Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi-Purpose Polyamine Functionalization.

2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10-30 nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm2 and GO layer thicknesses of ≈500 nm are fabricated, and they exhibited a stable dye water permeance of 75 L m-2 h-1 bar-1, rejection of >99.5% for Direct red and Congo red, and Na2SO4/dye separation factor of 300-500, superior to state-of-the-art commercial membranes. The versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.

Amine-Functionalized Metal-Free Nanocarbon to Boost Selective CO2 Electroreduction to CO in a Flow Cell.

Highly efficient electrochemical CO2-to-CO conversion is a promising approach for achieving carbon neutrality. While nonmetallic carbon electrocatalysts have shown potential for CO2-to-CO utilization in H-type cells, achieving efficient conversion in flow cells at an industrial scale remains challenging. In this study, we present a cost-effective synthesis strategy for preparing ultrathin 2D carbon nanosheet catalysts through simple amine functionalization. The optimized catalyst, NCNs-2.5, demonstrates exceptional CO selectivity with a maximum Faradaic efficiency of 98% and achieves a high current density of 55 mA cm-2 in a flow cell. Furthermore, the catalyst exhibits excellent long-term stability, operating continuously for 50 h while maintaining a CO selectivity above 90%. The superior catalytic activity of NCNs-2.5 is attributed to the presence of amine-N active sites within the carbon lattice structure. This work establishes a foundation for the rational design of cost-effective nonmetallic carbon catalysts as sustainable alternatives to metals in energy conversion systems.

New porous amine-functionalized biochar-based desiccated coconut waste as efficient CO2 adsorbents.

Climate change caused by the greenhouse gases CO2 remains a topic of global concern. To mitigate the excessive levels of anthrophonic CO2 in the atmosphere, CO2 capture methods have been developed and among these, adsorption is an especially promising method. This paper presents a series of amine functionalized biochar obtained from desiccated coconut waste (amine-biochar@DCW) for use as CO2 adsorbent. They are ethylenediamine-functionalized biochar@DCW (EDA-biochar@DCW), diethylenetriamine-functionalized biochar@DCW (DETA-biochar@DCW), triethylenetetramine-functionalized biochar@DCW (TETA-biochar@DCW), tetraethylenepentamine-functionalized biochar@DCW (TEPA-biochar@DCW), and pentaethylenehexamine-functionalized biochar@DCW (PEHA-biochar@DCW). The adsorbents were obtained through amine functionalization of biochar and they are characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, Brunauer-Emmett-Teller (BET), and thermogravimetric analysis (TGA). The CO2 adsorption study was conducted isothermally and using a thermogravimetric analyzer. From the results of the characterization analyses, a series of amine-biochar@DCW adsorbents had larger specific surface area in the range of 16.2 m2/g-37.1 m2/g as compare to surface area of pristine DCW (1.34 m2/g). Furthermore, the results showed an increase in C and N contents as well as the appearance of NH stretching, NH bending, CN stretching, and CN bending, suggesting the presence of amine on the surface of biochar@DCW. The CO2 adsorption experiment shows that among the amine modified biochar adsorbents, TETA-biochar@DCW has the highest CO2 adsorption capacity (61.78 mg/g) when using a mass ratio (m:m) of biochar@DCW:TETA (1:2). The adsorption kinetics on the TETA-biochar@DCW was best fitted by the pseudo-second model (R2 = 0.9998), suggesting the adsorption process occurs through chemisorption. Additionally, TETA-biochar@DCW was found to have high selectivity toward CO2 gas and good reusability even after five CO2 adsorption-desorption cycles. The results demonstrate the potential of novel CO2 adsorbents based on amine functionalized on desiccated coconut waste biochar.

Surface modifications of biopolymers for removal of per- and polyfluoroalkyl substances from water: Current research and perspectives.

