醇转化率和二元醇选择性,但也会生成大量乳酸等副产物.研究乳酸的生成途径,探索抑制乳酸生成的方法,对于提高山梨醇加氢裂解制备低碳二元醇的选择性具有重要意义.本文以Ni/C催化剂上山梨醇加氢裂解反应为模型反应,研究了碱性化合物添加剂类型及其用量对乳酸生成的影响.根据加氢裂解机理分析可知,糖醇氢解主要涉及以下关键步骤:在碱的存在下,多元醇在金属催化剂上发生脱氢反应生成相应的羰基中间体;然后,羰基中间体在碱性介质中通过逆羟醛缩合反应,发生C-C键断裂.因此,在糖醇氢解反应和C-C键断裂中,添加碱性化合物将会不可避免地生成乳酸.结果表明,以NaOH和Ca(OH)2为添加剂时,山梨醇加氢裂解生成乳酸的选择性分别为15.1％和8.9％.而以La(OH)3为添加剂时,生成乳酸的选择性仅为0.1％.以Ca(OH)2和La(OH)3为添加剂时反应具有高活性,山梨醇转化率均可达到99％以上.分别以Ca(OH)2和La(OH)3为添加剂,研究了碱性添加剂用量对山梨醇氢解反应的影响.结果表明,以Ca(OH)2为添加剂时,山梨醇转化率和乳酸选择性均随着Ca(OH)2用量增加而增加;当OH-投料量为11.06 mmol时,乳酸选择性可达11.7％.而以La(OH)3为添加剂时,即使La(OH)3用量仅为0.08 mmol时,山梨醇转化率也可高达99％;继续增加La(OH)3用量,对乳酸的选择性影响不大;当OH-投料量为11.06 mmol时,乳酸选择性也只有0.3％.对山梨醇加氢裂解反应分析可知,与Ca(OH)2相比,La(OH)3添加剂可使C2和C4产物的总选择性从20.0％增加到24.5％.上述结果表明La(OH)3可高效促进山梨醇加氢转化.为了探索Ca(OH)2或La(OH)3为添加剂时山梨醇加氢裂解产物分布不同的本质原因,以Ni/C催化剂催化的丙酮醛加氢转化为探针反应,探讨了乳酸形成的可能路径.结果表明,丙酮醛可能是山梨醇氢解反应的关键中间体之一.在仅以Ni/C催化加氢时,丙酮醛容易被转化为1,2-丙二醇;当只存在碱性添加剂时,丙酮醛可发生重排并被转化为乳酸主产物,这可能是乳酸生成的主要原因.进一步研究表明,以Ca(OH)2为添加剂时,乳酸选择性是以La(OH)3为添加剂时的1.9倍.在Ni/C催化剂和碱性添加剂共存时,由于碱性添加剂的区别,则会得到不同选择性的1,2-丙二醇和乳酸.结果表明,通过丙酮醛催化加氢可得到1,2-丙二醇,也可以通过重排反应生成乳酸;这两类反应是竞争性的.在山梨醇氢解反应中,以Ca(OH)2为添加剂时,加氢反应和重排反应均可发生.而以La(OH)3为添加剂时,丙酮醛加氢反应占主导,仅生成微量乳酸.该研究对提高山梨醇催化加氢裂解选择性具有参考意义.     

Template‐Engaged Solid‐State Synthesis of Barium Magnesium Silicate Yolk@Shell Particles and Their High Photoluminescence Efficiency

