Wide Pore Size Distribution Research Articles

Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States

AbstractThe first wide‐view image of multiple structural and phase transformations for MOFs, ranging from crystal state transformations to the extreme limit approaching liquid/glass phase, was presented. The process involves i) an initial crystalline transformation from square‐layer framework [Co2(pybz)2(CH3COO)2] ⋅ DMF (Co2) to a 3‐fold interpenetrated and ordered vacancies contained framework [Co(pybz)2(CH3OH)2] ⋅ 2CH3OH (CoM) due to in situ disassemble‐reassemble, ii) thermal induced departure of a pair of cis‐form coordinated methanol in CoM leads to amorphous framework a‐dCoM, iii) glass transition to super‐cooled liquid scl‐dCoM, iv) obtaining MOF glass g‐dCoM upon quenching the super‐cooled liquid, and v) re‐crystallization of super‐cooled liquid generates 6‐fold interpenetrated dia‐net framework [Co(pybz)2]6n (rec‐dCoM) under further heating. The access to glass from CoM, provides a new self‐perturbation strategy to create MOF glasses without melting. The wider pore size distribution in amorphous/glassy MOFs than crystalline precursor achieved the first time selective hydrocarbon gas separation by breakthrough experiments, which bring efficient separation of 1 : 99 C2H2/C2H4 by either a‐dCoM or g‐dCoM and produce polymer grade C2H4 with purity≥99.5 % after a single adsorption process. Furthermore, the mixture of 50 : 50 C3H6/C3H8 can be separated by a‐dCoM.

A novel use of incineration bottom ash for H2 aeration in the production of artificial lightweight aggregates

Cold bonding is an energy-efficient method for producing artificial aggregate (AA). However, the relatively high density of AA restricts its use in lightweight concrete products. This study aims to fully upcycle aluminum (Al) content in municipal solid waste incineration bottom ash (IBA) for H2 aeration in the production of lightweight artificial aggregate through alkali activation. To achieve this, the glass particles (GP) in IBA were ground into powder and used as the precursor for NaOH, while the remaining IBA (RIBA), rich in Al, served as the foaming agent. The results showed that RIBA particles (<300 μm) can be used to produce lightweight AA with a loose bulk density ranging from 780 to 840 kg/m3, comparable to sintered fly ash aggregates, and a wide pore size distribution ranging from 0.02 mm to over 1 mm. The inclusion of finer RIBA particles (<75 μm) enhanced the homogeneity of the pore structure, resulting in aggregate strengths of 0.4–0.6 MPa. Moreover, increasing the GP content in IBA up to 40% further boosted the aggregate strength to 1.1 MPa by refining the pore structure and promoting more (C)-N-A-S-H gels with Q4 structures. To ensure sufficient geopolymerization reactions and achieve high strength in the AAs, the alkali concentration should be kept above 3 mol/L. The proposed strategy for lightweight AA production reduced the global warming potential by about 20% compared to the conventional sintered method, offering a more environmentally friendly approach.

Catalytic Activity of Incorporated Palladium Nanoparticles on Recycled Carbon Black from Scrap Tires.

A stable support substrate for catalytically active metal nanoparticles (NPs) plays an important role in various chemical transformation reactions. This study describes the effective integration of catalytically active palladium nanoparticles (PdNPs) into recycled carbon black (rCB) obtained from scrap tires. The loading efficiency and dispersion degree of PdNPs prepared via a deposition-precipitation method are thoroughly compared to those prepared with conventional Vulcan CB. As the rCB powder exhibits relatively larger surface areas and wider pore size distributions, slightly polydisperse and more PdNPs are integrated across rCB than those on CB. These composite materials are subsequently tested as catalysts in the Suzuki coupling and styrene hydrogenation reactions. For the Suzuki reaction using phenylboronic acid and bromobenzene, the PdNPs on rCB exhibit slightly higher reactivity than those on CB (TOF of ∼9/h vs ∼8/h), presumably due to the structural features of the integrated PdNPs and the relatively hydrophobic characteristics of the rCB substrate. For the hydrogenation reaction, both composite materials easily result in over 99% yield under ambient conditions with similar activation energies of ∼32 kcal/mol. These composite materials are also recyclable in both reactions without a detectable loss of the PdNP catalyst and its activity. Understanding the physicochemical properties of rCB and demonstrating their potential use as a catalyst support substrate evidently suggest the possibility of replacing conventional CB, which also provides an idea of upcycling waste tires in the development of practical and green reaction systems.

Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States.

The first wide-view image of multiple structural and phase transformations for MOFs from crystal state transformations further to the extreme limit approaching liquid/glass phase, was presented based on a square-layer framework of [Co2(pybz)2(CH3COO)2]·DMF (Co2). The process involves i) an initial crystalline transformation brings to a 3-fold interpenetrated and ordered vacancies contained framework [Co(pybz)2(CH3OH)2]·2CH3OH (CoM) due to in-situ disassemble-reassemble, ii) thermal induced departure of a pair of cis-form coordinated methanol in CoM leads to amorphous framework (a-dCoM), iii) glass transition (Tg = 566 K) to super-cooled liquid (scl-dCoM, spanning 38 K), iv) obtaining MOF glass g-dCoM upon quenching the super-cooled liquid, and v) re-crystallization of super-cooled liquid to six-fold interpenetrated dia-net framework [Co(pybz)2]6n (rec-dCoM) under heating above 604 K. The access to glass from CoM, provides a new self-perturbation strategy to create more MOF glasses without melting. The wider pore size distribution in amorphous/glassy MOFs than crystalline precursor realized the first time selective hydrocarbon gas separation by breakthrough experiments, which bring efficient separation of 1:99 C2H2/C2H4 by either a-dCoM or g-dCoM and produce polymer grade C2H4 with purity ≥ 99.5% after a single adsorption process. Furthermore, the mixture of 50:50 C3H6/C3H8 can be separated by a-dCoM.

(Invited) Organic Electrochemical Bioelectronic Devices Based on 3D Conductive Polymer Scaffolds

The integration of 3D tissue-engineered microporous scaffolds based on conductive polymers (CPs) into bioelectronic devices have led to the possibility of dynamic monitoring of biological phenomena through electrical measurements. The 3D structure and morphology of the porous scaffolds mimics the topographical features of human physiology, while the electrically conductive nature of the polymers allows for electrical measurements for label-free monitoring and live-sensing of cells. 3D scaffolds based on the polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) prepared by the freeze drying process have been the focus of many studies and well integrated into bioelectronic devices such as electrodes[1] and organic electrochemical transistors[2].The influence of the different protocols and freezing rates on the pore size and structure was examined by scanning electron microscopy and micro computed tomography. Pores of circular and elongated ellipses were observed by SEM and a pore size distribution (the longest dimension of the ellipsoid) between 80 µm and 220 µm was measured. It was observed that a higher cooling rate generated larger pores with more elongated pore morphology as well as a wider pore size distribution. The pre-cooling treatment with 0.5°C/min cooling rate was most useful in generating scaffolds with a more homogenous pore structure and a pore size of approximately 100 µm.The different scaffolds were incorporated into electronic devices such as transmembrane electrodes to characterize the electrical properties and evaluate the reproducibility of the scaffolds prior to cell culture. No significant change in the electrochemical impedance spectra was observed despite the large difference in porosity of the different scaffolds. In addition, the different scaffolds were used to host and monitor biological cells like fibroblasts and endothelial cells. Cell growth and proliferation in the different scaffolds was also monitored by immunofluorescence microscopy. It was observed that a pre-cooling protocol and a freezing rate of 0.5°C/min helps to fabricate scaffolds with an optimized, uniform and homogenous pore morphology. This design protocol is highly beneficial in reducing the random artifacts of the nucleation process and generating scaffolds highly conducive to cell growth and survival and to create a versatile bioelectronic platform for studying in-vitro cell models.A new, sophisticated bioelectronic device was constructed with the scaffolds with the operation mode of an electrode and an organic electrochemical transistor. The device operation models an electrochemical cell with two or three electrodes and is used to build different in vitro organ models. In this presentation, I show the use of electrochemical techniques to monitor biological phenomenon based on 3D conducting polymer scaffolds.

An application of hierarchical MgAl hydrotalcite in the highly efficient treatment of oilfield macromolecular contaminants.