Per- and polyfluoroalkyl substances (PFAS) are highly recalcitrant organic contaminants that have attracted ever-increasing attention from the general public, government agencies and scientific communities. To remove PFAS from water, especially the enormous volume of drinking water, stormwater, and groundwater, sorption is the most practical approach. Success of this approach demands green, renewable, and sustainable materials for capturing PFAS at ng/L or µg/L levels. To meet this demand, this manuscript critically reviewed sorbents developed from biopolymers, such as chitosan (CTN), alginate (ALG), and cellulose (CEL) covering the period from 2008 to 2023. The use of different cross-linkers for the surface modifications of biopolymers were described. The underlying removal mechanism of biosorbents for PFAS adsorption from molecular perspectives was discussed. Besides reviewing and comparing the performance of different bio-based sorbents with respect to environmental factors like pH, and sorption kinetics and capacity, strategies for modifying biosorbents for better performance were proposed. Additionally, approaches for regeneration and reuse of the biosorbents were discussed. This was followed by further discussion of challenges facing the development of biosorbents for PFAS removal.

Reinforcement of Aminopropyl-Terminated Siloxane-Treated Carbon Nanotubes in Epoxy Thermosets: Mechanical and Thermal Properties.

The synthesis and characterization of aminopropyl-terminated polydimethylsiloxane- treated carbon nanotube (AFCNT)-reinforced epoxy nanocomposites are reported in the current study. The amine functionalization of the CNTs was performed with a reaction to PDMS-NH2. The AFCNTs were homogeneously dispersed in epoxy resin by using an emulsifier and a three-roller mill. The AFCNTs were characterized using Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The curing behavior of the epoxy/AFCNT was studied using a differential scanning calorimeter (DSC). The tensile and impact strengths of the 2.0 wt.% AFCNT-reinforced epoxy nanocomposite were enhanced by 43.2% and 370%, respectively. Moreover, the glass transition temperature (Tg) was also enhanced by 21 °C. Furthermore, significant enhancements were observed in the initial degradation and char yield values. SEM results confirmed that the AFCNTs were highly dispersed in the polymeric matrix.

Interfacial molecular regulation of TiO2 for enhanced and stable cocatalyst-free photocatalytic hydrogen production.

On the basis of the inherent property limitations of commercial P25-TiO2, many surface interface modification methods have attracted substantial attention for further improving the photocatalytic properties. However, current strategies for designing and modifying efficient photocatalysts (which exhibit complicated manufacturing processes and harsh conditions) are not efficient for production that is low cost, is nontoxic, and exhibits good stability; and therefore restrict practical applications. Herein, a facile and reliable method is reported for in situ amine-containing silane coupling agent functionalization of commercial P25-TiO2 by covalent surface modification for constructing a highly efficient photocatalyst. As a consequence, a high efficiency of H2 evolution was achieved for TiO2-SDA with 0.95 mmol h-1 g-1 (AQE ∼45.6 % at 365 nm) under solar light irradiation without a co-catalyst. The amination modification broadens the light absorption range of the photocatalyst, inhibits the binding of photogenerated carriers, and improves the photocatalytic efficiency; which was verified by photochemical properties and DFT theoretical calculations. This covalent modification method ensures the stability of the photocatalytic reaction. This work provides an approach for molecularly modified photocatalysts to improve photocatalytic performance by covalently modifying small molecules containing amine groups on the photocatalyst surface.

Amine-Modified Carbon Xerogels as Effective Carbon-Based Adsorbents of Anionic Dye from Aqueous Solutions.

Carbon xerogels were obtained by polycondensation of resorcinol and formaldehyde in a water medium. Their surface was oxidized by ammonium persulfate and then modified with amine groups. Four amines were used: methylamine, ethylamine, propylamine, and ethylenediamine, differing in carbon chain length and number of amine groups. The materials were characterized by low-temperature nitrogen sorption, elemental analysis, thermal analysis, X-ray diffraction, infrared spectroscopy, and determination of the surface oxygen group content with the use of the Boehm method. The final carbon adsorbents had surface areas ranging from 172-663 m2/g and acid-base nature. They were applied for adsorption of thymol blue from water solution. The sorption capacities of the studied adsorbents ranged from 83 to 140 mg/g. The presence of amine groups on the xerogel surface was found to increase its sorption capacity towards the dye studied. The dye adsorption process is endothermic and spontaneous, as indicated by the positive values of ΔH and the negative values of ΔG, respectively. The kinetics of adsorption of thymol blue was established to be described by the pseudo-second-order model. The equilibrium data were analyzed by the Langmuir and Freundlich models. The character of thymol blue adsorption is much better described by the Langmuir isotherm.

