Synthesis of Raspberry-like Nanoparticles via Surface Grafting of Positively Charged Polyelectrolyte Brushes: Colloidal Stability and Surface Properties.

A method to synthesize stable, raspberry-like nanoparticles (NPs), using surface grafting of poly(glycidyl methacrylate) (PGMA) brushes on a polystyrene (PS) core with varying grafting densities, is reported. A two-step functionalization reaction of PGMA epoxide groups comprising an amination step first using ethylene diamine and then followed by a quaternization using glycidyltrimethylammonium chloride generates permanently and positively charged polyelectrolyte brushes, which result in both steric and electrostatic stabilization. The dispersion stability of the brush-bearing NPs is dramatically improved compared to that of the pristine PS core in salt solutions at ambient (25 °C) and elevated temperatures (60 °C). Additionally, the grafted polyelectrolyte chains undergo a reversible swelling in the presence of different ionic strength (IS) salts, which modulate the surface properties, including roughness, stiffness, and adhesion. An atomic force microscope under both dry and wet conditions was used to image conformational changes of the polyelectrolyte chains during the swelling and deswelling transitions as well as to probe the nanomechanical properties by analyzing the corresponding force-sample separation curves. The quaternized polyelectrolyte brushes undergo a conformational transition from a collapsed state to a swelled state in the osmotic brush (OB) regime triggered by the osmotic gradient of mobile ions to the interior of the polymer chain. At IS ∼ 1 M, the brushes contract and the globules reform (salted brush state) as evidenced by an increase in the surface roughness and a reduction in the adhesion of the brushes. Beyond IS ∼ 1 M, quartz crystal microbalance with dissipation monitoring measurements show that salt uptake continues to take place predominantly on the exterior surface of the brush since salt adsorption is not accompanied by a size increase as measured by dynamic light scattering. The study adds new insights into our understanding of the behavior of NPs bearing salt-responsive polyelectrolyte brushes with adaptive swelling thresholds that can ultimately modulate surface properties.

Probing the Mechanism of Targeted Delivery of Molecular Surfactants Loaded into Nanoparticles after Their Assembly at Oil-Water Interfaces.

A targeted and controlled delivery of molecular surfactants at oil-water interfaces using the directed assembly of nanoparticles, NPs, is reported. The mechanism of NP assembly at the interface and the release of molecular surfactants is followed by laser scanning confocal microscopy and surface force spectroscopy. The assembly of positively charged polystyrene NPs at the oil-water interface was facilitated by the introduction of carboxylic acid groups in the oil phase (e.g., by adding 1 wt % stearic acid to hexadecane to produce a model oil). The presence of positively charged NPs consistently lowers the stiffness of the water-oil interface. The effect is lessened, when the NPs are present in a solution of NaCl or deionized water at pH 2, consistent with a less dense monolayer of NPs at the interface in the last two systems. In addition, the NPs reduce the interfacial adhesion (i.e., the "stickiness" of the interface or, put differently, the pull-off force experienced by the atomic force microscopy (AFM) tip during retraction). After the assembly, the NPs can release a previously loaded cargo of surfactant molecules, which then facilitate the formation of a much finer oil-water emulsion. As a proof of concept, we demonstrate the release of octadecyl amine, ODA, that has been incorporated into the NPs prior to the assembly. The release of ODA causes the NPs to detach from the interface altering the interfacial properties and leads to finer oil droplets. This approach can be exploited in applications in several fields ranging from pharmaceutical and cosmetics to hydrocarbon recovery and oil-spill remediation, where a targeted and controlled release of surfactants is wanted.

S and O Co-Coordinated Mo Single Sites in Hierarchically Porous Tubes from Sulfur-Enamine Copolymerization for Oxygen Reduction and Evolution.

