Crosslinking Reaction in the Formation of Porous Clays

Clay minerals are a class of hydrous layer aluminosilicates of the so-called phyllosilicate^[1] family made up of two basic types of layers, the SiO₄ tetrahedral sheet and the Al₂(OH)₆[or Mg₃(OH)₆] octahedral sheet, many of which posses interlayer cations capable of exchanging reaction with other cations. The preparation of porous clays are based on this reactivity of exchangeable interlayer cations by using the intercalation of polycations such as Al₁₃⁷⁺ oligomers^[2] into the galleries of clay minerals to form a microporous materials^[3] Here we reported a study on the interlayered crosslinking of a 2:1 type montmorillonites with a hydrolysed polycations Al in the formation of porous clays. Na-montmorillonite gel (Na-mont, particle size<2 μ) were purified by using sedimentation of Na-bentonite fines (400 mesh, Zhejiang, China) and subsequent extensively washing to remove any soluble Na⁺. Hydrolysed polycations Al was prepared by NaOH hydrolysis of AlCl₃ solutions in a condition^[2] of OH/Al=2.0 and then aging at 70-90℃ for 4 h by the following process^[3].     

新型芳香三嗪超交联多孔聚合物去除水溶液中甲基橙

Organic dyes, especially the harmful cationic dye methyl orange (MO), are emerging pollutants. The development of new materials for their efficient adsorption and removal is thus of great significance. Porous organic polymers (POPs) such as hyper-cross-linked polymers, covalent organic frameworks, conjugated microporous polymers, and polymers with intrinsic microporosity are a new class of materials constructed from organic molecular building blocks. To design POPs both with good porosity and task-specific functionalization is still a critical challenge. In this study, we have demonstrated a simple one-step method for the synthesis of the hyper-cross-linked aromatic triazine porous polymer (HAPP) via the Friedel-Crafts reaction. The resultant porous polymer was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, elemental analysis (EA), thermo-gravimetric analysis (TGA), solid-state ¹³C nuclear magnetic resonance (¹³C NMR), and nitrogen adsorption-desorption isotherms. The results show that HAPP is a rough, irregular morphology, porous organic polymer that is amorphous in nature. The novel polymer showed high Brunauer-Emmett-Teller surface area (of up to 104.36 m²∙g⁻¹), porosity, and physicochemical stability. Owing to the presence of N heteroatom pore surfaces in the network, the material exhibited a maximum adsorption capacity of 249.3 mg∙g⁻¹ for MO from aqueous solutions at room temperature. This is higher than that of some reported porous materials under the same conditions. To explain this phenomenon more clearly, theoretical quantum calculations were performed via the DFT method using Gaussian 09 software and Multiwfn version 3.4.1. It is performed to analyze the properties and electrostatic potential (ESP) of the HAPP monomer and MO. The results indicated that the N heteroatom of HAPP can easily develop strong interactions with MO, supporting the efficient adsorption of MO. The parameters studied include the physical and chemical properties of adsorption, pH, contact time, and initial concentrations. The percentage of MO removal increased as the pH was increased from 2 to 4. The optimum pH required for maximum adsorption was found to be 5.6. Adsorption kinetics data were modeled using the pseudo-first-order and pseudo-second-order models. The results indicate that the second-order model best describes the kinetic adsorption data. The adsorption isotherms revealed a good fit with the Langmuir model. More importantly, the HAPP can be regenerated effectively and recycled at least five times without significant loss of adsorption capacity. Therefore, it is believed that HAPPs with hierarchical porous structures, high surface areas, and physicochemical stability are promising candidates for the purification and treatment of dyes in solution.     

Nanofibrillar cellulose aerogels

Highly porous aerogels consisting of cellulose nanofibrils were prepared by dissolution/regeneration of cellulose in aq. calcium thiocyanate followed by regeneration and carefully controlled drying. The influence of drying method (regular freeze drying, rapid freeze drying, and solvent exchange drying) on resulting porosity was studied by electron microscopy and nitrogen adsorption. While regular freeze drying caused significant coalescence of microfibrillar units, solvent exchange drying gave highly porous aerogel composed of approx. 50 nm-wide cellulose microfibrils. Correspondingly, specific surface area of the solvent-exchange-dried aerogels ranged 160–190 m²/g, in contrast to 70–120 m²/g of regular freeze-dried materials. Rapid freeze technique using liquid nitrogen-cooled metal plate gave aerogel sheets with asymmetrical porosity, with the face contacted by copper having porous structure similar to those of solvent-exchange dried material.     

