Ordered Macro/Microporous Ionic Organic Framework for Efficient Separation of Toxic Pollutants from Water

In case of pollutant segregation, fast mass diffusion is a fundamental criterion in order to achieve improved performance. The rapid mass transport through porous materials can be achieved by availing large open pores followed by easy and complete accessibility of functional sites. Inducing macroporosity into such materials could serve as ideal solution providing access to large macropores that offer unhindered transport of analyte and full exposure to interactive sites. Moreover, the challenge to configure the ionic-functionality with macroporosity could emerge as an unparalleled avenue toward pollutants separation. Herein, we strategized a synthetic protocol for construction of a positively charged hierarchically-porous ordered interconnected macro-structure of organic framework where the size and number of macropores can easily be tuned. The ordered macropores with strong electrostatic interaction synergistically exhibited ultrafast removal efficiency towards various toxic pollutants.     

Core-shell copper hydroxide-polysaccharide composites with hierarchical macroporosity

A new method of preparation of polymeric-inorganic porous nanocomposites with core-shell morphology allowed to stabilise copper hydroxide salts in water. A shell of inorganic salts was formed around microspheres of alginate gel by migration of the metal ions from the core of the particles. The formation of the copper hydroxide nitrate shell was controlled by the kind of mineralisation treatment. The natural polysaccharide was an effective agent of inorganic growth control. The mineral shell stabilised the hydrated polymer gel by considerably limiting the drying and induced the formation of a hierarchical macroporosity when drying the microspheres under supercritical CO₂ conditions.     

Porosity and interior structure analysis of pellet-flocs

Pellet-flocs are the result of modified flocculation performance. They are spherically shaped and can reach several millimeters in size. Since pellet-floc aggregates are created from macroflocs and these from microflocs and these, in turn, from primary solid particles, it can be expected that the total porosity is composed of porosities resulting from spaces between all these sub-elements. Accordingly, micro- and macroporosity can be distinguished in the interior structure of pellet-flocs.

Although considerable attention has been given to total aggregate porosity measurement, no reports can be found about the full morphological characteristics of different types of pores. Moreover, there is no single reliable method that can accurately obtain values for the respective fractions of pore volume (microporosity, macroporosity) within a relatively big floc aggregate.

This work is an approach to probe the porosity within pellet-flocs at different size levels by combining the outcomes from different examination methods.

Pellet-floc aggregates were investigated using the following techniques: free settling, light microscopy of resin-embedded microtome slices and scanning electron microscopy (SEM).

The results confirmed that the biggest portion of porosity is composed of micropores in the size range of a few microns, which were first visible by SEM image analysis. Light microscopy of resin-embedded microtome slices is an accurate method to obtain so called macroporosity of a whole agglomerate with equivalent pore diameter above 50 μm. The study of free settling data revealed satisfactorily the total porosity of pellet-flocs. Finally, a multilevel porosity model of pellet-flocs could be obtained.     

Facile preparation of hierarchically porous carbon using diatomite as both template and catalyst and methylene blue adsorption of carbon products

Hierarchically porous carbons were prepared using a facile preparation method in which diatomite was utilized as both template and catalyst. The porous structures of the carbon products and their formation mechanisms were investigated. The macroporosity and microporosity of the diatomite-templated carbons were derived from replication of diatom shell and structure-reconfiguration of the carbon film, respectively. The macroporosity of carbons was strongly dependent on the original morphology of the diatomite template. The macroporous structure composed of carbon plates connected by the pillar- and tube-like macropores resulted from the replication of the central and edge pores of the diatom shells with disk-shaped morphology, respectively. And another macroporous carbon tubes were also replicated from canoe-shaped diatom shells. The acidity of diatomite dramatically affected the porosity of the carbons, more acid sites of diatomite template resulted in higher surface area and pore volume of the carbon products. The diatomite-templated carbons exhibited higher adsorption capacity for methylene blue than the commercial activated carbon (CAC), although the specific surface area was much smaller than that of CAC, due to the hierarchical porosity of diatomite-templated carbons. And the carbons were readily reclaimed and regenerated.     