The highly efficient bifunctional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is the key to achieving high-performance rechargeable Zn-air batteries. Non-precious-metal single-atom catalysts (SACs) have attracted intense interest due to their low cost and very high metal atomic utilization; however, high-activity bifunctional non-precious-metal SACs are still rare. Herein, we develop a new nanospace-confined sulfur-enamine copolymerization strategy to prepare a new type of bifunctional Mo SACs with O/S co-coordination (Mo-O2S2-C) supported on the multilayered, hierarchically porous hollow tubes. The as-prepared catalyst can not only expose more active sites and facilitate mass transfer due to their combined micropores, mesopores, and macropores but also have the S/O co-coordination structure for optimizing the adsorption energies of the ORR intermediates. Its ORR activity is among the highest, and it shows a low overpotential of 324 mV for the OER at 10 mA cm-2 in all of the reported Mo-based catalysts. When assembled in a Zn-air battery, it exhibits a high maximal power density of 197.3 mW cm-2 and a long service life of 50 hours, superior to those of Zn-air batteries using commercial Pt/C+IrO2.

Stimuli-Responsive, Hydrolyzable Poly(Vinyl Laurate-co-vinyl Acetate) Nanoparticle Platform for In Situ Release of Surfactants.

A stimuli-responsive, sub-100 nm nanoparticle (NP) platform with a hydrolyzable ester side chain for in situ generation of surfactants is demonstrated. The NPs were synthesized via copolymerization of vinyl-laurate and vinyl-acetate [p-(VL-co-VA), 3:1 molar ratio] and stabilized with a protective poly(ethylene-glycol) shell. The NPs are ∼55 nm in diameter with a zeta potential of -54 mV. Hydrolysis kinetics in an accelerated, base-catalyzed reaction show release of about 11 and 30% of the available surfactant at 25 and 80 °C, respectively. The corresponding values in seawater are 22 and 76%. The efficiency of the released surfactant in reducing the interfacial tension, altering wettability, and stabilizing oil-water emulsion was investigated through contact angle measurements and laser confocal scanning microscopy and benchmarked to sodium laurate, a commercially available surfactant. All these measurements demonstrate both the efficacy of the NP system for surfactant delivery and the ability of the released surfactant to alter wettability and stabilize an oil-water emulsion.

Hollow Multihole Carbon Bowls: A Stress-Release Structure Design for High-Stability and High-Volumetric-Capacity Potassium-Ion Batteries.

Potassium-ion batteries are potential alternatives to lithium-ion batteries for large-scale energy storage considering the low cost and high abundance of potassium. However, it is challenging to obtain stable electrode materials capable of undergoing long-term potassiation/depotassiation due to the high accumulated stress associated with the huge volume variation of the electrode. Here, we simulate the von Mises stress distributions of four different carbon three-dimensional models under an isotropic initial stress by the finite element method and reveal the critical role of the structure of a hollow multihole bowl on the strain-relaxation behavior. In this regard, nitrogen/oxygen codoped carbon hollow multihole bowls (CHMBs) are synthesized via hydrothermal carbonization coupled with an emulsion-templating strategy using biomass as the carbon source. Consistent with our simulation results, the CHMB anode remains stable for over 1000 cycles and delivers a high reversible capacity of 304 mAh g-1 at 0.1 A g-1. In addition to the reduced stress accumulation, the good electrochemical performances are also attributed to the surface capacitive mechanism and the shortened electron/ion transport distance in CHMBs. In particular, the CHMB composite electrode has a volumetric specific capacity 56% higher than that of hollow spheres due to the high tapped density of the bowl-shaped particles.

Scalable Synthesis of Switchable Assemblies of Gold Nanorod Lyotropic Liquid Crystal Nanocomposites.

A new class of solvent free, lyotropic liquid crystal nanocomposites based on gold nanorods (AuNRs) with high nanorod content is reported. Application of shear results in switchable, highly ordered alignment of the nanorods over several centimeters with excellent storage stability for months. For the synthesis, AuNRs are surface functionalized with a charged, covalently tethered corona, which induces fluid-like properties. This honey-like material can be deposited on a substrate and a high orientational order parameter of 0.72 is achieved using a simple shearing protocol. Switching shearing direction results in realignment of the AuNRs. For a film containing 75 wt% of AuNRs the alignment persists for several months. In addition to the lyotropic liquid crystal characteristics, the AuNRs films also exhibit anisotropic electrical conductivity with an order of magnitude difference between the conductivities in direction parallel and perpendicular to the alignment of the AuNRs.