Template Synthesis of Nano-structured Materials for Electrochemical Applications

As an important preparation method of nano-structured materials, template synthesis^[1] attracted great interests in recent years. Different kinds of template such as anodic porous alumina, polymer and nano-channel glass templates have been widely studied. Compared with other templates, the size of holes in the porous alumina template can be easily controlled by properly adjusting the condition of anodization. In addition, Nano-structured material prepared from the template also provides an ideal system^[2] to investigate the effects of size of materials toward electrode's performance. In this paper, various nano-structured materials such as spinel LiMn₂O₄ and carbon nanotubes by using porous alumina template have been prepared and characterized.     

Preparation of porous carbon directly from hydrothermal carbonization of fructose and phloroglucinol for adsorption of tetracycline

Hydrothermal carbonization of biomass is a promising method to prepare carbonaceous materials. Generally, post physical or chemical activation is necessary to increase surface area and porosity of the carbon. Herein, porous carbonaceous material (FPC) with large surface area (481.7 m²/g) and pore volume (0.73 cm³/g) was prepared directly from hydrothermal carbonization of fructose and phloroglucinol in hydroalcoholic mixture. Structure characteristics of the FPC and its adsorption capacity for a representative antibiotic tetracycline in aqueous solution were investigated. This work provides a green and efficient method to fabricate porous carbonaceous adsorbent that has great potential applications in chemical and environmental fields.     

富羧酸基团的共轭微孔聚合物:结构单元对孔隙和气体吸附性能的影响

Polar groups in the skeletons of conjugated microporous polymers (CMPs) play an important role in determining their porosity and gas sorption performance. Understanding the effect of the polar group on the properties of CMPs is essential for further advances in this field. To address this fundamental issue, we used benzene, the simplest aromatic system, as a monomer for the construction of two novel CMPs with multi-carboxylic acid groups in their skeletons (CMP-COOH@1 and CMP-COOH@2). We then explored the profound effect the amount of free carboxylic acid in each polymer had on their porosity, isosteric heat, gas adsorption, and gas selectivity. CMP-COOH@1 and CMP-COOH@2 showed Brunauer-Emmett-Teller (BET) surface areas of 835 and 765 m²·g^-1, respectively, displaying high potential for carbon dioxide storage applications. CMP-COOH@1 and CMP-COOH@2 exhibited CO₂ capture capabilities of 2.17 and 2.63 mmol·g^-1 (at 273 K and 1.05 × 10⁵ Pa), respectively, which were higher than those of their counterpart polymers, CMP-1 and CMP-2, which showed CO₂ capture capabilities of 1.66 and 2.28 mmol·g^-1, respectively. Our results revealed that increasing the number of carboxylic acid groups in polymers could improve their adsorption capacity and selectivity.     

负载氯的分级多孔炭制备及其脱汞性能的研究

以纳米碳酸钙为模板,水稻秸秆为碳前驱体,采用共热解法制备了负载氯的分级多孔生物质炭。在模拟烟气条件下,利用固定床实验台架研究了生物质碳材料对烟气中的单质汞（Hg⁰）的脱除性能。采用扫描电镜（SEM）、透射电镜（TEM）、N₂吸附-脱附（BET）、程序升温脱附（Hg-TPD）以及X射线光电子能谱（XPS）等方法对材料进行表征。结果表明,盐酸浸渍不仅可去除模板产物生成多孔结构,并且有效地将氯负载到材料表面。负载氯的分级多孔炭B1C1-Cl2的比表面积和总孔容分别达到398.1 m²/g和0.4923 cm³/g。在120℃,空速（GHSV）为225000 h^-1时,脱汞效率可达95%。多孔结构有利于气体扩散,高比表面积为材料提供了更多的反应位点,微孔-介孔内表面上的C-Cl共价键为脱汞的主要化学吸附活性位点。     

Reversible Adsorption of NOx on ZrO2-supported CeO2 Prepared in Water-in-oil Microemulsion

