The 50 most-cited articles in Langmuir, 2017

Abstract Understanding the competition between hydrogen evolution and CO2 reduction is of fundamental importance to increase the faradaic efficiency for electrocatalytic CO2 reduction in aqueous electrolytes. Here, by using a copper rotating disc electrode, we find that the major hydrogen evolution pathway competing with CO2 reduction is water reduction, even in a relatively acidic electrolyte (pH 2.5). The mass-transport-limited reduction of protons takes place at potentials for which there is no significant competition with CO2 reduction. This selective inhibitory effect of CO2 on water reduction, as well as the difference in onset potential even after correction for local pH changes, highlights the importance of differentiating between water reduction and proton reduction pathways for hydrogen evolution. In-situ FTIR spectroscopy indicates that the adsorbed CO formed during CO2 reduction is the primary intermediate responsible for inhibiting the water reduction process, which may be one of the main mechanisms by which copper maintains a high faradaic efficiency for CO2 reduction…

Janus particles are colloidal particles with more than a single type of surface chemistry or composition, ranging in size from hundreds of nanometers to a few micrometers. Like traditional colloids, they are large enough to be observed under optical microscopy in real time and small enough to diffuse by Brownian motion, but their interesting and useful new properties of directional interaction bring new research opportunities to the fields of soft matter and fundamental materials research as well as to applications in other disciplines and in technologies such as electronic paper and other multiphase engineering. In this review, a variety of methods that have been used to synthesize Janus particles are introduced. Following this, we summarize the use of Janus particles as basic units that assemble into novel structures and tune important material properties. The concluding sections highlight some of the technological applications, including recent progress in using Janus particles as microprobes, micromotors, electronic paper, and solid surfactants.

Single layered Ti 3 C 2 (OH) 2 nanosheets have been successfully fabricated by etching its Ti 3 AlC 2 precursor with KOH in the presence of a small amount of water. The OH group replaced the Al layer within the Ti 3 AlC 2 structure during etching, and Ti 3 C 2 (OH) 2 nanosheets could be easily and efficiently achieved through a simple washing process. The delaminated single-layered nanosheets are clearly revealed by atomic force microscopy to be several micrometers in lateral size. Interestingly, the exfoliated Ti 3 C 2 (OH) 2 nanosheets could be restacked to form a new layer-structured material after drying. When redispersing this restacked Ti 3 C 2 (OH) 2 materials in water again, it could be re-delaminated easily only after shaking for several hours. The easy delamination and restacking properties, coupled with intrinsic metallic conductivity and hydrophilicity, make it an ideal two-dimensional building block for fabricating a wide variety of functional materials.

Carbon dots (CDs) are a new class of photoluminescent (PL), biocompatible, environment-friendly, and low-cost carbon nanomaterials. Synthesis of highly efficient red-emitting carbon dots (R-CDs) on a gram scale is a great challenge at present, which heavily restricts the wide applications of CDs in the bioimaging field. Herein, R-CDs with a high quantum yield (QY) of 53% are produced on a gram scale by heating a formamide solution of citric acid and ethylenediamine. The as-prepared R-CDs have an average size of 4.1 nm and a nitrogen content of about 30%, with an excitation-independent emission at 627 nm. After detailed characterizations, such strong red fluorescence is ascribed to the contribution from the nitrogen- and oxygen-related surface states and the nitrogen-derived structures in the R-CD cores. Our R-CDs show good photostability and low cytotoxicity, and thus they are excellent red fluorescence probes for bioimaging both in vitro and in vivo.

The study of solid particles residing at fluid-fluid interfaces has become an established area in surface and colloid science recently, experiencing a renaissance since around 2000. Particles at interfaces arise in many industrial products and processes such as antifoam formulations, crude oil emulsions, aerated foodstuffs, and flotation. Although they act in many ways like traditional surfactant molecules, they offer distinct advantages also, and the area is now multidisciplinary, involving research in the fundamental science and potential applications. In this Feature Article, the flavor of some of this interest is given on the basis of recent work from our own group and includes the behavior of particles at oil-water, air-water, oil-oil, air-oil, and water-water interfaces. The materials capable of being prepared by assembling various kinds of particles at fluid interfaces include particle-stabilized emulsions, particle-stabilized aqueous and oil foams, dry liquids, liquid marbles, and powdered emulsions.

Pore volume is one of the main properties for the characterization of microporous crystals. It is experimentally measurable, and it can also be obtained from the refined unit cell by a number of computational techniques. In this work, we assess the accuracy and the discrepancies between the different computational methods which are commonly used for this purpose, i.e, geometric, helium, and probe center pore volumes, by studying a database of more than 5000 frameworks. We developed a new technique to fully characterize the internal void of a microporous material and to compute the probe-accessible and -occupiable pore volume. We show that, unlike the other definitions of pore volume, the occupiable pore volume can be directly related to the experimentally measured pore volumes from nitrogen isotherms.