In this work, salicylic acid (SA) was used to induce the self-assembly of octadecyl trimethyl ammonium chloride (OTAC), a cationic surfactant, into three-dimensional wormlike micelle aggregates. These aggregates act as a soft template for hierarchical MgAl hydrotalcite (LDH) to create a multi-level pore structure adsorption material. Scanning electron microscopy characterization showed that the surface of the hierarchical hydrotalcite exhibited a dense layered structure, unlike the monolayer structure of ordinary hydrotalcite. Furthermore, the hierarchical MgAl-LDH possesses a significantly larger specific surface area (113.94 m2/g) and wide pore size distribution ranging more extensively from 2 to 80nm, which significantly has an impressive adsorption effect on sulfonated lignite (SL), with a maximum adsorption capacity of 192.7mg/g at pH = 7. Extensive research has been conducted on the adsorption mechanism of hierarchical MgAl-LDH, attributing it to surface adsorption due to the unique multi-level structure of the adsorbent. After two cycles of regeneration experiments, the adsorption capacity of the adsorbent remained at a high level of 179.1mg/g, demonstrating the excellent renewability of hierarchical MgAl-LDH. Moreover, the hierarchical hydrotalcite showed high adsorption capacity in the adsorption of sulfonated lignite, which was attributed to its larger specific surface area and superior pore structure to expose more active sites.

Mesophase pitch-derived porous carbon constructed by template/activation synchronous pore-forming technology for electrochemical energy storage

Porous carbon materials with high specific surface area and wide pore size distribution play a crucial role in the energy storage process. In this paper, a mixed sol-gel system of carbon source, chemical activator and salt template agent was constructed using raw pitch, o-xylene soluble substance and their mesophase as carbon source, NaCl as template agent and KOH as activator. After one step process of high temperature treatment, porous carbon materials with high specific surface area (SBET 1969 m2/g) and wide nanopore distribution (0.4–6 nm) were obtained. The electrochemical properties of the prepared mesophase porous carbon materials were tested. At a charge-discharge rate of 80 mA/g, a specific capacitance of 102.5 F/g can be achieved for porous carbon materials obtained from the o-xylene soluble mesophase, indicating the feasibility of preparing porous carbon electrode materials by o-xylene soluble mesophase. The development of template/activation synchronous pore-forming technology can integrate the advantages of the two kinds of pore-forming technologies, reduce the demand for pore size control in porous carbon materials, and promote the one-step realization of porous carbon materials with high specific surface area, wide pore size distribution and controllable pore size.

Construction of Hydrogels with Highly Salt-Resistant Honeycomb Porous Structures for Solar Desalination and Steam Generation.

Interfacial solar desalination is a method for desalinating seawater using solar energy, and the long-term use of this technology requires a stable evaporation rate and some ability to prevent salt crystallization. To address these issues, carbonized polydopamine-coated bentonite (C@PBT), poly(vinyl alcohol), and cellulose nanofibers were used to construct a three-dimensional oriented hydrogel evaporator with a multilayered honeycomb porous structure for long-term desalination. Carbon nanoparticles transferred between the layers of the bentonite, which increases the spacing of the layers and confers a more effective solar light trapping ability. The evaporation rate was 2.26 kg m-2 h-1 in 20 wt % NaCl solution, and no salt crystals were precipitated from the surface of the evaporator in 12 h of continuous operation. This phenomenon occurs due to the wide distribution of pore sizes and the large size of the pores within the evaporator, which create ample space for salt ions to move freely. Furthermore, after undergoing 300 cycles of compression, its internal pore structure remains intact, and the rate of evaporation remains stable. It ensures the evaporator stability during outdoor cycles. The research work provides an effective method to solve the salt accumulation problem and shows its great potential for application.

