Engineering of Defective MOF-801 Nanostructures within Macroporous Spheres for Highly Efficient and Stable Water Harvesting.

Water harvesting using the metal-organic framework (MOF)-801 is restricted by limited working capacity, powder structuring, and finite stability. To overcome these issues, MOF-801 is crystallized on the surface of macroporous poly(N-isopropylacrylamide-glycidyl methacrylate) spheres, called P(NIPAM-GMA), through an in situ confined growth strategy, forming spherical MOF-801@P(NIPAM-GMA) composite with temperature-responsive function. By lowering the nucleation energy barrier, the average size of the MOF-801 crystals decreases by 20 times. Thus, abundant defects as adsorption sites for water can be installed in the crystals lattices. As a consequence, the composite provides an unprecedented high water harvesting efficiency. The composite is produced in the kilogram-scale and can capture 1.60 kg H2 O/kg composite/day from 20% relative humidity between 25 and 85 °C. This study provides an effective methodology for improving the adsorption capacity through controlled defects formation as adsorption sites and to improve the kinetics through the design of a composite with macroporous transport channel network.

Quaternary tannic acid with improved leachability and biocompatibility for antibacterial medical thermoplastic polyurethane catheters.

The surfaces of indwelling catheters offer sites for the adherence of bacteria to form biofilms, leading to various infections. Therefore, the development of antibacterial materials for catheters is imperative. In this study, combining the strong antibacterial effect of a quaternary ammonium salt (QAS) and the high biocompatibility of tannic acid (TA), we prepared a quaternary tannic acid (QTA) by grafting a synthesized quaternary ammonium salt, dimethyl dodecyl 6-bromohexyl ammonium bromide, onto TA. To prepare antibacterial catheters, QTA was blended with thermoplastic polyurethane (TPU) via melt extrusion, which is a convenient and easy-to-control process. Characterization of the TPU blends showed that compared with those of the QAS, dissolution rate and biocompatibility of QTA were significantly improved. On the premise that the introduction of QTA had only a slight effect on the original mechanical properties of pristine TPU, the prepared TPU/QTA maintained satisfactory antibacterial activities in vitro, under a flow state, as well as in vivo. The results verified that the TPU/QTA blend with a QTA content of 4% is effective, durable, stable, and non-toxic, and exhibits significant potential as a raw material for catheters.

A Highly Efficient and Stable Composite of Polyacrylate and Metal-Organic Framework Prepared by Interface Engineering for Direct Air Capture.

We present a kilogram-scale experiment for assessing the prospects of a novel composite material of metal-organic framework (MOF) and polyacrylates (PA), namely NbOFFIVE-1-Ni@PA, for trace CO2 capture. Through the interfacial enrichment of metal ions and organic ligands as well as heterogeneous crystallization, the sizes of microporous NbOFFIVE-1-Ni crystals are downsized to 200-400 nm and uniformly anchored on the macroporous surface of PA via interfacial coordination, forming a unique dual-framework structure. Specifically, the NbOFFIVE-1-Ni@PA composite with a loading of 45.8 wt % NbOFFIVE-1-Ni yields a superior CO2 uptake (ca. 1.44 mol·kg-1) compared to the pristine NbOFFIVE-1-Ni (ca. 1.30 mol·kg-1) at 400 ppm and 298 K, indicating that the adsorption efficiency of NbOFFIVE-1-Ni has been raised by 2.42 times. Meanwhile, the time cost for realizing a complete adsorption/desorption cycle in a fluidized bed has been shortened to 25 min, and the working capacity (ca. 0.84 mol·kg-1) declines only by 1.3% after 2000 cycles. The device is capable of harvesting 2.1 kg of CO2 per kilogram of composite daily from simulated air with 50% relatively humidity (RH). To the best of our knowledge, the excellent adsorption/desorption performances of NbOFFIVE-1-Ni@PA position it as the most advantageous and practically applicable candidate for trace CO2 capture.

Preparation of medical hydrophilic and antibacterial silicone rubber via surface modification.