Eutectic gallium-indium alloy (EGaIn, a room-temperature liquid metal) nanoparticles are of interest for their unique potential uses in self-healing and flexible electronic devices. One reason for their interest is due to a passivating oxide skin that develops spontaneously on exposure to ambient atmosphere which resists deformation and rupture of the resultant liquid particles. It is then of interest to develop methods for control of this oxide growth process. It is hypothesized here that functionalization of EGaIn nanoparticles with thiolated molecules could moderate oxide growth based on insights from the Cabrera-Mott oxidation model. To test this, the oxidation dynamics of several thiolated nanoparticle systems were tracked over time with X-ray photoelectron spectroscopy. These results demonstrate the ability to suppress gallium oxide growth by up to 30%. The oxide progressively matures over a 28 day period, terminating in different final thicknesses as a function of thiol selection. These results indicate not only that thiols moderate gallium oxide growth via competition with…

Abstract The pore size distribution (PSD) is one of the most important properties when characterizing and designing materials for gas storage and separation applications. Experimentally, one of the current standards for determining microscopic PSD is using indirect molecular adsorption methods such as nonlocal density functional theory (NLDFT) and N2 isotherms at 77 K. Because determining the PSD from NLDFT is an indirect method, the validation can be a nontrivial task for amorphous microporous materials. This is especially crucial since this method is known to produce artifacts. In this work, the accuracy of NLDFT PSD was compared against the exact geometric PSD for 11 different simulated amorphous microporous materials. The geometric surface area and micropore volumes of these materials were between 5 and 1698 m2/g and 0.039 and 0.55 cm3/g, respectively. N2 isotherms at 77 K were constructed using Gibbs ensemble Monte Carlo (GEMC) simulations. Our results show that the discrepancies between NLDFT and geometric PSD are significant. NLDFT PSD produced several artificial gaps and…

Covalent triazine frameworks (CTFs) are porous organic materials promising for applications in catalysis and separation due to their high stability, adjustable porosity, and intrinsic nitrogen functionalities. CTFs are prepared by ionothermal trimerization of aromatic nitriles; however, multiple side reactions also occur under synthesis conditions, and their influence on the material properties is still poorly described. Here we report the systematic characterization of nitrogen in CTFs using X-ray photoelectron spectroscopy. With the use of model compounds, we could distinguish several types of nitrogen species. By combining these data with textural properties, we unravel the influence that the reaction temperature, the catalyst, and the monomer structure and composition have on the properties of the resulting CTF materials.

Recently, all-inorganic cesium lead halide (CsPbX 3, X = Cl, Br, and I) nanocrystals (NCs) have drawn wide attention because of their excellent optoelectronic properties and potential applications. However, one of the most significant challenges of such NCs is their low stability against protonic solvents. In this work, we demonstrate that by incorporating a highly branched capping ligand, trioctylphosphine oxide (TOPO), into the traditional oleic acid/oleylamine system, monodisperse CsPbX 3 NCs with excellent optoelectronic properties can be achieved at elevated temperatures (up to 260 °C). The size of such NCs can be varied in a relatively wide range. The capping of TOPO on NCs has been verified through Fourier transform infrared spectroscopy measurement. More importantly, the presence of TOPO can dramatically improve the stability of CsPbX 3 NCs against ethanol treatment. After ethanol treatment for 100 min, the emission intensity of the TOPO-capped sample dropped only 5%, whereas that of non-TOPO-capped NCs dropped up to 86%. This work may shed some light on the preparation and…

In this work, we investigated the kinetic balance between ammonia-catalyzed hydrolysis of tetraethyl orthosilicate (TEOS) and subsequent condensation over the growth of silica particles in the Stöber method. Our results reveal that, at the initial stage, the reaction is dictated by TEOS hydrolysis to form silanol monomers, which is denoted as pathway I and is responsible for nucleation and growth of small silica particles via condensation of neighboring silanol monomers and siloxane network clusters derived thereafter. Afterward, the reaction is dictated by condensation of newly formed silanol monomers onto the earlier formed silica particles, which is denoted as pathway II and is responsible for the enlargement in size of silica particles. When TEOS hydrolysis is significantly promoted, either at high ammonia concentration (≥0.95 M) or at low ammonia concentration in the presence of LiOH as secondary catalyst, temporal separation of pathways I and II makes the Stöber method reminiscent of in situ seeded growth. This knowledge advance enables us not only to reconcile the most…

Recently, extremely small bubbles, referred to as nanobubbles, have drawn increased attention due to their novel properties and great potential for various applications. In this study, a novel method for the generation of bulk nanobubbles (BNBs) was introduced, and stability of fabricated BNBs was investigated. BNBs were created from CO 2 gas with a mixing method; the chemical identity and phase state of these bubbles can be determined via infrared spectroscopy. The presence of BNBs was observed with a nanoparticle tracking analysis (NTA). The ATR-FTIR spectra of BNBs indicate that the BNBs were filled with CO 2 gas. Furthermore, the BNB concentration and its ζ-potential were about 2.94 × 10 8 particles/mL and −20 mV, respectively (24 h after BNB generation with a mixing time of 120 min). This indicates the continued existence and stability of BNBs in water for an extended period of time.

pH-responsive oil-in-water Pickering emulsions were prepared simply by using negatively charged silica nanoparticles in combination with a trace amount of a zwitterionic carboxyl betaine surfactant as stabilizer. Emulsions are stable to coalescence at pH ≤ 5 but phase separate completely at pH > 8.5. In acidic solution, the carboxyl betaine molecules become cationic, allowing them to adsorb on silica nanoparticles via electrostatic interactions, thus hydrophobizing and flocculating them and enhancing their surface activity. Upon increasing the pH, surfactant molecules are converted to zwitterionic form and significantly desorb from particles' surfaces, triggering dehydrophobization and coalescence of oil droplets within the emulsion. The pH-responsive emulsion can be cycled between stable and unstable many times upon alternating the pH of the aqueous phase. The average droplet size in restabilized emulsions at low pH, however, increases gradually after four cycles due to the accumulation of NaCl. Experimental evidence including adsorption isotherms, zeta potentials, microscopy, and…

We establish a tool for direct measurements of the work needed to separate a liquid from a solid. This method mimics a pendant drop that is subjected to a gravitational force that is slowly increasing until the solid-liquid contact area starts to shrink spontaneously. The work of separation is then calculated in analogy to Tate's law. The values obtained for the work of separation are independent of drop size and are in agreement with Dupré's theory, showing that they are equal to the work of adhesion.