Ultramicroporous cardo-pendant polyamide nanofilms for enhanced organic solvent nanofiltration

Permeable, selective, and stable polymeric membranes are essential for efficient molecular separation in organic solvents. Polymers of intrinsic microporosity (PIMs) with rigid and twisted chain structures offer abundant pores for high solvent permeability and are emerging as an ideal membrane material. However, guaranteeing high separation selectivity and stability is challenging owing to the wide pore size distribution and low swelling resistance in organic solvents. In this work, we developed intrinsically ultramicroporous polyamides (PAs) with cardo-pendant groups to create crosslinking, ultrathin, and defect-free nanofilms for organic solvent nanofiltration. The molecular simulation confirmed the pivotal role of cardo-pendant group structures in the amine monomers and exhibited their effect in creating pore channel structures within the PAs. Distinctive rigid fluorenyl-based cardo-pendant groups were introduced in amine monomers to finely tailor the packing of PA chains for high ultramicroporosity and a finely tuned pore size. We further achieved the growth of such PAs using a cyclic deposition strategy, in-situ generating highly crosslinking nanofilms with an ultralow thickness of 23–36 nm without structure relaxation. As such, the typically-designed PA membranes demonstrated high and stable solvent permeance (e.g., 18 L m−2 h−1 bar−1 for methanol) and high solute rejection (up to 95 % rejection of 306 Da Azure I), which is superior to its counterparts and current PIM membranes, presenting a new perspective for efficient organic solvent nanofiltration.

Fluid entrapment during forced imbibition in a multidepth microfluidic chip with complex porous geometry

Understanding and controlling fluid entrapment during forced imbibition in porous media is crucial for many natural and industrial applications. However, the microscale physics and macroscopic consequences of fluid entrapment in these geometric-confined porous media remain poorly understood. Here, we introduce a novel multidepth microfluidic chip, which can mitigate the depth confinement of traditional two-dimensional (2-D) microfluidic chips and mimic the wide pore size distribution as natural-occurring three-dimensional (3-D) porous media. Based on microfluidic experiments and direct numerical simulations, we observe the fluid-entrapment scenarios and elucidate the underlying complex interaction between geometric confinement, capillary number and wettability. Increasing depth variation can promote fluid entrapment, whereas increasing capillary number and contact angle yield the opposite effect, which seemingly contradicts conventional expectations in traditional 2-D microfluidic chips. The fluid-entrapment scenario in depth-variable microfluidic chips stems from microscopic interfacial phenomena, classified as snap-off and bypass events. We provide theoretical analyses of these pore-scale events and validate corresponding phase diagrams numerically. It is shown that increasing depth variation triggers snap-off and bypass events. Conversely, a higher capillary number suppresses snap-off events under strong imbibition, and an increased contact angle inhibits bypass events under imbibition. These macroscopic imbibition patterns in microfluidic porous media can be linked with these pore-scale events by improved dynamic pore-network models. Our findings bridge the understanding of forced imbibition between 2-D and 3-D porous media and provide design principles for newly engineered porous media with respect to their desired imbibition behaviours.

Sunflower-like missing-linker covalent organic framework for efficient extraction of non-steroidal anti-inflammatory drugs.

As excellent crystalline materials, covalent organic frameworks (COFs) are widely used in drug adsorption. In this work, a defective engineering strategy was proposed for designing and preparing the functionalized end-capping monomer and missing-linker COFs. The missing-linker COF 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde compound with glycidyltrimethyl ammonium chloride modified benzene-1,4-diamine (TpPa-GTA) was synthesized through Schiff base reaction with wide pore size distribution for adsorption of four nonsteroidal anti-inflammatory drugs (NSAIDs). The adsorption process follows pseudo-second-order kinetics, and the four drugs reached adsorption equilibrium within 10 min. The sunflower-like structure helps to promote intraparticle diffusion during the adsorption process, thereby realizing the rapid adsorption of TpPa-GTA. The equilibrium isotherms fit well with both the Freundlich and Langmuir models, with a maximum adsorption capacity of 83.3-315 mg g-1 calculated from the Langmuir model. Based on the detection results of Zeta potential and XPS, the adsorption mechanism was inferred, and the rapid capture of NSAIDs in the wide pH range of 4.0 to 7.5 was realized under electrostatic interaction, hydrogen bonding, and π-π interaction. The detection of lake and river samples using the missing adapter TpPa-GTA has a recovery rate of 84.2-117%, which provides a new approach to the adsorption of pollutants with COFs.

Highly dispersed ultrafine PtCo alloy nanoparticles on unique composite carbon supports for proton exchange membrane fuel cells.