Adsorption of CO2 by a novel zeolite doped amine modified ternary aerogels.

Novel amine functionalized materials can capture greenhouse gas CO2. In this study, SiO2-Al2O3-ZrO2 ternary composite aerogel was prepared by sol-gel method, supercritical drying, ultrasonic non-in-situ synthesis and other processes using aluminum chloride hexahydrate as aluminum source, ethyl orthosilicate as silicon source and tetrabbutyl zirconate as zirconium source. The composite material was used as the carrier material. By impregnation method, the modified agent bis - (3-trimethoxy-silpropyl) amine and the composite were fully mixed and modified, and the novel zeolite doped amine functionalized ternary composite aerogel was obtained by doping acidification activation zeolite. The results show that the prepared novel zeolite amine-modified ternary aerogels have rich microporous structure and ordered mesoporous structure. After loading different contents of amine-based materials (CAA-X) in the ternary aerogels, the comparison between CAAZ-X and zeolite amine-modified ternary aerogels is conducted. Zeolite doped CAAZ-30 material shows the best adsorption performance, with a maximum adsorption capacity of 5.30 mmol/g. In the presence of water vapor, CAAZ-30 material also showed the best adsorption performance, with a maximum adsorption capacity of 5.33 mmol/g. This can help us design suitable adsorbent materials for CO2 capture in different practical applications.

NH2-CuO-MCM-41 covalently cross-linked multipurpose membrane for applications in water treatment: Removal of hazardous pollutants from water, water desalination and anti-biofouling performance.

The current study was planned to fabricate a new set of membranes to target multiple application areas such as desalting, removal of micropollutants and antibiofouling performance. In-situ incorporated copper oxide to MCM-41 (CuO-MCM-41) was synthesized and amine (-NH2) functionalized by reacting with N1-(3-trimethoxy silylpropyl) diethylenetriamine (NTSDETA) yielding NH2-CuO-MCM-41. Different concentrations of NH2-CuO-MCM-41 were covalently cross-linked in polyamide active layer during interfacial polymerization (IP) between N, N'-bis(3-aminopropyl)ethylenediamine and terephthaloyl chloride (TPC) on polysulfone/poly ester terephthalate (PS/PET) support. The membranes were extensively characterized by Water Contact Angle (WCA), Scanning Electron Microscopy (SEM), Fourier Transform Infra-red (FTIR) spectroscopy, Energy Dispersive X-ray (EDX) analysis, Elemental mapping and Powder X-ray Diffraction (PXRD). From among the different versions of X-CuO-MCM-41/PA@PS/PET membranes, the 0.05%-CuO-MCM-41/PA@PS/PET membrane showed best performance in terms of rejecting a variety of salts, micropollutants and antibiofouling. The 0.05%-CuO-MCM-41/PA@PS/PET showed >98% rejection of MgCl2 and 78% rejection of caffeine with a permeate flux of 16 LMH at 25 bar. The 0.1-NH2-CuO-MCM-41inhibited S. aureus growth by 51.7%. Hence, the current strategy of membrane fabrication proved to be highly efficient for multipurpose applications in water treatment.

Facile preparation of amine -functionalized corn husk derived activated carbon for effective removal of selected heavy metals from battery recycling wastewater.