Nanoengineered hydrogels offer the potential to design shear-thinning bioinks for three-dimensional (3D) bioprinting. Here, we have synthesized colloidal bioinks composed of disk-shaped two-dimensional (2D) nanosilicates (Laponite) and poly(ethylene glycol) (PEG). The addition of Laponite reinforces the PEG network and increases viscosity, storage modulus, and network stability. PEG-Laponite hydrogels display shear-thinning and self-recovery characteristics due to rapid internal phase rearrangement. As a result, a range of complex patterns can be printed using PEG-Laponite bioinks. The 3D bioprinted structure has similar mechanical properties compared to the as-casted structure. In addition, encapsulated cells within the PEG-Laponite bioink show high viability after bioprinting. Overall, this study introduces a new class of PEG-Laponite colloidal inks for bioprinting and cell delivery.

A mussel-inspired interlayer of polydopamine (PDA)/polyethylenimine (PEI) is codeposited on the ultrafiltration substrate to tune the interfacial polymerization of piperazine and trimesoyl chloride for the preparation of thin-film composite (TFC) nanofiltration membranes (NFMs). This hydrophilic interlayer results in an efficient adsorption of piperazine solution in the substrate pores. The solution height increases with the PDA/PEI codeposition time from 45 to 135 min due to the capillary effect of the substrate pores. The prepared TFC NFMs are characterized with thin and smooth polyamide selective layers by ATR/IR, XPS, FESEM, AFM, zeta potential, and water contact angle measurements. Their water permeation flux measured in a cross-flow process increases to two times as compared with those TFC NFMs without the mussel-inspired interlayer. These TFC NFMs also show a high rejection of 97% to Na 2 SO 4 and an salt rejection order of Na 2 SO 4 ≈ MgSO 4 > MgCl 2 > NaCl.

Direct delivery of proteins and peptides into living mammalian cells has been accomplished using phospholipid liposomes as carrier particles. Such liposomes are usually taken up via endocytosis where the main part of their cargo is degraded in lysosomes before reaching its destination. Here, fusogenic liposomes, a newly developed molecular carrier system, were used for protein delivery. When such liposomes were loaded with water-soluble proteins and brought into contact with mammalian cells, the liposomal membrane efficiently fused with the cellular plasma membrane delivering the liposomal content to the cytoplasm without degradation. To explore the key factors of proteofection processes, the complex formation of fusogenic liposomes and proteins of interest and the size and zeta potential of the formed fusogenic proteoliposoms were monitored. Intracellular protein delivery was analyzed using fluorescence microscopy and flow cytometry. Proteins such as EGFP, Dendra2, and R-phycoerythrin or peptides such as LifeAct-FITC and NTF2-AlexaFluor488 were successfully incorporated into…

Changes in protein expression levels and protein structure may indicate genomic mutations and may be related to some diseases. Therefore, the precise quantification and characterization of proteins can be used for disease diagnosis. Compared with several other alternative methods, surface-enhanced Raman scattering (SERS) spectroscopy is regarded as an excellent choice for the quantification and structural characterization of proteins. Herein, we review the main advance of using plasmonic nanostructures as SERS sensing platform for this purpose. Three design approaches, including direct SERS, indirect SERS, and SERS-encoded nanoparticles, are discussed in the direction of developing new precise approaches of quantification and characterization of proteins. While this Review is focused on proteins, in order to highlight concepts of SERS-based sensors also detection of other biomolecules will be discussed.

Blue luminescent carbon dots (CDs) with a high photoluminescence (PL) quantum yield (48.3 ± 5.3%) were prepared by the one-pot hydrothermal reaction of citric acid with poly(ethylenimine) (PEI). The CDs display bright PL, narrow emission spectra, pH-dependent PL intensity, high photostability, and up-converted luminescence. The CDs exhibit a quenching of both down- and up-conversion PL in the presence of morin and thus serve as useful probes for morin detection. Both down- and up-conversion measurements allow the quantification of concentrations from 0 to 300 μmol/L with a detection limit of 0.6 μmol/L, and this dual-mode detection increases the reliability of the measurement. The proposed method of determination is simple, sensitive, and cost-effective, with potential applications in clinical and biochemical assays.