Superhydrophilic Wrinkle-Free Cotton Fabrics via Plasma and Nanofluid Treatment.

We demonstrate in this study a wrinkle-free, superhydrophilic cotton fabric (contact angle ∼0°) by uniformly attaching specially engineered nanoparticles to plasma-pretreated cotton fabric. Because of their highly charged nature, the nanoparticles are firmly anchored on the fabric via electrostatic interactions, as confirmed by microscopy and chemical analyses. The durability of wetting behavior and wrinkle-free property of the nanoparticle-coated fabrics were evaluated via aging, laundering, and abrasion tests. The strongly attached coatings are stable enough to maintain their superhydrophilic nature even after 60 days of aging at room temperature, 50 laundering cycles, and 25 000 abrasion cycles. Moreover, the nanoparticle-coated superhydrophilic fabrics exhibit great wrinkle-recovery property, tensile strength, and abrasion resistance performance up to 25 000 abrasion cycles.

Preparation and photovoltaic properties of CdS quantum dot-sensitized solar cell based on zinc tin mixed metal oxides.

The present study reports a new type of quantum dot sensitized solar cells (QDSSCs) using the zinc tin mixed metal oxides (MMO) as the anode materials, which were obtained from the layered double hydroxide (LDH) precursor. The successive ionic layer adsorption and reaction (SILAR) method is applied to deposit CdS quantum dots. The effects of sensitizing cycles on the performance of CdS QDSSC are studied. Scanning electron microscopy (SEM), Transmission electron microscope (TEM) and X-ray diffraction (XRD) are used to identify the surface profile and crystal structure of the mixed metal oxides anode. The photovoltaic performance of the QDSSC is studied by the electrochemical method. The new CdS QDSSC exhibits power conversion efficiency (PCE) up to 0.48% when the anode was sensitized for eight cycles.

Sponges with covalently tethered amines for high-efficiency carbon capture.

Adsorption using solid amine sorbents is an attractive emerging technology for energy-efficient carbon capture. Current syntheses for solid amine sorbents mainly based on physical impregnation or grafting-to methods (for example, aminosilane-grafting) lead to limited sorbent performance in terms of stability and working capacity, respectively. Here we report a family of solid amine sorbents using a grafting-from synthesis approach and synthesized by cationic polymerization of oxazolines on mesoporous silica. The sorbent with high amount of covalently tethered amines shows fast adsorption rate, high amine efficiency and sorbent capacity well exceeding the highest value reported to date for low-temperature carbon dioxide sorbents under simulated flue gas conditions. The demonstrated efficiency of the new amine-immobilization chemistry may open up new avenues in the development of advanced carbon dioxide sorbents, as well as other nitrogen-functionalized systems.

In situ formation of silver nanoparticles on thin-film composite reverse osmosis membranes for biofouling mitigation.

The potential to incorporate silver nanoparticles (Ag-NPs) as biocides in membranes for water purification has gained much interest in recent years. However, a viable strategy for loading the Ag-NPs on the membrane remains challenging. This paper presents a novel, facile procedure for loading Ag-NPs on thin-film composite (TFC) reverse osmosis membranes. Reaction of silver salt with a reducing agent on the membrane surface resulted in uniform coverage of Ag-NPs, irreversibly bound to the membrane, as confirmed by XPS, TEM, and SEM analyses. Salt selectivity of the membrane as well its surface roughness, hydrophilicity, and zeta potential were not impacted by Ag-NP functionalization, while a slight reduction (up to 17%) in water permeability was observed. The formed Ag-NPs imparted strong antibacterial activity to the membrane, leading to reduction of more than 75% in the number of live bacteria attached to the membrane for three model bacteria strains. In addition, confocal microscopy analyses revealed that Ag-NPs significantly suppressed biofilm formation, with 41% reduction in total biovolume and significant reduction in EPS, dead, and live bacteria on the functionalized membrane. The simplicity of the method, the short reaction time, the ability to load the Ag-NPs on site, and the strong imparted antibacterial activity highlight the potential of this method in real-world RO membrane applications.