Bacterial adhesion of medical indwelling devices shortens their service life and brings about infections in patients. The combination of hydrophilic and antibacterial modifications can not only kill the bacteria in contact with the surface, but also avoid the adhesion of dead bacteria. From this view, with a self-made quaternary ammonium salt and a zwitterion as the modifiers, a modified silicone rubber, SR-g-(DMAPS-co-QA), was prepared via random co-grafting. The static water angle test and antibacterial assays proved the enhancement of both the hydrophilicity and antibacterial activity. In addition, compared with the unmodified silicone rubber, after 7 days of co-cultivation in E. coli suspension, SR-g-(DMAPS-co-QA) demonstrated good resistance to biofilm formation. Furthermore, to simulate the real situation, its antibacterial effect in dynamic flow condition was measured, confirming that SR-g-(DMAPS-co-QA) still maintained good antibacterial performance after a 48 hour cyclic flow of E. coli bacterial suspension.

Synthesis of Dimethyl Octyl Aminoethyl Ammonium Bromide and Preparation of Antibacterial ABS Composites for Fused Deposition Modeling.

Additive manufacturing (AM) demonstrates benefits in the high-precision production of devices with complicated structures, and the modification of materials for AM is an urgent need. To solve the bacterial infection of medical devices in their daily application, dimethyl octyl aminoethyl ammonium bromide (octyl-QDED), an organic antibacterial agent, was synthesized via the quaternary ammonium reaction. Then, the synthesized octyl-QDED was blended with acrylonitrile butadiene styrene (ABS) through the melt extrusion process to prepare antibacterial composite filaments for fused deposition modeling (FDM). The entire preparation processes were convenient and controllable. Characterizations of the structure and thermal stability of octyl-QDED confirmed its successful synthesis and application in the subsequent processes. The introduced maleic acid in the blending process acted as a compatibilizer, which improved the compatibility between the two phases. Characterizations of the rheological and mechanical properties proved that the addition of octyl-QDED made a slight difference to the comprehensive performance of the ABS matrix. When the content of octyl-QDED reached 3 phr, the composites showed excellent antibacterial properties. The prepared antibacterial composite filaments for FDM demonstrated great potential in medical and surgical areas.

Fabrication of branching poly (butylene succinate)/cellulose nanocrystal foams with exceptional thermal insulation.

Branching poly (butylene succinate) (BPBS) nanocomposite foams incorporated with cellulose nanocrystals (CNCs) were prepared by supercritical CO2. Surface modification of CNCs by acetylation was achieved through replacing hydrophilic hydroxyl groups with hydrophobic acetyl groups, which improved the dispersibility of CNCs significantly. The crystallite sizes of CNCs and acetylated CNCs were calculated by Scherrer's formula as 25 and 19 nm, respectively. The initial crystallization temperature of diverse poly (butylene succinate) (PBS) specimens, a crucial factor for regulating cell nucleation type, increased remarkably by 11.8 °C as well as their storage modulus increased by 2 orders of magnitudes, due to branching reaction and bio-filler addition. BPBS/CNCs foam possessed a high volume expansion ratio as 37.1 times and displayed an exceptional thermal conductivity as 0.021 W(m K)-1. This study provided a promising potential strategy to develop exceptional thermal-insulation polymer foams for composite structures, energy conservation and environment protection.

Anisotropic Dynamics of Binary Particles in Confined Geometries.

The diffusion dynamics of colloidal particles in a good solvent confined between two parallel quartz walls have been studied within the framework of dynamical density functional theory. The highly ordered density layers induced by interfacial effects give rise to the oscillating dynamics, resulting in position-dependent structural relaxations and diffusivities. Further investigation reveals that particle size, particle-wall interaction, and slitpore width play different roles in affecting the oscillating behaviors along different directions. As a result, the theory yields the local mean square displacements in perpendicular and parallel directions, which agree remarkably well with prior experimental measurements. The results indicate that the mean square displacements can be quantitatively predicted based on the knowledge of inhomogeneous thermodynamics and dynamics. The local and averaged free energy evolution of the binary particles has been described and presented to understand their dynamic mechanism in confined geometry.

Construction of Oxygen-Rich Carbon Foams for Rapid Carbon Dioxide Capture.

