The 50 most-cited articles in Langmuir, 2023

In this feature article, we critically review the physical properties of porous hydrogels and their production methods. Our main focus is nondense hydrogels that have physical pores besides the space available between adjacent cross-links in the polymer network. After reviewing theories on the kinetics of swelling, equilibrium swelling, the structure-stiffness relationship, and solute diffusion in dense hydrogels, we propose future directions to develop models for porous hydrogels. The aim is to show how porous hydrogels can be designed and produced for studies leading to the modeling of physical properties. Additionally, different methods that are used for making hydrogels with physically incorporated pores are briefly reviewed while discussing the potentials, challenges, and future directions for each method. Among kinetic methods, we discuss bubble generation approaches including reactions, gas injection, phase separation, electrospinning, and freeze-drying. Templating approaches discussed are solid-phase, self-assembled amphiphiles, emulsion, and foam methods.

Bacterial fouling is a persistent problem causing the deterioration and failure of functional surfaces for industrial equipment/components; numerous human, animal, and plant infections/diseases; and energy waste due to the inefficiencies at internal and external geometries of transport systems. This work gains new insights into the effect of surface roughness on bacterial fouling by systematically studying bacterial adhesion on model hydrophobic (methyl-terminated) surfaces with roughness scales spanning from ∼2 nm to ∼390 nm. Additionally, a surface energy integration framework is developed to elucidate the role of surface roughness on the energetics of bacteria and substrate interactions. For a given bacteria type and surface chemistry; the extent of bacterial fouling was found to demonstrate up to a 75-fold variation with surface roughness. For the cases showing hydrophobic wetting behavior, both increased effective surface area with increasing roughness and decreased activation energy with increased surface roughness was concluded to enhance the extent of bacterial adhesion. For…

Swelling in polymer materials is a ubiquitous phenomenon. At a molecular level, swelling is dictated by solvent-polymer interactions, and has been thoroughly studied both theoretically and experimentally. Favorable solvent-polymer interactions result in the solvation of polymer chains. For polymers in confined geometries, such as those that are tethered to surfaces, or for polymer networks, solvation can lead to swelling-induced tensions. These tensions act on polymer chains and can lead to stretching, bending, or deformation of the material both at the micro- and macroscopic scale. This Invited Feature Article sheds light on such swelling-induced mechanochemical phenomena in polymer materials across dimensions, and discusses approaches to visualize and characterize these effects.

Metal-organic frameworks (MOFs) are promising candidates for membrane gas separation. MOF-based membranes include pure MOF membranes and MOF-based mixed matrix membranes (MMMs). This Perspective discusses the challenges for the next stage of the development of MOF-based membranes based on research conducted in the past decade. We focused on three major issues associated with pure MOF membranes. First, some MOF compounds have been overstudied, despite the availability of numerous MOFs. Second, gas adsorption and diffusion in MOFs are often independently investigated. The correlation between adsorption and diffusion has seldom been discussed. Third, we identify the importance of characterizing the gas distribution in MOFs to understand the structure-property relationships for gas adsorption and diffusion in MOF membranes. For MOF-based MMMs, engineering the MOF-polymer interface is essential for achieving the desired separation performance. Various approaches to modify the MOF surface or polymer molecular structure have been proposed to improve the MOF-polymer interface. Herein, we…

In this perspective paper, we highlight the numerous open problems in the topic of stability of emulsions and foams, focusing on the simplest case of dispersions stabilized by surfactants. There are three main destabilization processes, gravity induced evolution, Ostwald ripening, and drops or bubble coalescence, which are analyzed separately. The discussion is restricted to the case of Newtonian fluids, deprived of microstructure, except for the presence of micelles. Thanks to continuing efforts and recent breakthroughs, we show that the understanding of emulsion and foam stability is progressing. Many problems are still open, however, and much work remains to be done along the lines outlined in the paper.

The fabrication of defect rich S-scheme binary heterojunction system with enhanced space charge separation and mobilization is a pioneering approach for improving photoreduction efficiency towards the production of value added chemicals. Herein, we have rationally fabricated an atomic sulfur defect-rich hierarchical UiO-66(−NH 2 )/CuInS 2 n-p heterojunction system by uniform dispersion of UiO-66(−NH 2 ) (UN66) nanoparticles over the surface of hierarchical CuInS 2 nanosheets under mild conditions. The designed heterostructures are characterized by using different structural, microscopic, and spectroscopic techniques. The hierarchical CuInS 2 (CIS) component shows surface sulfur defects leading to creation of more surface exposed active sites with improved absorption of visible light and augmented diffusion of charge carriers. The photocatalytic performance of prepared UiO-66(−NH 2 )/CuInS 2 heterojunction materials is explored for N 2 fixation and O 2 reduction reactions (ORR). The optimal UN66/CIS20 heterostructure photocatalyst exhibited outstanding N 2 fixation and O 2 reduction…

The droplet size in emulsions is known to affect the rheological properties and plays a crucial role in many applications of emulsions. Despite its importance, the underlying mechanisms governing droplet size in emulsification remain poorly understood. We investigate the average drop size and size distribution upon emulsification with a high-shear mixer for model oil-in-water emulsions stabilized by a surfactant. The size distribution is found to be a log-normal distribution resulting from the repetitive random breakup of drops. High-shear emulsification, the usual way of making emulsions, is therefore found to be very different from turbulent emulsification given by the Kolmogorov-Hinze theory, for which power-law distributions of the drop size are expected. In agreement with this, the mean droplet size does not follow a scaling with the Reynolds number of the emulsification flow but rather a capillary number scaling based on the viscosity of the continuous phase.