Nitric oxides (NOx) storage catalyst^[1] provides an alternative route for abatement of NO in presence of oxygen by first adsorbing NOx and then desorbing it by temperature swing or pressure swing. YBa₂Cu₃Oy^[2] and Mn-Zr mixed oxides^[3] were reported to have large NOx adsorption capacity, but the former suffered from a great amount of coexisting CO₂ gases. The author previously reported that high NOx adsorption capacity could be obtained on Ce modified TiO₂-pillared montmorillonite without deactivation by CO₂^[1]. Microemulsion method was reported to be effective to control particle sizes and microstructures of the metal oxides^[4]. In this paper, a thermal stable ZrO₂ with high surface area was prepared in water-in-oil microemulsion, and NOx adsorption capacity was tested on the above ZrO₂ sample after impregnating with manganese nitrate and cerium nitrate.     

氮硫双掺杂活性炭材料的制备和电容性能

以头发和蔗糖为原料, 通过水热碳化和KOH活化两步法制备了氮硫双掺杂微孔炭材料. 利用扫描电子显微镜, 透射电子显微镜, 氮气吸脱附, X射线光电子能谱, 电子能谱和傅里叶交换红外光谱等手段系统表征了所制备活性炭材料的微观形貌, 孔隙结构和表面化学性质. 并在6 mol·L^-1 KOH溶液中研究了所制备活性炭材料的电容性能. 氮气吸脱附测试表明, 所制备活性炭材料的比表面积最高可达1849.4 m²·g^-1, 孔道以微孔为主. 所制备活性炭材料氮元素含量为1.6%-2.5% (原子分数(x))), 硫元素含量为0.2%-0.5% (x). 由于N、O、S官能团的协同作用, 所制备碳材料表现出明显的赝电容. 活性炭材料的比电容值最高可达200 F·g^-1, 对应的能量密度为6.9 Wh·kg^-1. 功率密度达到10000 W·kg^-1时, 能量密度仍达到4.1 Wh·kg^-1. 本文的工作表明以生物质为原料可以方便制备氮硫双掺杂活性炭电极材料.     

Fabrication and Adsorption Properties of Hybrid Material with Micropores from SBA-15

A novel hybrid material with microporous structure was fabricated from SBA-15 with mesopores via silane modification and hydrolysis. Two kinds of pores with diameters of 6.5 and 1.9 nm were found in the hybrid material. Compared to that of SBA-15, the surface area of the hybrid material increased from 395.9 m²/g to 667.4 m²/g while its porous volume decreased. The new hybrid material was found to have high efficiency in removing NaCl from solution, and the maximum adsorption capacity of it was ca. 517.5 mg/g.     

Involvement of unusual noncovalent interactions in the self-assembly of cucurbit[6]uril with[CdCl4]2- anions

The [CdCl_4]~(2-) anion as a structure inducer has proved to be useful in the construction of cucurbit[n]urilmetal coordination architectures and materials. In order to better understand the role and influence of the structure inducer in Q[n] systems, we report herein the self-assembly of Q[6] solely in the presence of[CdCl_4]~(2-)anions and in the presence of both a linear cationic organic guest and [CdCl_4]~(2-)anions. X-ray diffraction analysis revealed that 1D Q[6] porous channels were formed by the noncovalent interactions between Q[6] and [CdCl_4]~(2-)anions, but the ‘‘honeycomb effect' was not observed in the present study.However, it seems that the ‘‘honeycomb effect' and the self-assembly of Q[6] with [CdCl_4]~(2-)anions can be significantly modified and switched in the presence of a linear cationic dibutylamine guest through some unusual noncovalent interactions.     

Microporous Zinc Formate for Efficient Separation of Acetylene over Carbon Dioxide

Separation of acetylene(C₂H₂) from carbon dioxide(CO₂) by adsorbents is very challenging owing to their high similarity on molecular shape and dimension. Exploring inexpensive and easily available porous materials is of importance to facilitate the practical implementation of the challenging but energy-efficient separation. Herein, we utilize an easily available porous material[Zn₃(HCOO)₆] for the selective separation of C₂H₂ over CO₂. Because of the pore confinement in[Zn₃(HCOO)₆](pore size of 0.47 nm) and accessible oxygen sites for preferential binding of C₂H₂, this material exhibits high low-pressure uptake for C₂H₂(63 cm³/cm³ at 10 kPa and 298 K) and high C₂H₂/CO₂ selectivity(7.4 under ambient conditions) that is comparable to those of out-performing porous materials. The efficient separation of[Zn₃(HCOO)₆] for C₂H₂/CO₂ mixture has also been confirmed by the breakthrough experiments.     