As carbon dioxide (CO2) adsorbents, porous materials with high specific surface areas and abundant CO2-philic groups always exhibit high CO2 capacities. Based on this consensus, a category of oxygen-rich macroporous carbon foams was fabricated from macroporous resorcinol-formaldehyde resins (PRFs), which were obtained via an oil-in-water concentrated emulsion. By the active effect of potassium hydroxide (KOH) at high temperatures, the resultant carbon foams (ACRFs) possessed abundant micropores with rich oxygen content simultaneously. At the same time, most of the ACRFs could retain the marcoporous structure of their precursor. It is found that porosity of ACRFs was mainly determined by carbonization temperature, and the highest specific surface areas and total pore volume of ACRFs could reach 2046 m2/g and 0.900 cm3/g, respectively. At 273 k, ACRFs showed highest CO2 capacity as 271 mg/g at 1 bar and 91.5 mg at 15 kPa. Furthermore, it is shown that the ultra-micropore volume was mainly responsible for the CO2 capacities of ACRFs at 1 bar, and CO2 capacities at 15 kPa were mainly affected by the oxygen content. It is also found that the presence of macropores would accelerate ACRFs adsorbing CO2. This study provides ideas for designing a porous CO2 adsorbent.

Nanocellular Foaming Behaviors of Chain-Extended Poly(lactic acid) Induced by Isothermal Crystallization.

Recently, the fabrication of semicrystalline polymer foams with a nanocellular structure by supercritical fluids has been becoming a newly developing research hotspot, owing to their peculiar properties and prospective applications. In this work, a facile and effective isothermal crystallization-induced method was proposed to prepare nanocellular semicrystalline poly(lactic acid) (PLA) foams using CO2 as a physical blowing agent. Styrene-acrylonitrile-glycidyl methacrylate (SAG) as a chain extender (CE) was introduced into PLA through a melt-mixing method to improve the crystallization behavior and melt viscoelasticity of PLA. The chain extension reaction between PLA and SAG occurred successfully as well as the branching and micro cross-linking structures were generated in chain-extended PLA (CPLA) samples, which were confirmed by Fourier transform infrared spectra, gel fraction, and intrinsic viscosity measurements. Owing to the nucleation effect of branching points and the restricted movement of PLA molecular chains by the formation of branching and/or microcross-linking structures, a large number of small spherocrystals were generated in CPLA samples, which was beneficial to produce nanocells. Nanocellular CPLA foams were prepared successfully, when the foaming temperature was 125 °C. As the SAG content increased, the cell size of various PLA foams decreased from 364 ± 198 to 249 ± 100 nm and their volume expansion ratio increased from 1.15 ± 0.05 to 2.22 ± 0.01 times, gradually. When the foaming temperature increased from 125 to 127 °C, an interesting transition from nanocells to microcells could be observed in CPLA foam with the CE content of 2 wt %. Finally, the formation mechanism of nanocells in various PLA foams was proposed and clarified using a schematic diagram.

Multiple actions of poly(ethylene octene) grafted with glycidyl methacrylate on the performance of poly(lactic acid).

Poly(ethylene octene) grafted with glycidyl methacrylate (POE-g-GMA) was employed to improve the rheological and thermal properties, toughness, and foaming behaviors of poly(lactic acid) (PLA) through a chain extension effect. The dynamic rheological properties of PLA were improved significantly with increasing content of POE-g-GMA, due to the chain extension reaction between PLA and POE-g-GMA. As the content of POE-g-GMA increased, the cold crystallization temperature of PLA decreased by more than 10 °C and the crystallinity of PLA increased slightly from 1.2% to 4.7%, respectively. The impact strength of PLA with a POE-g-GMA content of 10 wt% increased by more than 4 times, compared with that of pure PLA. A sea-island structure could be observed in the PLA/POE-g-GMA blends and the distribution of POE-g-GMA was uniform. PLA foams with various POE-g-GMA contents were prepared in a stainless-steel autoclave using supercritical CO2 as a physical blowing agent. The cellular morphology of PLA foam was obviously improved when the concentration of POE-g-GMA increased from 5 wt% to 10 wt%.

The mechanism of roughness-induced CO2 microbubble nucleation in polypropylene foaming.