The design of highly efficient and robust platinum-based electrocatalysts is pivotal for proton exchange membrane fuel cells (PEMFC). One of the long-standing issues for PEMFC is the rapid deactivation of the catalyst under working conditions. Here, we report a simple synthesis strategy for ultrafine PtCo alloy nanoparticles loaded on a unique carbon support derived from a zeolitic imidazolate framework-67 (ZIF-67) and Ketjen Black (KB) composite, exhibiting a remarkable catalytic performance toward the oxygen reduction reaction (ORR) and PEMFC. Benefitting from the N-doping and wide pore size distribution of the composite carbon supports, the growth of PtCo nanoparticles can be evenly restricted, leading to a uniform distribution. The Pt-integrated catalyst delivers an outstanding electrochemical performance with a mass activity that is 8.6 times higher than that of the commercial Pt/C catalyst. Impressively, the accelerated durability test (ADT) demonstrates that the hybrid carbon support can significantly enhance the durability. Theoretical simulations highlight the synergistic contribution between the supports and the PtCo nanoparticles. Moreover, hydrogen-oxygen fuel cells assembled with the catalyst exhibited a high power density of 1.83 W cm-2 at 4 A cm-2. These results provide a new opportunity to design advanced catalysts for PEMFC.

Unveiling the Potential: Selecting Optimal Materials for Physical Pools in a Pavement-Runoff-Integrated Treatment System

Pavement runoff contains complex pollutants that can lead to environmental pollution and health risks. A pavement-runoff-integrated treatment system has been recognized as an effective way to deal with pavement runoff pollution. However, there is little support for selecting appropriate materials for physical pools due to a lack of understanding of the selective filtration and physical adsorption characteristics. In this study, gravel and activated carbon were chosen as the substrate materials for physical filtration and adsorption pools, and their corresponding purification characteristics were investigated using an indoor scaled down model. The results showed that the removal rate of all pollutants was related to the size of the gravel used. This was mainly due to the increased gravel particle size and voids, which resulted in a higher water velocity, shorter hydraulic retention time, and inadequate filtration. Compared with coconut shell granular activated carbon (GAC) and coal column activated carbon (EAC), analytically pure granular activated carbon (ARAC) showed a better removal rate for petroleum and heavy metals. This is mainly because ARAC has a larger specific surface area, higher pore volume, and wider pore size distribution, resulting in a remarkable adsorption capacity for pollutants. Overall, the combination of 0.3 mm gravel and ARAC was found to be the most suitable for use as filtration and adsorption materials for physical pools. These findings offer a gravel- and ARAC-based pavement-runoff-integrated treatment system, which has excellent potential to enhance the removal of pollutants from pavement runoff.

Highly efficient ethylene/ethane separation via molecular sieving using chitosan-derived ultramicroporous carbon

The selective separation of C2H4/C2H6 pair is of paramount importance in the petrochemical industry, which is yet challenged by their similar polarities, shapes, and kinetic diameters. The use of carbonaceous adsorbents with molecular sieving capability holds great promise in achieving the desired selectivity and economically feasibility. However, such progress has been hindered by the typically wide pore size distribution observed in traditional carbons. Herein, we report a series of chitosan-based ultramicroporous carbons with C2H4/C2H6 molecular sieving performance through an activating reagents-free method. The hydrothermal process of chitosan was initially employed to prepare condensed carbonaceous hydrochar rich in heteroatoms. The subsequent thermal etching led to the formation of sieving-based ultramicropores, stemming from the decomposition of heteroatoms and hot-shrinkage of pores at high temperature. The as-synthesized optimal CNC-700 sample achieved a high C2H4 uptake of 32.3 cm3 (STP) g−1 and negligible C2H6 adsorption at 298 K and 1.0 bar. The isosteric heat of C2H4 on CNC-700 reached 34.5 kJ mol−1, significantly lower than other thermodynamically driven carbonaceous adsorbents. The fixed-bed breakthrough experiments further validated the efficient separation of equimolar C2H4/C2H6 mixture under dynamic conditions. This work provides an important guideline to fabricate carbons with adjustable ultramicropore size derived from biomass for the highly effective separation of light hydrocarbons via molecular sieving.