Biomimetic dual templating of silica by polysaccharide/protein assemblies

The control of silica growth by living organisms such as diatoms is known to involve the templating effect of several biomolecules working concomitantly. However, until now, biomimetic studies involving model molecules have mainly been performed with single templates. We show here that the addition of two biopolymers, gelatin and alginic acid, to silicate solutions allows the formation of complex structures resulting from the combined templating effect of both components at different scales. Gelatin is able to activate silica formation resulting in hybrid aggregates at the nanoscale. Alginic acid does not interfere with silica condensation but is able to control silica morphology through the assembly of these gelatin-silica aggregates at the microscale. For all materials, calcination up to 700 degrees C degrades the polymer component of the hybrid material and opens macroporosity in the silica network. In parallel, the high thermal stability of gelatin allows a good preservation of initial silica nanoparticle size upon heating whereas a coarsening process is observed in the sole presence of alginate. These results correlate well with previous models of biosilicification and suggest that the use of multiple templates is a suitable approach to elaborate more complex silica architectures.     

All-clay photonic crystals

Hierarchically structured "all-clay" 1D and 3D inverse photonic crystals were fabricated, featuring the crystalline layered microstructure of the phyllosilicate Laponite combined with crystalline macroporosity on the submicron scale. By using simple hard-templating protocols based on monodisperse polystyrene spheres, periodic layered silicate and inverse opal architectures with photonic crystal properties are accessible, which exhibit reflectivities of the stop band in excess of 50%. The combination of intrinsic chemical functionality with structural color makes such hierarchical "all-clay" architectures potential scaffolds in color-tunable chemo-optical devices.     

Mesoporous alginate/silica biocomposites for enzyme immobilisation

Alginate/silica biocomposites were synthesised by impregnation of mesoporous silica particles with alginic acid solution, followed by Ca²⁺-induced biopolymer gelation. They consist of alginate trapped in the open macroporosity of the silica network, whose porous structure is maintained, as indicated by X-ray diffraction and nitrogen sorption measurements. β-galactosidase enzymes incorporated in the initial biopolymer solution maintain their catalytic activity towards 4-nitrophenyl-β-d-galactopyranoside hydrolysis. When compared to the pure Ca-alginate gel, the biocomposites exhibit a better stability upon ageing, limiting enzyme leaching.     

One-pot synthesis of network supported catalyst using supramolecular gel as template

<正>A simple and general strategy is described for preparing network supported catalyst through a one-pot synthetic procedure using supramolecular gel as template.This procedure directly attaches ligand to support during fabricating the support.Using this strategy,supported CuBr/di-(2-picolyl) amine catalyst with U-shaped fibrillar network was prepared and used in atom transfer radical polymerization of methyl methacrylate.XPS and SEM characterization of the catalyst revealed homogeneous distribution of ligand,sufficient reactive sites,adequate mechanical strength and macroporosity.The polymerization results demonstrated high activity and reusability of such catalyst.This strategy might be extended to other supported catalysts used in column reactors.     

Semi-micro-monolithic columns using macroporous silica rods with improved performance

Monolithic silica columns in semi-micro-format have been synthesized using poly(acrylic acid) as a phase-separation inducer via a sol–gel route. The absence of a thick skin layer accompanied by deformation of the micrometer-sized gelling skeletons on the outermost part of the macroporous silica rod contributed to improve the efficiency of monolithic silica columns as thick as 2.4 mm in diameter. The kinetic plot analysis revealed that monolithic silica columns with macropore diameter of 1 μm and skeleton thickness of 1 μm with decreased macroporosity behave similarly to columns packed with 3 μm particles with slightly lower back pressure.     

Synthesis and Characterization of Alginate/Silica Biocomposites

We have investigated the formation of silica/alginate biocomposites. The silica gel was first obtained by the sol-gel route using aqueous precursors, in the presence of the polymer. Gelation of the trapped alginate could be consequently performed by addition of a divalent metal cation. Thermogravimetric analysis, SEM and nitrogen adsorption-desorption experiments indicated that the polymer is located in the macroporosity of the biocomposites so that it can be partially removed by citrate treatment. Even though only weak hydrogen bonds are expected, the morphological features of the composites revealed to depend on the biopolymer content of the initial solution.     