Within the framework of classical density functional theory, the thermodynamic driving forces for CO2 microbubble nucleation have been quantitatively evaluated in the foaming of polypropylene containing amorphous and crystalline structures. After the addition of fluorinated polyhedral oligomeric silsesquioxane particles into the polypropylene matrix, we construct different composite surfaces with nanoscale roughness for bubble nucleation. Meanwhile, as the dissolved CO2 molecules increase, the corresponding CO2/PP binary melts can be formulated in the systems. Due to the roughness effect coupled with the weak interactions of particle-PP, PP chains in the binary melts are depleted from the surfaces, leading to a significant enhancement of osmotic pressure in depletion regions. During the foaming process, a large number of dissolved CO2 molecules are squeezed into the regions, thus local supersaturations are dramatically improved, and the energy barriers for bubble nucleation are dramatically reduced. Moreover, when the nanocomposite surfaces display ordered nanoscale patterns, the energy barriers can be further reduced to their respective minimum values, and the bubble number densities reach their maximum. Accordingly, the bubble number densities can be enhanced by 4 or 5 orders of magnitude for bubbles nucleated on the crystalline or amorphous PP nanocomposite surface. In contrast, when the foaming pressure is increased from 15 to 20 MPa, the elevated bubble number density in the foaming PP matrix is less than one order of magnitude. As a result, the enhancement of local supersaturation induced by the controlled nanoscale roughness is much more effective than that of bulk supersaturation given by high pressure.

Diffusive dynamics of polymer chains in an array of nanoposts.

We present a dynamic density functional approach to study polymer chain diffusion in a good solvent in the confinement of a nanopost array. Three key results emerge from our study. First, we show different scaling laws of the chains moving toward, close to, and around the posts. Second, in the flux process of polymer chains, the head, side, and middle segments display different scaling laws. As the chains come in contact with the posts, an enlarged motion discrepancy emerges between the head and middle segments perpendicular to the posts. For instance, the motion of head segments transforms from Zimm to reputation type, whereas the middle segments almost retain the Zimm motion. Third, as the spacing crack between two posts narrows down, a climbing effect along the posts can be clearly observed in the polymer motion.

Control of Uniform and Interconnected Macroporous Structure in PolyHIPE for Enhanced CO2 Adsorption/Desorption Kinetics.

The highly uniform and interconnected macroporous polymer materials were prepared within the high internal phase hydrosol-in-oil emulsions (HIPEs). Impregnated with polyethylenimine (PEI), the polyHIPEs were then employed as solid adsorbents for CO2 capture. Thermodynamic and kinetic capture-and-release tests were performed with pure CO2, 10% CO2/N2, and moist CO2, respectively. It has shown that the polyHIPE with suitable surface area and PEI impregnation exhibits high CO2 adsorption capacity, remarkable CO2/N2 selectivity, excellent adsorption/desorption kinetics, enhanced efficiency in the presence of water, and admirable stability in capture and release cycles. The results demonstrate the superior comprehensive performance of the present PEI-impregnated polyHIPE for CO2 capture from the postcombustion flue gas.

Understanding Controls on Wetting at Fluorinated Polyhedral Oligomeric Silsesquioxane/Polymer Surfaces.

Fluorinated polyhedral oligomeric silsesquioxane (F-POSS) nanoparticles have been widely used to enhance the hydrophobicity or oleophobicity of polymer films via constructing the specific micro/nanoscale roughness. In this work, we study the oleophobicity of pure and F-POSS-decorated poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) films using a dynamic density functional theory approach. The role of nanoparticle size and coverage and the chemical features of F-POSS and the polymer film in the wetting behavior of diiodomethane droplets has been integrated to the remaining ratio of surface potential to quantitatively characterize the corner effect. It is shown that, on the basis of universal force field parameters, the theoretically predicted contact angles are in general agreement with the available experimental data.

Density Functional Theory of Polymer Structure and Conformations.

We present a density functional approach to quantitatively evaluate the microscopic conformations of polymer chains with consideration of the effects of chain stiffness, polymer concentration, and short chain molecules. For polystyrene (PS), poly(ethylene oxide) (PEO), and poly(methyl methacrylate) (PMMA) melts with low-polymerization degree, as chain length increases, they display different stretching ratios and show non-universal scaling exponents due to their different chain stiffnesses. In good solvent, increase of PS concentration induces the decline of gyration radius. For PS blends containing short (m1 = 1 - 100) and long (m = 100) chains, the expansion of long chains becomes unobvious once m 1 is larger than 40, which is also different to the scaling properties of ideal chain blends.

Understanding the microstructure of particle dispersion in confined copolymer nanocomposites.