Aqueous lubrication has emerged as an active research area in recent years due to its prevalence in nature in biotribological contacts and its enormous technological soft-matter applications. In this study, we designed aqueous dispersions of biocompatible whey-protein microgel particles (WPM) (10–80 vol %) cross-linked via disulfide bonding and focused on understanding their rheological, structural and biotribological properties (smooth polydimethylsiloxane (PDMS) contacts, R a < 50 nm, ball-on-disk set up). The WPM particles ( D h = 380 nm) displayed shear-thinning behavior and good lubricating performance in the plateau boundary as well as the mixed lubrication regimes. The WPM particles facilitated lubrication between bare hydrophobic PDMS surfaces (water contact angle 108°), leading to a 10-fold reduction in boundary friction force with increased volume fraction (ϕ ≥ 65%), largely attributed to the close packing-mediated layer of particles between the asperity contacts acting as “true surface-separators”, hydrophobic moieties of WPM binding to the nonpolar surfaces, and…

Mussel-inspired polydopamine (PDA) coatings have been broadly exploited for constructing functional membrane surfaces. One-step codeposition of PDA with antifouling polymers, especially zwitterionic polymers, has been regarded as a promising strategy for fabricating antifouling membrane surfaces. However, one challenge is that the codeposition is usually a slow process over 10 h or even several days. Herein, we report that CuSO 4 /H 2 O 2 is able to notably accelerate the codeposition process of PDA with poly(sulfobetaine methacrylate) (PSBMA). In our case, PSBMA is facilely anchored to the polypropylene microporous membrane (PPMM) surfaces within 1 h with the assistance of PDA because of its strong interfacial adhesion. The PDA/PSBMA-coated PPMMs show excellent surface hydrophilicity, high water permeation flux (7506 ± 528 L/m 2 ·h at 0.1 MPa), and an outstanding antifouling property. Moreover, the antifouling property is maintained after the membranes are treated with acid and alkali solutions as well as organic solvents. To recap, it provides a facile, universal, and time-saving…

Adsorption of interfacially active components at the water/oil interface plays critical roles in determining the properties and behaviors of emulsion droplets. In this study, the droplet probe atomic force microscopy (AFM) technique was applied, for the first time, to quantitatively study the interaction mechanism between water-in-oil (W/O) emulsion droplets with interfacially adsorbed asphaltenes. The behaviors and stability of W/O emulsion droplets were demonstrated to be significantly influenced by the asphaltene concentration of organic solution where the emulsions were aged, aging time, force load, contact time, and solvent type. Bare water droplets could readily coalesce with each other in oil (i.e., toluene), while interfacially adsorbed asphaltenes could sterically inhibit droplet coalescence and induce interfacial adhesion during separation of the water droplets. For low asphaltene concentration cases, the adhesion increased with increasing asphaltene concentration (≤100 mg/L), but it significantly decreased at relatively high asphaltene concentration (e.g., 500 mg/L).…

Mesoporous sulfur-doped graphitic carbon nitride (MCNS) materials were successfully synthesized using thiourea as a low-cost precursor and SiO 2 gel solution as a template through a simple thermal condensation method. The effects of three synthesis key factors, namely, the reaction temperature, the reaction time, and the weight ratio of SiO 2 /thiourea, and also their interactions on the removal rate of methyl orange (MO) were investigated using response surface methodology, and the samples were subjected to several characterization techniques. Results showed that the optimized physicochemical properties could be achieved for the MCNS samples by controlling the synthesis key factors, and it was found that the reaction temperature and the reaction time had significant influences on the MO photocatalytic removal. Among bulk graphitic carbon nitride (g-C 3 N 4 ), CN (undoped g-C 3 N 4 ), CNS (sulfur-doped g-C 3 N 4 without template), and TiO 2 (Degussa P25) samples, the optimized MCNS-4 illustrated the highest photocatalytic activity toward the removal of MO under visible light…

A comprehensive overview of the process of digestive ripening that is known to convert polydisperse nanocrystals to monodisperse ones is presented. Apart from highlighting the role of organic molecules (ligands) in achieving size control, the roles of other parameters such as the nanocrystal-ligand binding strength and the temperature at which the reaction is carried out in accomplishing size control are also delineated. The generality of the procedure is illustrated by providing examples of how it is used to prepare monodisperse nanocrystals of different metals, alloy systems, and ultrasmall nanocrystals and also to narrow the size distribution in complex binary and ternary nanocrystal systems. Finally, the current status as far as the theoretical understanding of how size control is being achieved by digestive ripening is laid out, emphasizing at the same time the necessity to undertake more systematic studies to completely realize the full potential of this practically very useful procedure.

Elucidating the intrinsic water wettability of the graphitic surface has increasingly attracted research interests, triggered by the recent finding that the well-established hydrophobicity of graphitic surfaces actually results from airborne hydrocarbon contamination. Currently, static water contact angle (WCA) is often used to characterize the intrinsic water wettability of graphitic surfaces. In the current paper, we show that because of the existence of defects, static WCA does not necessarily characterize the intrinsic water wettability. Freshly exfoliated graphite of varying qualities, characterized using atomic force microscopy and Raman spectroscopy, was studied using static, advancing, and receding WCA measurements. The results showed that graphite of different qualities (i.e., defect density) always has a similar advancing WCA, but it could have very different static and receding WCAs. This finding indicates that defects play an important role in contact angle measurements, and the static contact angle does not always represent the intrinsic water wettability of pristine…