Study of the effect of the morphology of initial powders on the structural and dimensional characteristics of SiC-based porous ceramic materials

The realization of the necessary energy-efficient technological solutions for the production of highly porous SiC-ceramic materials requires appropriate research. The results of developing energy-efficient one-step methods for the synthesis of porous SiC-based ceramics and studying the characteristics of the obtained ceramics are presented. The effect of the morphology of initial powders on the synthesized product is considered. Ultrafine silicon carbide powders of two types, identical in characteristic particle size, but quite different in the surface morphology, were used as fillers in the synthesis of experimental samples of porous ceramics. The first one was obtained by the traditional furnace method (SiCf), the second one was synthesized by the technology of self-propagating high-temperature synthesis (SiCshs). It is shown that the particle morphology of initial powder components determines the structural parameters and characteristics of synthesized porous ceramics. The pore space parameters (average pore size, specific surface area, equivalent hydraulic diameter, permeability, etc.) can vary significantly. Porous ceramic materials synthesized on the basis of SiCf have an open porosity of 47%, high liquid permeability (up to 2 mDarcy), overwhelming dominance of α-SiC phase, and a narrow pore distribution with an average pore size of about 1 μm. High open porosity (more than 58 %), highly developed nanostructured pore space surface with an area of more than 12 m2/g, and wider pore size distribution (average pore size — 140 nm) are observed in porous ceramic materials based on SiCshs. The obtained results can be used to improve energy-efficient synthesis technologies and methods for predicting the properties of highly porous SiC-based ceramic materials. This will make it possible to create highly porous SiC ceramics within a priory predicted limits of effective applicability for the processes of ultrafiltration or catalysis.

Activate the filtration capability of 3.5 nm ultra-large pores and eliminate the requirement of pore homogeneity for carbon nanotube array membranes

Vertical array carbon nanotube (VACNT) membrane is considered as one of the most promising materials for seawater desalination due to its excellent porosity, strong mechanical properties and atomic smoothness of the inner wall. However, in practical applications, the synthesis of highly oriented VACNT arrays with uniform pore sizes (< 1.1 nm) needs to be strictly controlled, and achieving high permeability-retention for large pores (> 1.1 nm) is a great challenge. Here, we use molecular dynamics simulations to introduce the oscillation paradigm into VACNT filtration membranes with a heterogeneous pore network with a wide pore size distribution (ranging from 1 nm to 3.5 nm). Notably, the oscillating heterogeneous VACNT membrane achieved ultra-high permeability of 1421.8 L/cm2/day/MPa (~5 times speed increase in comparison with homogeneous VACNT and ~ 2 times over state-of-the-art CNT membranes), while maintaining a selectivity of 97.5 %. This method activates the filtration capacity of 3.5 nm ultra-large pores, eliminating the requirement for pore homogeneity in VACNT, and achieves the effect of “killing two birds with one stone”. In addition, the filtration performance of specific heterogeneous VACNT membrane was successfully predicted by water permeability curve fitting, which provided valuable theoretical guidance for the design of high-performance VACNT reverse osmosis desalination system.

Effect of acid/alkali treatment on the structure and catalytic performance of 3DOM CeCo0.7Mn0.3O3 catalyst.

In this work, Ce was used as the A-site element and three-dimensional ordered macroporous (3DOM) materials as the template to obtain 3DOM CeCo0.7Mn0.3O3 catalyst via excessive impregnation method. The catalyst was subjected to acid/alkali treatment with dilute nitric acid and sodium hydroxide solutions. The results revealed that the catalysts subjected to acid/alkali treatment exhibited better structural and catalytic activity characteristics than the bulk catalyst. Specifically, the specific surface area of the catalyst treated with acid increased from 34.86 to 60.67 m2·g-1, and the relative contents of Oads and Mn4+ species increased. Moreover, the T90% further decreased to 174 °C. As for the catalyst treated with alkali, it exhibited a rougher surface and a wider pore size distribution, producing more lattice defects which were favorable for reaction progress. The T90% was 183 °C, indicating that acid/alkali treatment both had a positive effect on the catalytic oxidation of toluene.

Facile Preparation of Dense Polysulfone UF Membranes with Enhanced Salt Rejection by Post-Heating.