The microstructures of diblock copolymer/particle composites confined in slitpores have been investigated using a density functional theory approach. It has been shown that, under the condition of confinement, particles display different distributions near the solid surfaces, in the microdomains of two blocks, and at the microphase interfaces. The final dispersion depends on the balance between the enthalpic contribution arising from the particle-segment attraction as well as the entropy-driven depletion attraction induced by the polymer conformation and the confinement environment. For the systems in which particles weakly attract one block but repel another block, particle dispersion can be enhanced by the increasing confinement effect, and the enhancement becomes more obvious as the size asymmetries of particles and two blocks increase. If the attraction increases, however, particle dispersion declines as the confinement effect increases.

Theoretical Insight into Dispersion of Silica Nanoparticles in Polymer Melts.

Silica nanoparticles dispersed in polystyrene, poly(methyl methacrylate), and poly(ethylene oxide) melts have been investigated using a density functional approach. The polymers are regarded as coarse-grained semiflexible chains, and the segment sizes are represented by their Kuhn lengths. The particle-particle and particle-polymer interactions are calculated with the Hamaker theory to reflect the relationship between particles and polymer melts. The effects of particle volume fraction and size on the particle dispersion have been quantitatively determined to evaluate their dispersion/aggregation behavior in these polymer melts. It is shown that theoretical predictions are generally in good agreement with the corresponding experimental results, providing the reasonable verification of particle dispersion/agglomeration and polymer depletion.

Effect of chain topology of polyethylenimine on physisorption and chemisorption of carbon dioxide.

Polyethylenimine (PEI) is a promising candidate for CO2 capture. In this work, the physisorption and chemisorption of CO2 on various low-molecular-weight PEIs are investigated to identify the effect of chain architecture on sorption. The reliability of theoretical calculations are partially supported by our experimental measurements. Physisorption is calculated independently by the reference interaction-site model integral equation theory; chemisorption is distinguished from the total sorption given by the quantum density functional theory. It is shown that, as the chain length increases, both chemisorption and physisorption drop off nonlinearly, but the decay amplitude of chemisorption is more apparent. Conversely, as the amine group approaches the central triamine unit of each oligomer, the sorption capacity decreases, affecting the sorption equilibrium in a complex way. This arises from the cooperative contribution of an increased steric effect and renormalized electronic distribution.

Evaluation of macroscale wetting equations on a microrough surface.

The wettability of critical droplets on microscale geometric rough surfaces has been investigated using a density functional theory approach. In order to analyze the effect of roughness on nucleation free-energy barriers, the local density fluctuations at liquid-solid interfaces induced by the multi-interactions of a corner substrate are presented to interpret the interfacial free-energy variations, and the vapor-liquid-solid contact line tensions are derived from the contact angles of nuclei to account for the three-phase contact energies. The corresponding wetting diagrams have been constructed in Cassie, Wenzel, and impregnation regions. It is shown that, under the same condition, modest deviations between the microscale and the macroscale models can be observed within the Cassie region, whereas these deviations have been enlarged in the Wenzel and impregnation regions as well as the Cassie-Wenzel transition region. These deviations are also correlated to the roughness of the surface. The reason can be attributed to the cooperative effect of the liquid-solid interfacial free energy and line tension. This study offers a fundamental understanding of wettability of ultrasmall droplets on a microscale geometric rough surface.

Thermodynamics of ice nucleation in liquid water.

We present a density functional theory approach to investigate the thermodynamics of ice nucleation in supercooled water. Within the theoretical framework, the free-energy functional is constructed by the direct correlation function of oxygen-oxygen of the equilibrium water, and the function is derived from the reference interaction site model in consideration of the interactions of hydrogen-hydrogen, hydrogen-oxygen, and oxygen-oxygen. The equilibrium properties, including vapor-liquid and liquid-solid phase equilibria, local structure of hexagonal ice crystal, and interfacial structure and tension of water-ice are calculated in advance to examine the basis for the theory. The predicted phase equilibria and the water-ice surface tension are in good agreement with the experimental data. In particular, the critical nucleus radius and free-energy barrier during ice nucleation are predicted. The critical radius is similar to the simulation value, suggesting that the current theoretical approach is suitable in describing the thermodynamic properties of ice crystallization.