Abstract The Marangoni contraction of sessile drops of a binary mixture of a volatile and a nonvolatile liquid has been investigated experimentally and theoretically. The origin of the contraction is the locally inhomogeneous evaporation rate of sessile drops. This leads to surface tension gradients and thus to a Marangoni flow. Simulations show that the interplay of Marangoni flow, capillary flow, diffusive transport, and evaporative losses can establish a quasistationary drop profile with an apparent nonzero contact angle even if both liquid components individually wet the substrate completely. Experiments with different solvents, initial mass fractions, and gaseous environments reveal a previously unknown universal power-law relation between the apparent contact angle and the relative undersaturation of the ambient atmosphere: θapp ∼ (RHeq – RH)1/3. This experimentally observed power law is in quantitative agreement with simulation results. The exponent can also be inferred from a scaling analysis of the hydrodynamic-evaporative evolution equations of a binary mixture of liquids…

A comprehensive analysis of experimental data relating to so-called "soft sparking" mode of plasma electrolytic oxidation (PEO) has been undertaken. The transition to the soft sparking mode is accompanied by a number of characteristic effects, such as a decrease in anodic voltage, acoustic and light emission, increase in hysteresis in transient current-voltage curves, improved uniformity of the discharge distribution on the surface, disappearance of atomic lines, and development of continuous radiation in the optical emission spectra. An explanation of the main features of PEO process operated under soft sparking conditions is proposed assuming the existence of a specific narrow region in the coating thickness, where the main anodic voltage drops. Because of high electric field in this "active zone", both anodic oxidation of the metal substrate and high-energy processes may take place. According to this assertion, the soft sparking mode of PEO is caused by cathodic polarization (a) eliminating the potential barrier at the oxide-electrolyte interface due to local acidification and…

A facile and effective approach for the preparation of functionalized born nitride quantum dots (BNQDs) with blue fluorescence was explored by the hydrothermal treatment of the mixture of boric acid and melamine at 200 °C for 15 h. The as-prepared BNQDs were characterized by transmission electron microscopy (TEM), high-resolution TEM, atomic force microscopy, X-ray photoelectron spectroscopy, UV–vis spectroscopy, and fluorescence spectroscopy. The single layered BNQDs with the average size of 3 nm showed a blue light emission under the illumination of the UV light. The BNQDs could be easily dispersed in an aqueous medium and applied as fluorescent probes for selective detection of Fe 3+ with remarkable selectivity and sensitivity (the lowest detection limit was 0.3 μM). The fluorescence fiber imaging demonstrated that the as-prepared quantum dots could be used as a valuable fluorchrome. Therefore, the BNQDs could be envisioned for potential applications in many fields such as biocompatible staining, fluorescent probes, and biological labeling.

The interactions of emulsion drops and gas bubbles in complex fluids play important roles in a wide range of biological and technological applications, such as programmable drug and gene delivery, emulsion and foam formation, and froth flotation of mineral particles. In this feature article, we have reviewed our recent progress on the quantification of surface forces and interaction mechanisms of gas bubbles and emulsion drops in different material systems by using several complementary techniques, including the drop/bubble probe atomic force microscope (AFM), surface forces apparatus (SFA), and four-roll mill fluidic device. These material systems include the bubble-self-assembled monolayer (SAM), bubble-polymer, bubble-superhydrophobic surface, bubble-mineral, water-in-oil and oil-in-water emulsions with interface-active components in oil production, and oil/water wetting on polyelectrolyte surfaces. The bubble probe AFM combined with reflection interference contrast microscopy (RICM) was applied for the first time to simultaneously quantify the interaction forces and…

Studies on the adsorption of biopolymers onto halloysite nanotubes (HNTs) in water were conducted. Three polymers with different charges-anionic (pectin), neutral (hydroxypropyl cellulose), and cationic (chitosan)-were chosen. The thermodynamic parameters for the adsorption of polymers onto the HNT surface were determined by isothermal titration calorimetry (ITC). The experimental data were interpreted based on a Langmuir adsorption model. The standard variations in free energy, enthalpy, and entropy of the process were obtained and discussed. Turbidimetry was used to evaluate the stability of functionalized nanoparticles in water. The ζ-potential clarified the surface charge properties of functionalized nanotubes upon polymer adsorption. The interaction of modified nanotubes with polymers led to the formation of a colloidal system with tunable stability and surface properties, which offers different perspectives on new applications of these dispersions, such as carriers for substances to be released in response to external stimuli.

Microsecond simulations have been performed to investigate CH 4 hydrate formation from gas/water two-phase systems between silica and graphite surfaces, respectively. The hydrophilic silica and hydrophobic graphite surfaces exhibit substantially different effects on CH 4 hydrate formation. The graphite surface adsorbs CH 4 molecules to form a nanobubble with a flat or negative curvature, resulting in a low aqueous CH 4 concentration, and hydrate nucleation does not occur during 2.5 μs simulation. Moreover, an ordered interfacial water bilayer forms between the nanobubble and graphite surface thus preventing their direct contact. In contrast, the hydroxylated-silica surface prefers to be hydrated by water, with a cylindrical nanobubble formed in the solution, leading to a high aqueous CH 4 concentration and hydrate nucleation in the bulk region; during hydrate growth, the nanobubble is gradually covered by hydrate solid and separated from the water phase, hence slowing growth. The silanol groups on the silica surface can form strong hydrogen bonds with water, and hydrate cages need…