In this work, an efficient and eco-friendly amine functionalized corn husk derived activated carbon with high adsorption capacity was prepared and utilized for Pb (II), Cu(II) and Ni(II) ions removal from battery recycling wastewater. The developed adsorbent was characterized to determine the surface morphology, elemental composition, surface chemistry and surface area using SEM/EDS, FTIR and BET techniques. The BET surface area of the corn husk (CH) and amine-functionalized corn husk activated carbon (AF-CHAC) was found to be 92.11 and 442.70 m2/g, respectively. The effect of adsorption variables which includes temperature, pH, contact time, and adsorbent dosage on uptake behaviour were all examined. Langmuir, Freundlich, Harkin-Jura, Elovich, and D-R isotherm models were fitted to the adsorption data. The adsorption of Pb (II), Cu(II), and Ni (II) ions followed a pseudo-second order kinetic and fit well to the Freundlich isotherm, indicating multi-layer adsorption and chemisorption. The maximum adsorption capacity of Pb(II), Cu(II), and Ni(II) ions, was 2.814, 0.724, and 0.337 mg/g, respectively. According to the thermodynamic parameter values, the adsorption process was spontaneous, exothermic, and physical in nature, with an increase in randomness at the adsorbates-adsorbent interaction. The desorption and reusability experiments revealed that the AF-CHAC has a greater potential as an adsorbent, with a removal efficiency of 99 % after three cycles. Overall, the prepared amine functionalized corn husk derived activated carbon has advantages such as ease of preparation, cost effectiveness, and excellent recyclability, as well as high adsorption capacity, providing a new approach for efficiently treating battery recycling wastewater contaminated with heavy metal ions.

Kinetics and Adsorption Isotherms of Amine-Functionalized Magnesium Ferrite Produced Using Sol-Gel Method for Treatment of Heavy Metals in Wastewater.

This study is focused on the kinetics and adsorption isotherms of amine-functionalized magnesium ferrite (MgFe2O4) for treating the heavy metals in wastewater. A sol-gel route was adopted to produce MgFe2O4 nanoparticles. The surfaces of the MgFe2O4 nanoparticles were functionalized using primary amine (ethanolamine). The surface morphology, phase formation, and functionality of the MgFe2O4 nano-adsorbents were studied using the SEM, UV-visible, FTIR, and TGA techniques. The characterized nanoparticles were tested on their ability to adsorb the Pb2+, Cu2+, and Zn2+ ions from the wastewater. The kinetic parameters and adsorption isotherms for the adsorption of the metal ions by the amine-functionalized MgFe2O4 were obtained using the pseudo-first-order, pseudo-second-order, Langmuir, and Freundlich models. The pseudo-second order and Langmuir models best described the adsorption kinetics and isotherms, implying strong chemisorption via the formation of coordinative bonds between the amine groups and metal ions. The Langmuir equation revealed the highest adsorption capacity of 0.7 mmol/g for the amine-functionalized MgFe2O4 nano-adsorbents. The adsorption capacity of the nanoadsorbent also changed with the calcination temperature. The MgFe2O4 sample, calcined at 500 °C, removed the most of the Pb2+ (73%), Cu2+ (59%), and Zn2+ (62%) ions from the water.

Amine-Wetting-Enabled Dendrite-Free Potassium Metal Anode.

Considered as an imperative alternative to the commercial LiFePO4 battery, the potassium metal battery possesses great potential in grid-scale energy storage systems due to the low cost, low standard redox potential, and high abundance of potassium. The potassium dendrite growth, large volume change, and unstable solid electrolyte interphase (SEI) on the potassium metal anode have, however, hindered its applications. Although conductive scaffolds coupling with potassium metal have been widely proposed to address the above issues, it remains challenging to fabricate a uniform composite with uncompromised capacity. Herein, we propose a facile and efficient strategy to construct dendrite-free and practical carbon-based potassium composite anodes via amine functionalization of the carbon scaffolds that enables fast molten potassium infusion within several seconds. On the basis of experiments and theoretical calculations, we show that highly potassiophilic amine groups immediately transform carbon scaffolds from nonwetting to wetting to postassium. Our carbon-cloth-based potassium composite anode (K@CC) can accommodate volume fluctuation, provide abundant nucleation sites, and lower the local current density, achieving nondendritic morphology with a stable SEI. The fabricated K0.7Mn0.7Ni0.3O2|K@CC full cell displays excellent rate capability and an ultralong lifespan over 8000 cycles (68.5% retention) at a high current of 1 A g-1.