Sintering Aerogels

Studies of the densification kinetics and structural evolution of non-crystalline aerogels during sintering are examined in light of theory. In most respects, the theory of viscous sintering is capable of quantitatively accounting for the experimentally observed behavior, as long as the initial pore size distribution is known. Unfortunately, it is difficult to obtain adequate structural information; in particular, measurements using nitrogen desorption and thermoporometry often erroneously indicate the presence of macroporosity. Some authors have claimed that large pores contract more quickly than small pores during sintering; under certain circumstances this is predicted by the theory.     

Theoretical description of pores in the simulation of composite materials

The influence of porosity on the electric conductivity and the dielectric constants of composite materials was studied using computer simulation (the Monte Carlo method). A new approach to the simulation of porous systems that treats pores as a component equivalent to the solid phase components was proposed. Within the framework of this approach, an analysis of the influence of the micro- and macroporosity on the electric conductivity was carried out. It was established that the concept of a barrier-disordered system is also valid for pores. It was shown for the first time that pores can serve as one of the factors that forms the contact barrier distribution function. The proposed theoretical models were in good agreement with the experimental data.     

Polybenzimidazole as a promising support for metal catalysis: morphology and molecular accessibility in the dry and swollen state

Polybenzimidazole (PBI) in beaded form (250-500 microm) has been characterized in the dry state by scanning electron microscopy (SEM), BET, and nitrogen porosimetry. In the swollen state, it has been characterized by inverse steric exclusion chromatography (ISEC) in tetrahydrofuran, toluene, and water, by ESR of TEMPONE (2,2,6,6-tetramethyl-4-oxo-1-oxypiperidine), and pulse field gradient spin echo (PGSE) NMR spectroscopy, toluene, in tetrahydrofuran, ethanol and water. The dry-state results are in good agreement with the ISEC results obtained in tetrahydrofuran, toluene, and water with regard to the 40-80 nm macroporosity. The swelling-dependent surface area and pore volume detected by ISEC in toluene and water reveal the amphiphilic nature of PBI.     

Effect of steam activation on the porosity and chemical nature of activated carbons from Eucalyptus globulus and peach stones

The effect of steam activation of chars prepared from Eucalyptus globulus (EU) and peach stones (PS) on both the porosity development and the amount of oxygen surface groups is presented. The N₂ (77 K) and CO₂ (273 K) adsorption isotherms and the mercury intrusion measurements show that, apart from the differences in macroporosity caused by the different texture of the original precursors, the development of porosity upon activation is small for the EU char and important for the PS char. A somewhat parallel behaviour is found for the oxygen surface groups, as determined by infrared spectroscopy and temperature programmed decomposition (TPD): the development of microporosity for PS chars is accompanied by an increase in the number of oxygen surface groups stable at the activation temperature, the number being low for activated carbons from EU chars. This behaviour indicates the more important role of diffusion control of the water molecule to the interior of the particle when activating the EU char in respect to the PS char.     

Facile Fabrication of Nanoparticles Confined in Graphene Films and Their Electrochemical Properties

The development of novel nanostructured electrode materials with high performance and based on abundant elements is a key element in the societal pursuit of sustainable energy. Graphene‐based structures with rich macroporosity and high conductive networks are promising components to develop novel electrode materials. Herein, we described a facile procedure to confine Ni(OH)₂ particles in a graphene film, leading to a new sandwich‐like hybrid structure. The hybrid film offers simultaneously ordered ion diffusion channels and high electrical conductivity, which facilitate the improvement of both electrode kinetics and electrochemical stability, thus leading to high capacitance, fast rate capability, and stable cycle life as supercapacitor materials. This work provides a facile pathway for optimized structures for electrode materials, and represents a benefit for the global issues of energy shortage and environmental pollution.     

Hierarchical Porous ZSM‐5 Zeolite Synthesized by in situ Zeolitization and Its Coke Deposition Resistance in Aromatization Reaction

Hierarchical ZSM‐5 zeolites with micro‐, meso‐ and macroporosity were prepared from diatomite zeolitization through a vapor‐phase transport process on solid surfaces. The aromatization performance of the catalysts was investigated on a fixed bed reactor by using FCC gasoline as feedstock. The crystal phase, morphology, pore structures, acidity and coke depositions of the hierarchical ZSM‐5 zeolites were characterized by means of X‐ray diffraction (XRD), scanning electron microscope (SEM), N₂ adsorption/desorption, Fourier transform infrared (FT‐IR) and thermogravimetry‐mass spectrogram (TG‐MS), respectively. The results show that the prepared hierarchical ZSM‐5 zeolite possesses excellent porosity and high crystallinity, displaying an improved aromatization performance and carbon deposition resistance due to its meso‐ and macroporous structures.     