Electron–hole pair separation efficiency and adsorption performance of photocatalysts to CO 2 are the two key factors affecting the performance of photocatalytic CO 2 reduction with H 2 O. Distinct from conventional promoter addition, this study proposed a novel approach to address these two issues by tuning the own surface features of semiconductor photocatalyst. Three ZnO samples with different morphologies, surface area, and defect content were fabricated by varying preparation methods, characterized by XRD, TEM, and room-temperature PL spectra, and tested in photoreduction of CO 2 with H 2 O. The results show that the as-prepared porous ZnO nanosheets exhibit a much higher activity for photoreduction of CO 2 with H 2 O when compared to ZnO nanoparticles and nanorods attributed to the existence of more defect sites, that is, zinc and oxygen vacancies. These defects would lower the combination rate of electron–hole pair as well as promote the formation of basic zinc carbonate by Lewis acid–base interaction, which is the active intermediate species for photoreduction of CO 2 . ZnO…

The influence of inorganic anions on the photoreactivity and aggregation of titanium dioxide nanoparticles (NPs) was assessed by dosing carbonate, chloride, nitrate, phosphate, and sulfate as potassium salts at multiple concentrations. NP stability was monitored in terms of aggregate morphology and electrophoretic mobility (EPM). Aggregate size and fractal dimension were measured over time by laser diffraction, and the isoelectric point (IEP) as a function of anion and concentration was obtained by measuring EPM versus pH. Phosphate, carbonate, and to a lesser extent, sulfate decreased the IEP of TiO 2 and stabilized NP suspensions owing to specific surface interactions, whereas this was not observed for nitrate and chloride. TiO 2 NPs were exposed to UV-A radiation, and the photoreactivity was assessed by monitoring the production of reactive species over time both at the NP surface (photogenerated holes) and in the bulk solution (hydroxyl radicals) by observing their reactions with the selective probe compounds iodide and terephthalic acid, respectively. The generation of…

We demonstrate a facile method to induce water droplet motion on an wedge-shaped superhydrophobic copper surface combining with a poly(dimethylsiloxane) (PDMS) oil layer on it. The unbalanced interfacial tension from the shape gradient offers the actuating force. The superhydrophobicity critically eliminates the droplet contact line pinning and the slippery PDMS oil layer lubricates the droplet motion, which makes the droplet move easily. The maximum velocity and furthest position of droplet motion were recorded and found to be influenced by the gradient angle. The mechanism of droplet motion on the shape gradient surface is systematically discussed, and the theoretical model analysis is well matched with the experimental results.

Abstract The effectiveness of water flooding oil recovery depends to an important extent on the competitive wetting of oil and water on the solid rock matrix. Here, we use macroscopic contact angle goniometry in highly idealized model systems to evaluate how brine salinity affects the balance of wetting forces and to infer the microscopic origin of the resultant contact angle alteration. We focus, in particular, on two competing mechanisms debated in the literature, namely, double-layer expansion and divalent cation bridging. Our experiments involve aqueous droplets with a variable content of chloride salts of Na+, K+, Ca2+, and Mg2+, wetting surfaces of muscovite and amorphous silica, and an environment of ambient decane containing small amounts of fatty acids to represent polar oil components. By diluting the salt content in various manners, we demonstrate that the water contact angle on muscovite, not on silica, decreases by up to 25° as the divalent cation concentration is reduced from typical concentrations in seawater to zero. Decreasing the ionic strength at a constant…

Giant unilamellar vesicles (GUVs) represent a versatile model system to emulate the fundamental properties and functions associated with the plasma membrane of living cells. Deformability and shape transitions of lipid vesicles are closely linked to the mechanical properties of the bilayer membrane itself and are typically difficult to control under physiological conditions. Here, we developed a protocol to form cell-sized vesicles from an azobenzene-containing phosphatidylcholine (azo-PC), which undergoes photoisomerization on irradiation with UV-A and visible light. Photoswitching within the photolipid vesicles enabled rapid and precise control of the mechanical properties of the membrane. By varying the intensity and dynamics of the optical stimulus, controlled vesicle shape changes such as budding transitions, invagination, pearling, or the formation of membrane tubes were achieved. With this system, we could mimic the morphology changes normally seen in cells, in the absence of any molecular machines associated with the cytoskeleton. Furthermore, we devised a mechanism to…

A novel magnetic nanocomposite was synthesized using graphene oxide (GO), polyethylenimine (PEI), and Fe 3 O 4 to removal hexavalent chromium (Cr(VI)) from water and soil. Therein, GO was functionalized with plenty of −NH 2 by the modification of PEI through an amidation reaction, and the resulting GO/PEI reacted with FeSO 4 ·7H 2 O and NaBH 4 to obtain RGO/PEI/Fe 3 O 4 (the optimal one is designated as ORPF) through an oxidation–reduction reaction. ORPF could effectively adsorb Cr(VI) through electrostatic attraction, and the adsorbed Cr(VI) ions were partially reduced to trivalent chromium (Cr(III)) with low toxicity by RGO (π electron). Afterward, the resulting ORPF-Cr could be conveniently removed from water with a magnet, achieving the maximum Cr(VI) removal capacity of 266.6 mg/g. Importantly, ORPF, once carried by sponge particles, could efficiently remove Cr(VI) from soil, and the resulting mixture could be facilely collected with a magnet on a filter net. Besides, the leaching experiment suggested that, when supported by filter paper, ORPF was able to decrease the number of…

An alkaline environment and the presence of oxygen are essential requirements for dopamine polymerization. In this study, we are the first to demonstrate the self-polymerization of dopamine through plasma-activated water (PAW) under acidic environments (pH < 5.5). Resulting poly(dopamine) (PDA) was characterized using Nanosizer, SEM, FTIR, UV–vis, 1 H NMR, and fluorescence spectrophotometers and proved to have similar physical and chemical properties to those polymerized under a basic condition, except that the PDA particles formed in PAW were more stable and hardly aggregated at varied pHs. The PAW polymerization method avoids alkaline solutions and the presence of oxygen and thus extends the applications of dopamine polymerization, particularly in biomedical and pharmaceutical sciences.