Synthesis of Carbon Nanotubes:A New Solid-state Approach

In recent years, investigation on layered double hydroxide materials (LDHs, anionic clays) becomes an active field in layered materials research owing to their many important applications^[1-7]. Among the LDHs, hydrotalcite-like compounds (HTlcs) have attracted great attention due to their synthetic flexibility in preparing catalyst and ceramic precursors, and in tailor-making adsorbents, medicine stabilizers, and ion exchangers^[1,2]. In the structure of HTlcs, divalent and trivalent cations are located in the center of oxygen octahedron formed by six hydroxyl groups of the two-dimensional brucite-like sheets^[1,2]. To balance the extra charges carried by trivalent cations, anions have to be intercalated into the inter-brucite-like-sheet space (interlayer space) during the synthesis, which leads to the formation of a sandwich-like structure alternatively stacked in vertical direction of the sheets (c-axis), forming a 3D structure.     

Porous Organic Frameworks-derived Porous Carbons with Outstanding Gas Adsorption Performance

A series of porous carbon materials was synthesized via high temperature pyrolysis from well-defined and thermally stable precursors, namely porous organic frameworks(POFs), in inert atmosphere. The porous carbon materials showed enhanced gas adsorption capacities together with increased heat of adsorption and stronger affinity between the frameworks and the gases as compared to the precursor materials. To exemplify, sample C-POF-TBBP-1000 with a high BET surface area of 1290 m²/g can adsorb 2.8 mmol/g CH₄(273 K, 101.325 kPa), 5.4 mmol/g CO₂(273 K, 101.325 kPa) and 2.2% H₂(mass fraction, 77 K, 101.325 kPa), thereby surpassing most other porous adsorbent materials reported till date. The study highlights the potential of porous carbons derived from novel porous organic framework structures for gas adsorption applications.     

Self-assembled Alkylation of Atomically Flat Hydrogen-terminated Silicon (111) Surface By Using Highly Polarized Fluoroalkylsilane

Hydrogen-terminated silicon surface is of technological importance to semiconductor processes such as pre-gate^[1]. Re-contamination and re-oxidation on silicon surface become more stringent issues in order to meet the requirements in the process for producing reduced size IC chips. The modification of silicon surfaces by various strategies has attracted more attention in the past few years^[2-4]. The frequently used techniques to attach functional groups to silicon surfaces are via chemical^[2], photochemical^[3] and electrochemical reactions^[4]. Various ways to attach monlayers to silicon surfaces has been reported, including alkylation of silicon with alkenes, alkyenes, aldehydes, alcohols and Grigard reagents under photoactivated or catalytic reactions. Particularly, porous silicon prepared by chemical or electrochemical treatments has been extensively studied. Preparation of passivated layers on porous silicon surfaces has disadvantages that the silicon surfaces are damaged by reactive agents during the reaction or become porous for attachment of molecules. Recently, self-assembled monolayer of alcohols on porous silicon was reported at modest heating without the aid of catalyst or photoexcitation or potential^[5]. In the paper, we report a novel method to attach highly polarized fluoroalkylsilane on atomically flat Si(111) surface at room temperature and to form a self-assembled monolayer to prevent the silicon surface from re-contamination and re-oxidation.     

Two-dimensional cobalt metal-organic frameworks for efficient C3H6/CH4 and C3H8/CH4 hydrocarbon separation

A Co-based two-dimensional (2D) microporous metal-organic frameworks (UPC-32) with narrow distance between layers and layers (3.8 Å) exhibits high selectivity of C₃H₆/CH₄ (31.46) and C₃H₈/CH₄ (28.04) at 298 K and 1 bar. It is the first 2D Co-MOF that showed selective separation of C3 hydrocarbon from CH₄.     