An Elastic Monolithic Catalyst: A Microporous Metalloporphyrin‐Containing Framework‐Wrapped Melamine Foam for Process‐Intensified Acyl Transfer

The advent of conjugated microporous polymers (CMPs) has had significant impact in catalysis. However, the presence of only micropores in these polymers often imposes diffusion limitations, which has resulted in the low utilization of CMPs in catalytic reactions. Herein, the preparation of a foam‐supporting CMP composite with interconnective micropores and macropores and elastic properties is reported. Metalloporphyrin‐based CMP organogels are synthesized within the melamine foam by a room‐temperature oxidative homocoupling reaction of terminal alkynes. Upon drying, the CMP‐based xerogels tightly wrap the framework skeletons of the foam, while the foam cells are still open to allow for the preservation of elasticity and macroporosity. Such a hierarchical structure is efficient for acyl transfer, facilitates substrate diffusion within interpenetrative macropores and micropores, and could be used to intensify catalytic processes.     

Monolithic macroporous catalysts--a new route for miniaturization of water-gas shift reactor

Monolithic macroporous Pt/CeO2/Al2O3 catalysts were prepared using concentrated emulsions synthesis route, and the obtained samples were characterized with SEM, TG, TEM, XRD and TPR techniques. These monolithic catalysts were applied to water gas shift (WGS) reaction in reformed gases. The SEM and TEM results indicated that the monoliths possessed macroporosity, and that the platinum particles homogeneously dispersed on the supports with the particle size in the range of 1−2 nm. The reducibility of the catalysts was characterized by TPR method, and it was shown that the monolithic PtOx/CeO2/Al2O3 exhibited the similar reducibility property to that of the particle PtOx/CeO2 reported in literatures. The CO conversion over the monolithic catalysts is higher than that over micro-reactor catalysts for WGS reaction in the reformed gases conditions, indicating that the monolithic macroporous catalysts is a potential new route for miniaturization of WGS reactor.     

Multiscale Porosity from Thermoreversible Poly(vinylidene fluoride) Gels in Diethyl Azelate

Poly(vinylidene fluoride) (PVF₂) produces thermoreversible gels in a series of diesters. The polymer-solvent complexation occurred for intermittent number of carbon atoms n ⩾ 2 and the enthalpy of complexation increased with increasing n. The gels were dried by replacing the diesters with low boiling solvent like cyclohexane (bp. 80 °C) and methylcyclohexane (bp. 99 °C). The porosity of the dried gels was measured using Poremaster-60. For PVF₂-DEAZ gel meso and macro porosity have been observed. The former pore dimensions have been attributed for polymer-solvent complexation while the macroporosity has been attributed for caging of solvent between the PVF₂ fibrils The porosity measured from nitrogen adsorption isotherms using BJH method indicate presence of minimum pore diameter of 3.8 nm for the 10% dried gel of PVF₂.     

Facile synthesis of meso-substituted dipyrromethanes and porphyrins using cation exchange resins

The macroporosity and acidity of cation exchange resins play a crucial role in the synthesis of dipyrromethanes and porphyrins; for the first time, cation exchange resins have been used as heterogeneous solid acid catalysts to produce dipyrromethanes and porphyrins in good yields. The reaction, at room temperature, of substituted aromatic aldehydes with pyrrole catalysed by cation exchange resin afforded the corresponding meso-substituted dipyrromethane in yields ranging from 70 to 80%, indicating the broad scope of the reaction. Further, the condensation of meso-substituted dipyrromethane with similar or different substituted aromatic aldehydes, using cation exchange resins furnished meso-tetrakis-symmetrical and mixed porphyrins, respectively. One-pot synthesis of porphyrins can also be carried out directly from the aldehydes and pyrrole under the above conditions. Acidolysis of the dipyrromethane is negligible under the conditions of the porphyrin-forming reaction.