Superhydrophobic surfaces have myriad industrial applications, yet their practical utilization has been limited by their poor mechanical durability and longevity. We present a low-cost, facile process to develop superhydrophobic copper-based coatings via an electrodeposition route, that addresses this limitation. Through electrodeposition, a stable, multiscale, cauliflower shaped fractal morphology was obtained and upon modification by stearic acid, the prepared coatings show extreme water repellency with contact angle of 162 ± 2° and roll-off angle of about 3°. Systematic studies are presented on coatings fabricated under different processing conditions to demonstrate good durability, mechanical and underwater stability, corrosion resistance, and self-cleaning effect. The study also presents an approach for rejuvenation of slippery superhydrophobic nature (roll-off angle <10°) on the surfaces after long-term water immersion. The presented process can be scaled to larger, durable coatings with controllable wettability for diverse applications.

Some polyzwitterionic brushes exhibit a strong “anti-polyelectrolyte effect” and ionic specificity that make them versatile platforms to build smart surfaces for many applications. However, the structure–property relationship of zwitterionic polymer brushes still remains to be elucidated. Herein, we aim to study the structure-dependent relationship between different zwitterionic polymers and the anti-polyelectrolyte effect. To this end, a series of polyzwitterionic brushes with different cationic moieties (e.g., imidazolium, ammonium, and pyridinium) in their monomeric units and with different carbon spacer lengths (e.g., CSL = 1, 3, and 4) between the cation and anion were designed and synthesized to form polymer brushes via the surface-initiated atom transfer radical polymerization. All zwitterionic brushes were carefully characterized for their surface morphologies, compositions, wettability, and film thicknesses by atomic force microscopy, contact angle measurement, and ellipsometry, respectively. The salt-responsiveness of all zwitterionic brushes to surface hydration and…

Design of new materials with sophisticated nanostructure has been proven to be an efficient strategy to improve their properties in many applications. Herein, we demonstrate the successful combination of high electron conductive materials of NiCo 2 O 4 with high capacitance materials of MnMoO 4 by forming a core–shell nanostructure. The NiCo 2 O 4 @MnMoO 4 core–shell nanoarrays (CSNAs) electrode possesses high capacitance of 1169 F g –1 (4.24 F cm –2 ) at a current density of 2.5 mA cm –2, obviously larger than the pristine NiCo 2 O 4 electrode. The asymmetric supercapacitors (ASCs), assembled with NiCo 2 O 4 @MnMoO 4 CSNAs as binder-free cathode and active carbon (AC) as anode, exhibit high energy density of 15 Wh kg –1 and high power density of 6734 W kg –1 . Cycle performance of NiCo 2 O 4 @MnMoO 4 CSNAs//AC ASCs, conducted at current density of 20 mA cm –2, remain 96.45% of the initial capacitance after 10,000 cycles, demonstrating its excellent long-term cycle stability. Kinetically decoupled analysis reveals that the capacitive capacitance is dominant in the total capacitance…

Abstract We measured the transbilayer diffusion of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) in large unilamellar vesicles, in both the gel (Lβ′) and fluid (Lα) phases. The choline resonance of headgroup-protiated DPPC exchanged into the outer leaflet of headgroup-deuterated DPPC-d13 vesicles was monitored using 1H NMR spectroscopy, coupled with the addition of a paramagnetic shift reagent. This allowed us to distinguish between the inner and outer bilayer leaflet of DPPC, to determine the flip-flop rate as a function of temperature. Flip-flop of fluid-phase DPPC exhibited Arrhenius kinetics, from which we determined an activation energy of 122 kJ mol–1. In gel-phase DPPC vesicles, flip-flop was not observed over the course of 250 h. Our findings are in contrast to previous studies of solid-supported bilayers, where the reported DPPC translocation rates are at least several orders of magnitude faster than those in vesicles at corresponding temperatures. We reconcile these differences by proposing a defect-mediated acceleration of lipid translocation in supported bilayers,…

Abstract High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl2 concentration. Using DLVO theory with charge regulation, we determine from the measured force–distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca2+ ion adsorption, while Cl– adsorption at higher CaCl2 concentrations partially neutralizes the surface charge. Atomic resolution imaging…

A facile route to synthesize hydrophilically or hydrophobically grafted graphitic carbon nitride (g-CN) is reported. For this purpose, functionalized olefinic molecules with a low polymerization tendency are utilized for grafting onto the surface to preserve the features of g-CN while improving its dispersibility. One-pot, visible light-induced grafting yields highly dispersible g-CNs either in aqueous or organic media. Moreover, functional groups such as amines can be introduced, which yields pH-dependent dispersibility in aqueous media. Compared with unfunctionalized g-CN, low sonication times are sufficient to redisperse g-CN. In addition, because of increased dispersion stability, higher amounts of functionalized g-CN can be dispersed (up to 10% in aqueous dispersion and 2% in organic dispersion) when compared to unfunctionalized g-CN.