Side Chain Functional Conjugated Porous Polymers for NIR Controlled Carbon Dioxide Adsorption and Release

Conjugated porous polymers exhibit considerable advantage as attractive candidate for carbon dioxide(CO₂) capture. However, the regeneration of the CO₂ still faces the problem of high energy cost. Here we synthesize a near-infrared region(NIR) light responsive conjugated porous polymer(PDPP-Gu) {DPP=3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione} by constructing porous amorphous networks with a side chain engineering strategy to regulate CO₂ adsorption and release through photothermal conversion. The PDPP-Gu is featured by a torsional conjugated backbone as well as a functional side chain of guanidino group. The donor-acceptor configuration of PDPP-Gu afforded strong absorption in the NIR and an excellent photothermal conversion capability of up to 48.8%, as well as a high surface energy. Moreover, guanidine modified side chain further enhanced the CO₂-polymers interactions, resulting in a high CO₂ selective adsorption capacity(0.8 mmol/g) at 273 K, 1 bar(1 bar=10⁵ Pa). The adsorbed CO₂ can be released under NIR light irradiation. This strategy of molecule design combined the dual features of photothermal conversion and gas adsorption, which is beneficial for the development of materials to dynamically control the adsorption and release of CO₂ through NIR light.     

Fibre-Optic pH Probe Based on the Use of An Immobilized Amino Fluoresecein Indicator

Optical sensors can offer advantages over electrochemical sensors with respect to reduced interferences and ease of use for remote sensing^[1]. The first fiber optic pH sensor was developed for in vivo measurements by Peterson et al^[2]. This sensor relates pH to the absorbance of the base from of an immobilized dye. Subsequently, a pH sensor based on the fluorescence of immobilized fluoreseinamine was reported. The sensor involves immobilizing the amino fluoresecein (AF) complex within a porous sol-gel-processed film. Sol-gel process has many advantages as a method of immobilization^[3]. At ambient temperature, it allows the fabrication of a tough, inert, porous glass material with a high surface area. Sol-gel technology provides a viable approach to prepare stable, optically transparent host matrices for the design of materials for sensor, optical, chromatographic^[4], and catalytic applications. Alternatively, organosilicon precursors of the general formula can be hydrolyzed and co-condensed with tetraethoxysilane to form an organic-inorganic hybrid. An aliquot of the resultant sol can be spin cast or dip coated on a planar substrate to form a thin film.     

Polyfunctional Conjugated Microporous Polymers for Applications in Direct C-H Arylation of Unactivated Arenes and Aqueous Adsorption of Aromatic Amines

Salen-porphyrin-based conjugated microporous polymers(CMPs) have been demonstrated to be an attractive material platform for predesigned structures and promising applications. Herein, a new salen-porphyrin-based conjugated microporous polymer(SP-CMP-L) was solvothermally prepared by porphyrin-forming condensation reaction of pyrrole and salen-dialdehyde derivative. The SP-CMP-L was characterized by spectroscopy technologies, and also exhibited excellent thermal and chemical stability. The porosity of SP-CMP-L was examined by N₂ adsorption/desorption isotherms. The BET specific surface area of the CMP material was calculated to be 290.4 m²/g with the pore volume of 0.19 cm³/g. The microstructure property of the resulting material was further evaculated by scanning electron microscopy(SEM) and transmission electron microscopy(TEM). The SP-CMP-L with salen and porphyrin multidentate coordination sites was proposed to serve as an initiator to promote the cross-coupling between aryl halides with unactivated arenes under base-mediated conditions. The transition-metal-free catalytic protocol provided high catalytic activity for direct C-H arylation reaction of unactivated arenes, and thus offered a convenient and efficient alternative for the construction biaryl scaffolds. In addition, the salen-porphyrin-based CMP material possessed remarkable adsorption capability for the removal of organic amines from water.     

A Three-dimensional Covalent Organic Framework for CO2 Uptake and Dyes Adsorption

Environmental pollution is one of the most severe problems facing today, including water pollution and the greenhouse effect. Therefore, developing materials with high-efficiency dyes adsorption and CO₂ uptake is significant. Covalent organic frameworks(COFs), as a burgeoning class of crystalline porous polymers, present a promising application potential in areas related to pollution regulation due to their exciting surface properties. Herein, we report a 3D COF with a high specific surface area(BET about 2072 m²/g) by utilizing tetrahedral and rectangle building blocks connected through[4+4] imine condensation reactions to synthesize. The obtained COF not only can separate dyes from water effectively but also shows a remarkable CO₂ uptake capacity. This research thus provides a promising material to remove dyes and adsorb CO₂ in environmental remediation.