Polysulfone (PSf) membranes typically have a negligible rejection of salts due to the intrinsic larger pore size and wide pore size distribution. In this work, a facile and scalable heat treatment was proposed to increase the salt rejection. The influence of heat treatment on the structure and performance of PSf membranes was systematically investigated. The average pore size decreased from 9.94 ± 5.5 nm for pristine membranes to 1.18 ± 0.19 nm with the increase in temperature to 50 °C, while the corresponding porosity decreased from 2.07% to 0.13%. Meanwhile, the thickness of the sponge structure decreased from 20.20 to 11.5 μm as the heat treatment temperature increased to 50 °C. The MWCO of PSf decreased from 290,000 Da to 120 Da, whereas the membrane pore size decreased from 5.5 to 0.19 nm. Correspondingly, the water flux decreased from 1545 to 27.24 L·m-2·h-1, while the rejection ratio increased from 3.1% to 74.0% for Na2SO4, from 1.3% to 48.2% for MgSO4, and from 0.6% to 23.8% for NaCl. Meanwhile, mechanism analysis indicated that the water evaporation in the membranes resulted in the shrinkage of the membrane pores and decrease in the average pore size, thus improving the separation performance. In addition, the desalting performance of the heat-treated membranes for real actual industrial wastewater was improved. This provides a facile and scalable route for PSf membrane applications for enhanced desalination.

Manufacture of mirco-meso-macroporous ACNF/PANI/MIL-101(Cr)-NH2 composites with exceptional adsorption phenomenon for indomethacin

Exploiting advanced adsorbents for the elimination of the alarming level of nonsteroidal anti-inflammatory drugs (NSAIDs) pollution has sparked extensive research attention. Herein, taking acid-treated carbon nanofiber (ACNF) as composite skeleton, a unique ACNF/polyaniline/MIL-101(Cr)-NH2 (ACNF/PANI/MIL-101(Cr)-NH2) with robust 3D-supporting framework and tertiary pore structure was synthesized to remove indomethacin (IDM). Considering the large BET surface area (SBET), wide pore size distribution, highly-exposed active sites and affluent functional groups, ACNF/PANI/MIL-101(Cr)-NH2 depicted a standout adsorption capacity of 400.1 mg/g for IDM, which was far superior to most reported adsorbents. Moreover, ACNF/PANI/MIL-101(Cr)-NH2 acquired rapid adsorption kinetics, wonderful reusability and stability. Ulteriorly, inspired by the electrode fabrication craft, one easy-to-recyclable ACNF/PANI/MIL-101(Cr)-NH2 taking graphite felt (GF) as carrier was manufactured and achieved superior adsorption capacity as well as satisfactory reusability. The adsorption mechanism was appraised via Fourier-transformed infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The experimental data disclosed that the superior adsorption capability mainly depended on the electrostatic interaction, hydrogen bonding and π-π interaction. Overall, this work sheds light on one feasible strategy to develop advanced adsorbents in practical wastewater treatment.

Mechanism of heel build-up on adsorbents through oxygen induced reactions

Oxygen induced reactions during the desorption of volatile organic compounds (VOCs) from adsorbents (such as activated carbon) promote heel buildup and reduce the adsorbent’s lifetime. This study aims to improve the understanding of heel build-up mechanisms in the presence of oxygen in the desorption purge gas. Three activated carbons (ACs) and one zeolite adsorbent were exposed to an extreme condition of 1,2,4-trimethylbenzene (TMB) and high oxygen concentration at three temperatures (150, 200, and 250 °C). Thermogravimetric analysis and gas chromatography-mass spectrometry (GC–MS) were used to assess the thermal stability and chemical structure of the formed heel, respectively. Additionally, nitrogen adsorption was performed to evaluate the effect of heel formation on the adsorbent’s pore properties. Increasing the desorption temperature in the presence of oxygen was found to reduce the BET surface area and increase the oxygen-induced reactions on the adsorbents. Among the three tested temperatures, minimum heel formation was obtained at the intermediate temperature, 200 °C. Compared to zeolite, ACs were more susceptible to oxygen induced reactions at elevated temperatures due to their wide pore size distribution. Further analysis using GC–MS revealed that oxygen presence during the desorption process can form a broad range of organic species in terms of molecular weight, chemical structure, and functional group.