Design and development of biomimetic electrospun sulphonated polyether ether ketone nanofibrous scaffold for bone tissue regeneration applications: in vitro and in vivo study.

Bone defect restoration remains challenging in orthopedic medical practices. In this study an attempt is carried out to probe the use of new biomimetic SPEEK (sulfonated polyether ether ketone) based nanofibrous scaffold to deliver amine functionalized hydroxyapatite nanoparticles loaded resveratrol for its potent functionality in osteogenic differentiation. SPEEK polymer with reactive functional group SO3H was synthesized through process of sulphonation reaction. Amine functionalized nanoparticles with protonated amino groups revamp the molecular interaction by the formation of hydrogen bonds that in turn intensify the bioactivity of the nanofibrous scaffold. Osteoconductive functionalized nanohydroxyapatite enhances the cell proliferation and osteogenicity with improved cell attachment and spreading. The results of FT-IR, XRD, Carbon-Silica NMR and EDX analysis confirmed the amine functionalization of the hydroxyapatite nanoparticles. Surface morphological analysis of the fabricated nanofibers through SEM and AFM analysis shows vastly interconnected porous structure that mimics the bone extracellular matrix, which enhances the cell compatibility. Cell adhesion and live dead assay of the nanoscaffolds express less cytotoxicity. Mineralization and alkaline phosphatase assay establish the osteogenic differentiation of the nanofibrous scaffold. The in vitro biocompatibility studies reveal that the fabricated scaffold was osteo-compatible with MG63 cell lines. Hemocompatibility study further proved that the designed biomimetic nanofibrous scaffold was highly suitable for bone tissue engineering. The results of in vivo analysis in zebrafish model for the fabricated nanofibers demonstrated significant increase in the caudal fin regeneration indicating mineralization of osteoblast. Thus, the commending results obtained instigate the potentiality of the composite nanofibrous scaffold as an effective biomimetic substrate for bone tissue regeneration.

Amine-Functionalized Silver Nanoparticles: A Potential Antiviral-Coating Material with Trap and Kill Efficiency to Combat Viral Dissemination (COVID-19).

The outbreak of COVID-19 has drastically affected the daily lifestyles of people globally where specific Coronavirus-2 transmits primarily by respiratory droplets. Structurally, the SARS-CoV-2 virus is made up of four types of proteins in which S-protein is indispensable among them, as it causes rapid replication in the host body. Therefore, the glycine and alanine composed of HR1 of S-protein is the ideal target for antiviral action. Different forms of surface-active PPEs can efficiently prevent this transmission in this circumstance. However, the virus can survive on the conventional PPEs for a long time. Hence, the nanotechnological approaches based on engineered nanomaterials coating on medical equipments can potentially prevent the dissemination of infections in public. Silver nanoparticles with tuneable physicochemical properties and versatile chemical functionalization provide an excellent platform to combat the disease. The coating of amine-functionalized silver nanoparticle (especially amine linked to aliphatic chain and trialkoxysilane) in its nanostructured form enables cloths trap and kill efficient. PPEs are a primary and reliable preventive measure, although they are not 100% effective against viral infections. So, developing and commercializing surface-active PPEs with trap and kill efficacy is highly needed to cope with current and future viral infections. This review article discusses the COVID-19 morphology, antiviral mechanism of Ag-NPs against SARS-CoV-2 virus, surface factors that influence viral persistence on fomites, the necessity of antiviral PPEs, and the potential application of amine-functionalized silver nanoparticles as a coating material for the development of trap and kill-efficient face masks and PPE kits.

Amine-Functionalized Carbon Nanodot Electrocatalysts Converting Carbon Dioxide to Methane.