Different metal chalcogenides, being a potential candidate for hydrogen evolution catalysts, have attracted enormous attention in the field of water splitting. In the present study, Ag 2 S/Ag is revealed as an efficient catalyst for hydrogen evolution. When a sacrificial template of the CuS nanostructure is used, Ag 2 S/Ag heterostructures are synthesized following a simple wet-chemical technique. Two different routes, wet chemical and hydrothermal, are followed to modulate the morphology of the CuS templates from flower ball to wirelike structures, which subsequently results in the formation of Ag 2 S nanostructure. Finally, the Ag layer is deposited on Ag 2 S with the help of a photoreduction technique. The unique heterostructure of Ag 2 S/Ag shows efficient catalytic activity in the H 2 evolution reaction. A Ag 2 S/Ag wire can successfully generate a 10 mA/cm 2 current density at a −0.199 V potential. Ag 2 S/Ag contains the micronanostructure where nanoplates of Ag 2 S/Ag assemble to give rise to microstructures such as flower balls and wire.

The self-assembly process in cellulose nanocrystal (CNC) film formation was studied as a function of evaporation time. It is known that the total evaporation time of CNC dispersions affects the structure of the film obtained, but the extension of different phases of the evaporation has not been explored. By extending the evaporation time of CNC suspensions after the onset of liquid crystallinity, the homogeneity of the resulting films could be improved as observed by polarized optical microscopy and scanning electron microscopy. Here, we show that an intermediate stage of self-assembly, between phase separation and gel vitrification, called tactoid annealing, helps explain the discrepancies in order for chiral nematic CNC films dried at varying evaporation times. This intermediate stage of self-assembly may be useful for designing highly ordered and homogenous CNC-based materials.

In the search for new building blocks of nanofibrillar hydrogels, cellulose nanocrystals (CNCs) have attracted great interest because of their sustainability, biocompatibility, ease of surface functionalization, and mechanical strength. Making these hydrogels fluorescent extends the range of their applications in tissue engineering, bioimaging, and biosensing. We report the preparation and properties of a multifunctional hydrogel formed by CNCs and graphene quantum dots (GQDs). We show that although CNCs and GQDs are both negatively charged, hydrogen bonding and hydrophobic interactions overcome the electrostatic repulsion between these nanoparticles and yield a physically cross-linked hydrogel with tunable mechanical properties. Owing to their shear-thinning behavior, the CNC-GQD hydrogels were used as an injectable material in 3D printing. The hydrogels were fluorescent and had an anisotropic nanofibrillar structure. The combination of these advantageous properties makes this hybrid hydrogel a promising material and fosters the development of new manufacturing methods such as 3D…

In many liposome applications, the nanomechanical properties of the membrane envelope are essential to ensure, e.g., physical stability, protection, or penetration into tissues. Of all factors, the lipid composition and its phase behavior are susceptible to tune the mechanical properties of membranes. To investigate this, small unilamellar vesicles (SUV; diameter < 200 nm), referred to as liposomes, were produced using either unsaturated 1,2-dioleoyl- sn -glycero-3-phosphocholine (DOPC) or saturated 1,2-dipalmitoyl- sn -glycero-3-phosphocholine (DPPC) in aqueous buffer at pH 6.7. The respective melting temperatures of these phospholipids were −20 and 41 °C. X-ray diffraction analysis confirmed that at 20 °C DOPC was in the fluid phase and DPPC was in the gel phase. After adsorption of the liposomes onto flat silicon substrates, atomic force microscopy (AFM) was used to image and probe the mechanical properties of the liposome membrane. The resulting force–distance curves were treated using an analytical model based on the shell theory to yield the Young’s modulus ( E ) and the…

The controllable and efficient electrochemical preparation of highly crystalline graphene quantum dots (GQDs) in an aqueous system is still challenging. Here, we developed a weak electrolyte-based (typically an ammonia solution) electrochemical method to enhance the oxidation and cutting process and therefore achieve a high yield of GQDs. The yield of GQDs (3–8 nm) is 28%, approximately 28 times higher than the yield of GQDs prepared by other strong electrolytes. The whole preparation process can be accomplished within 2 h because of the effective free radical oxidation process and the suppressed intercalation-induced exfoliation in weakly ionized aqueous electrolytes. The GQDs also showed excellent crystallinity which is obviously better than the crystallinity of GQDs obtained via bottom-up approaches. Moreover, amino-functionalization of GQDs can be realized by manipulating the electrolyte concentration. We further demonstrate that the proposed method can also be expanded to other weak electrolytes (such as HF and H 2 S) and different anode precursor materials (such as…

Nanocellulose (NC) suspensions can form rigid volume-spanning arrested states (VASs) at very low volume fractions. The transition from a free-flowing dispersion to a VAS can be the result of either an increase in particle concentration or a reduction in interparticle repulsion. In this work, the concentration-induced transition has been studied with a special focus on the influence of the particle aspect ratio and surface charge density, and an attempt is made to classify these VASs. The results show that for these types of systems two general states can be identified: glasses and gels. These NC suspensions had threshold concentrations inversely proportional to the particle aspect ratio. This dependence indicates that the main reason for the transition is a mobility constraint that, together with the reversibility of the transition, classifies the VASs as colloidal glasses. If the interparticle repulsion is reduced, then the glasses can transform into gels. Thus, depending on the preparation route, either soft and reversible glasses or stiff and irreversible gels can be formed.