This study presents a new synthetic method for fabricating yolk@shell‐structured barium magnesium silicate (BMS) particles through a template‐engaged solid‐state reaction. First, as the core template, (BaMg)CO₃ spherical particles were prepared based on the coprecipitation of Ba²⁺ and Mg²⁺. These core particles were then uniformly shelled with silica (SiO₂) by using CTAB as the structure‐directing template to form (BaMg)CO₃@SiO₂ particles with a core@shell structure. The (BaMg)CO₃@SiO₂ particles were then converted to yolk@shell barium magnesium silicate (BMS) particles by an interfacial solid‐state reaction between the (BaMg)CO₃ (core) and the SiO₂ (shell) at 750 °C. During this interfacial solid‐state reaction, Kirkendall diffusion contributed to the formation of yolk@shell BMS particles. Thus, the synthetic temperature for the (BaMg)SiO₄:Eu³⁺ phosphor is significantly reduced from 1200 °C with the conventional method to 750 °C with the proposed method. In addition, the photoluminescence intensity of the yolk@shell (BaMg)SiO₄:Eu³⁺phosphor was found to be 9.8 times higher than that of the conventional (BaMg)SiO₄:Eu³⁺ phosphor. The higher absorption of excitation light by the structure of the yolk@shell phosphor is induced by multiple light‐reflection and ‐scattering events in the interstitial void between the yolk and the shell. When preparing the yolk@shell (BaMg)SiO₄:Eu³⁺ phosphor, a hydrogen environment for the solid‐state reaction results in higher photoluminescence efficiency than nitrogen and air environments. The proposed synthetic method can be easily extended to the synthesis of other yolk@shell multicomponent metal silicates.     

Quantitative Modelization of Hydrogen-Bonding in Polyoxometalate Chemistry

The PACHA (Partial Atomic Charges and Hardnesses Analysis) formalism is applied to polyoxometalate chemistry. Using the Ca₂(H₃O)₂[V₁₀O₂₈]16H₂O crystal structure, it was shown that the relative affinity for protons of the various oxygen sites may be quantitatively determined. The charge distribution was also found to be in good agreement with ¹⁷O and ⁵¹V NMR measurements. The H-bond energy in this kind of compound was found to be about –17 kJmol^–1, i.e., about 20% lower than in hexagonal ice. Finally, the 57 H-atom coordinates characterizing this structure were successfully recovered from a crystal structure optimization in the solid-state through electrostatic balance minimization. The importance of considering neutral clusters for a good modelization was demonstrated not only in the case of the decavanadate structure, but also in polysilicate chemistry. For the first time a clear picture emerges explaining the widespread occurrence of four- and five-membered rings in zeolite and silicate chemistry. The possibility of forming much larger polyanions with transition metal cations, is well explained using the crystal structure of the superfullerene keplerate [Mo₁₃₂O₃₇₂(HCO₂)₃₀(H₂O)₇₂]^42– as a benchmark compound. The possibility of performing an ab-initio retrosynthetic analysis of this cage is demonstrated.     

A new resin containing benzimidazolylazo group and its use in the separation of heavy metals

A new resin incorporating benzimidazolylazo group into a matrix of polystyrene divinylbenzene has been prepared. The exchange capacity of the resin for the ions mercury(II), silver(I) and palladium(II) as a function of pH has been determined. The resin exhibits no affinity for alkali or alkaline earth metals. It is highly selective for Hg(II), Ag(I) and Pd(II). In column operation, it has been observed that Hg(II), Ag(I) and Pd(II) in trace quantities can be selectively separated from geological, medicinal and environmental samples.     

Thin ORMOSIL Films with Different Organics

Structural, optical and electrical properties of silicate films modified by structure fragments containing different organic groups were studied. The ORMOSILs were produced by a cohydrolysis of tetraethoxysilane with different types of alkyl (aryl) substituted alkoxysilanes. Film structure and its evolution during heat treatment were studied by ellipsometry and IR spectroscopy. For methyl- and phenyl-modified silicate films the shrinkage is lower than for silicate ones in the range of annealing temperature from 200 to 500°C. The shrinkage of phenyl-modified silicate film is more than three times lower than of methyl- and trimethyl-modified ones. The presence of single or double C=C bonds in the organic chain leads to an increase in the film shrinkage due to the thermodestruction of the bond as it is confirmed by IR data. In the case of phenyl- and methyl-modified silicate films this process starts from 500°C and it is accompanied by abrupt film shrinkage. The dielectric constant and the loss tangent of methyl and phenyl groups decrease due to reduction of hydroxyl content and film density. Other groups are not effective due to their thermodestruction at lower temperatures.