The electrochemical conversion of carbon dioxide (CO2 ) to methane (CH4 ), which can be used not only as fuel but also as a hydrogen carrier, has drawn great attention for use in supporting carbon capture and utilization. The design of active and selective electrocatalysts with exceptional CO2 -to-CH4 conversion efficiency is highly desirable; however, it remains a challenge. Here a molecular tuning strategy-in situ amine functionalization of nitrogen-doped graphene quantum dots (GQDs) for highly efficient CO2 -to-CH4 conversion is presented. Amine functionalized nitrogen-doped GQDs achieve a CH4 Faradic efficiency (FE) of 63% and 46%, respectively, at CH4 partial current densities of 170 and 258 mA cm-2 , approximating to or even outperforming state-of-the-art Cu-based electrocatalysts. These GQDs also convert CO2 to C2 products mainly including C2 H4 and C2 H5 OH with a maximum FE of ≈10%. A systematic analysis reveals that the CH4 yield varies linearly with amine group content, whereas the C2 production rate is positively dependent on pyridinic N dopant content. This work provides insight into the rational design of carbon catalysts with CO2 -to-CH4 conversion efficiency at the industrially relevant level.

Synthesis of highly fluorescent, amine-functionalized carbon dots from biotin-modified chitosan and silk-fibroin blend for target-specific delivery of antitumor agents.

Carbon dots (CDs) have been a promising theranostic tool with high biocompatibility and a tailorable fluorescence profile. Herein, we report the synthesis of highly fluorescent amine-functionalized CDs from low molecular weight chitosan (LMWC) and silk-fibroin (SF) blends. The synthesized CDs were quasi-spherical in shape with a size of 3 ± 1.5 nm. A significant increase in fluorescent intensity and quantum yield was achieved upon increasing the SF content due to nitrogen doping. For inducing target specificity to cancer cells, biotin was covalently conjugated to the CDs, and the conjugation was determined by FTIR spectroscopy. The conjugate was further loaded with 5-fluorouracil (5-FU) as a model anti-cancer drug. The MTT assay showed increased cytotoxicity of the conjugated CDs in cancer cells compared to normal cells. The live-cell imaging in MCF-7 cell lines showed bright blue-colored fluorescence and increased internalization of the conjugated CDs than the non-conjugate ones due to receptor-mediated endocytosis.

Tailoring Amine-Functionalized Ti-MOFs via a Mixed Ligands Strategy for High-Efficiency CO2 Capture.

Amine-functionalized metal-organic frameworks (MOFs) are a promising strategy for the high-efficiency capture and separation of CO2. In this work, by tuning the ratio of 1,3,5-benzenetricarboxylic acid (H3BTC) to 5-aminoisophthalic acid (5-NH2-H2IPA), we designed and synthesized a series of amine-functionalized highly stable Ti-based MOFs (named MIP-207-NH2-n, in which n represents 15%, 25%, 50%, 60%, and 100%). The structural analysis shows that the original framework of MIP-207 in the MIP-207-NH2-n (n = 15%, 25%, and 50%) MOFs remains intact when the mole ratio of ligand H3BTC to 5-NH2-H2IPA is less than 1 to 1 in the resulting MOFs. By the introduction of amino groups, MIP-207-NH2-25% demonstrates outstanding CO2 capture performance up to 3.96 and 2.91 mmol g-1, 20.7% and 43.3% higher than those of unmodified MIP-207 at 0 and 25 °C, respectively. Furthermore, the breakthrough experiment indicates that the dynamic CO2 adsorption capacity and CO2/N2 separation factors of MIP-207-NH2-25% are increased by about 25% and 15%, respectively. This work provides an additional strategy to construct amine-functionalized MOFs with the maintenance of the original MOF structure and high performance of CO2 capture and separation.

Tailoring the CO2-selectivity of interfacial polymerized thin film nanocomposite membrane via the barrier effect of functionalized boron nitride.