Synthesis and carbon dioxide sorption of layered double hydroxide/silica foam nanocomposites with hierarchical mesostructure.

Layered double hydroxides (LDHs) with a hierarchical mesostructure are successfully synthesized on mesoporous silica foams by simple impregnation and hydrothermal treatment. The as-synthesized LDH/silica foam nanocomposites show well-defined mesostructures with high surface areas, large pore volumes, and mesopores of 6-7 nm. The nanocomposites act as carbon dioxide (CO2 ) sorbents under simulated flue gas conditions. They also exhibit significantly enhanced CO2 capacities under high-pressure conditions and high CO2 /N2 and CO2 /CH4 selectivities.

Facile synthesis and application of a carbon foam with large mesopores.

By combining elements of hard- and soft-templating, a facile synthesis method for carbon foams with large mesopores has been demonstrated. A commercial Pluronic surfactant was used as the structure-directing agent as well as the carbon precursor. No micelle swelling agent or post treatment is necessary to enlarge mesopores. As such this method requires fewer synthesis steps and is highly scalable. The as-synthesized meso-carbons showed potential applications in the fields of carbon oxide capture and lithium-sulfur batteries.

Using magnetically responsive tea waste to remove lead in waters under environmentally relevant conditions.

We report the use of a simple yet highly effective magnetite-waste tea composite to remove lead(II) (Pb(2+)) ions from water. Magnetite-waste tea composites were dispersed in four different types of water-deionized (DI), artificial rainwater, artificial groundwater and artificial freshwater-that mimic actual environmental conditions. The water samples had varying initial concentrations (0.16-5.55 ppm) of Pb(2+) ions and were mixed with the magnetite-waste tea composite for at least 24 hours to allow adsorption of the Pb(2+) ions to reach equilibrium. The magnetite-waste tea composites were stable in all the water samples for at least 3 months and could be easily removed from the aqueous media via the use of permanent magnets. We detected no significant leaching of iron (Fe) ions into the water from the magnetite-waste tea composites. The percentage of Pb adsorbed onto the magnetite-waste tea composite ranged from ∼70% to 100%; the composites were as effective as activated carbon (AC) in removing the Pb(2+) ions from water, depending on the initial Pb concentration. Our prepared magnetite-waste tea composites show promise as a green, inexpensive and highly effective sorbent for removal of Pb in water under environmentally realistic conditions.

Formation of SnO2 hollow nanospheres inside mesoporous silica nanoreactors.

We report an interesting approach for efficient synthesis of SnO(2) hollow spheres inside mesoporous silica "nanoreactors". The as-prepared products are shown to have a uniform size distribution and good structural stability. When evaluated for their lithium storage properties, these SnO(2) hollow spheres manifest improved capacity retention.

Enzyme-initiated miniemulsion polymerization.

Enzyme-catalyzed polymerization in vitro has gained considerable attention in the last two decades as an efficient tool in the polymerization of various monomers, such as saccharides, esters, phenols, and aromatic anilines; however, the polymerization of vinyl monomers using enzymes has been more limited, perhaps due to the hydrophobicity of most common vinyl monomers. Enzyme-initiated miniemulsion polymerization is demonstrated herein as a way to polymerize hydrophobic vinyl monomers such as styrene. By application of enzyme-initiated radical polymerization in miniemulsion, stable poly(styrene) latexes are prepared with a particle size near 50 nm. A very small amount of enzyme and surfactant is required to facilitate the miniemulsion polymerization, whereas a relatively high polymerization rate and conversion are achieved.

On the stability of miniemulsions in the presence of RAFT agents.

The colloidal stability of miniemulsions in the presence of RAFT or other control agents for controlled free radical polymerization is examined. A derivation, based on Lifshitz-Slyozov-Wagner (LSW) theory, is proposed here to evaluate the effect of a RAFT agent on the diffusional stability of the miniemulsions before the onset of polymerization. Results indicate that, depending on the hydrophobicity of the control agent, its presence may augment or detract from the effectiveness of the costabilizer in preventing diffusional instability due to Ostwald ripening.