Membrane-based separation is an appealing solution to mitigate CO2 emission sustainably due to its energy efficiency and environmental friendliness. Attributed to its excellent separation endowed by nanomaterial incorporation, nanocomposite membrane is rigorously developed. This study explored the feasibility of boron nitride (BN) embedment and changes to formation mechanism of ultrathin selective layer of thin film nanocomposite (TFN) are investigated. The effects of amine-functionalization on nanosheet-polymer interaction and CO2 separation performance are also identified. Participation of nanosheets during interfacial polymerization reduced the crosslinking of selective layer, hence, improved TFN permeance while the formation of contorted diffusion paths by the nanosheets favors transport of small gases. Amine-functionalization enhanced the nanosheet-polymer interaction and elevated the membrane affinity towards CO2 which led to enhanced CO2 selectivity. The best TFN prepared in this study exhibited 37% and 20% increment in permeability and selectivity, respectively with respect to neat thin film composite (TFC). It is found that the CO2 separation performance of BN incorporated TFN is on par with many non-porous nanosheet-incorporated TFNs reported in literatures. The transport and barrier effects of BN and functionalized BN are discussed in detail to provide further insights into the development of commercially attractive CO2 selective TFN membranes.

Understanding Correlation Between CO2 Insertion Mechanism and Chain Length of Diamine in Metal-Organic Framework Adsorbents.

Although CO2 insertion is a predominant phenomenon in diamine-functionalized Mg2 (dobpdc) (dobpdc4- =4,4-dioxidobiphenyl-3,3'-dicarboxylate) adsorbents, a high-performance metal-organic framework for capturing CO2 , the fundamental function of the diamine carbon chain length in the mechanism remains unclear. Here, Mg2 (dobpdc) systems with open metal sites grafted by primary diamines NH2 -(CH2 )n -NH2 were developed, with en (n=2), pn (n=3), bn (n=4), pen (n=5), hn (n=6), and on (n=8). Based on CO2 adsorption and IR results, CO2 insertion is involved in frameworks with n=2 and 3 but not in systems with n≥5. According to NMR data, bn-appended Mg2 (dobpdc) exhibited three different chemical environments of carbamate units, attributed to different relative conformations of carbon chains upon CO2 insertion, as validated by first-principles density functional theory (DFT) calculations. For 1-hn and 1-on, DFT calculations indicated that diamine inter-coordinated open metal sites in adjacent chains bridged by carboxylates and phenoxides of dobpdc4- . Computed CO2 binding enthalpies for CO2 insertion (-27.8 kJ mol-1 for 1-hn and -20.2 kJ mol-1 for 1-on) were comparable to those for CO2 physisorption (-19.3 kJ mol-1 for 1-hn and -20.8 kJ mol-1 for 1-on). This suggests that CO2 insertion is likely to compete with CO2 physisorption on diamines of the framework when n≥5.

Improving hydraulic permeability, mechanical properties, and chemical functionality of cellulose acetate-based membranes by co-polymerization with tetraethyl orthosilicate and 3-(aminopropyl)triethoxysilane.

Composite cellulose acetate (CA) membranes are widely used but their multiphase nature results in additive losses, poor mechanical strength, low chemical resistance and thermal stability, limiting their separation/purification yields. To overcome this, we fabricated monophasic hybrid membranes using a modified phase inversion technique, where tetraethylorthosilicate and 3-(aminopropyl)triethoxysilane were added to the CA casting solution. The resulting co-polymerization between CA, silanols and amine-functionalized silica groups, through sol-gel chemistry, was proved by ATR-FTIR (1118 cm-1, ν(SiOC)). The presence of propyl-amine groups increases the hydraulic permeability (3×), the rupture elongation (×1.5), and decreases the Young modulus (×1/2), due to the disruption of the CA-silica 3D network. For high propyl-amine contents this behaviour is reversed due to intensive cross-linking between CA-silica chains (decrease in 903 cm-1, ν(CH3COOC-)). The addition of silica- and amine-based structures to the CA framework increases the system degrees of freedom, opening the door to the design of new CA membranes.