Herein, we report a hydrothermal method to synthesize pristine and Ag-doped WO 3 nanoplates and study their multifunctional competence in the accomplishment of enhanced catalytic organic conversion and highly efficient photocatalytic and electrocatalytic H 2 evolution reactions. The as-synthesized nanoplates were characterized by using various techniques including X-ray diffraction, field emission scanning electron microscopy-energy-dispersive X-ray analysis, transmission electron microscopy, UV–vis diffuse reflectance spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and BET surface area studies. The significant catalytic performance was shown by 1% Ag-doped WO 3 nanoplates with 100% glycerol conversion and 90% triacetin selectivity. The photocatalytic activity was also examined toward water splitting H 2 evolution reaction which demonstrates the highest H 2 evolution of 12.06 mmol g –1 catalyst for 1% Ag-doped WO 3 nanoplates in a time span of 8 h. Moreover, the electrocatalytic hydrogen evolution reaction was also monitored in acidic media (0.1 M H 2 SO 4 )…

High Resolution Image Download MS PowerPoint Slide Researchers have made significant efforts over the past few decades to understand adsorption by developing various simple adsorption isotherm models. However, though many contaminants usually occur as multicomponent mixtures in nature, multicomponent adsorption isotherms have received limited attention and remain an area of inadequate research. We have presented here in a new multicomponent adsorption isotherm model, named the Jeppu Amrutha Manipal Multicomponent (JAMM) isotherm, that can alleviate this problem. We first developed the JAMM multicomponent isotherm using our experimental data sets of arsenic and fluoride competitive adsorption on activated carbon. We then tested the JAMM multicomponent isotherm for a case study of cadmium and zinc competitive adsorption. Next, we further assessed the JAMM isotherm using another competitive adsorption case study of copper and chromium. Through extensive validation studies and error analysis, the JAMM isotherm was able to demonstrate its efficacy in predicting the adsorption behavior in…

Currently, more than 100 isotherm models coexist for the six IUPAC isotherm types. However, no mechanistic insights can be reached when several models, each claiming a different mechanism, fit an experimental isotherm equally well. More frequently, popular isotherm models [such as the site-specific models like Langmuir, Brunauer-Emmett-Teller (BET), and Guggenheim-Anderson-de Boer (GAB)] have been applied to real and complex systems that break their basic assumptions. To overcome such conundrums, we establish a universal approach to model all isotherm types, attributing the difference to the sorbate-sorbate and sorbate-surface interactions in a systematic manner. We have generalized the language of the traditional sorption models (such as the monolayer capacity and the BET constant) to the model-free concepts of partitioning and association coefficients that can be applied across the isotherm types. Through such a generalization, the apparent contradictions, caused by applying the site-specific models alongside with cross-sectional area of sorbates for the purpose of surface area…

The green hydrogen economy is expected to play a crucial role in carbon neutrality, but industrial-scale water electrolysis requires improvements in efficiency, operation costs, and capital costs before broad deployment. Electrolysis operates at a high current density and involves the substantial formation of gaseous products from the electrode surfaces to the electrolyte, which may lead to additional resistance and a resulting loss of efficiency. A detailed clarification of the bubble departure phenomena against the electrode surface and the surrounding electrolytes is needed to further control bubbles in a water electrolyzer. This study clarifies how electrolyte properties affect the measured bubble detachment sizes from the comparisons with analytical expressions and dynamic simulations. Bubble behavior in various electrolyte solutions and operating conditions was described using various physical parameters. A quantitative relationship was then established to connect electrolyte properties and bubble departure diameters, which can help regulate the bubble management through…

This study investigates the influence of physical parameters such as porosity, permeability, pore-throat radius, and specific surface area/volume on the adsorption capacity of surfactants in the pore surface of reservoirs. In the meantime, the hydraulic fracturing-assisted oil displacement (HFAD) technique can effectively improve the permeability and porosity of pores in the reservoir, which may affect the adsorption capacity of surfactants in low-permeability reservoirs. This may help to reduce the adsorption loss of surfactants in low-permeability reservoirs. Based on physical simulation methods, dynamic adsorption experiments were conducted to clarify the dynamic saturation adsorption capacity effect of high-pressure and low-pressure displacement agents by the HFAD technique. In addition, the molecular dynamics simulation method was used to study the effect of high-pressure conditions of HFAD on the adsorption capacity of surfactants on weakly lipophilic silica walls. Under the condition of high injection pressure by the HFAD technique, the fluid flow velocity and the initial…

Detecting the types and concentrations of dissolved gases in insulating oil by resistivity-type sensors is an extremely effective means for diagnosing faults in an oil-immersed transformer. However, further breakthroughs and innovations are needed in gas-sensitive materials for preparing high-performance resistivity-type sensors. In this investigation, the application possibility of using Pt-doped HfS 2 (Pt-HfS 2 ) as gas-sensitive materials for the detection of dissolved H 2, CO 2, CH 4, and C 2 H 2 in oil has been verified by analyzing the adsorption energy ( E ad ), differential charge density (DCD), density of states (DOS), frontier molecular orbital, and desorption time based on density functional theory (DFT). The outcomes suggest that the band gap of HfS 2 is obviously narrowed after doping Pt at the position of the bridge between the S and Hf atoms, resulting in a significant increase in the conductivity of HfS 2 . The low adsorption energy implies that there is only weak physical adsorption between Pt-HfS 2 and CO 2 (−0.783 eV). In contrast, the highly hybridized atomic…

Recently the focus of the Langmuir-Blodgett technique as a method of choice to transfer monolayers from the air/water interface onto solid substrates in a controllable fashion has been shifting toward purely hydrophobic gold and silver nanoparticles. The fundamental interactions between particles that become relevant in the absence of polar groups range from dispersive attractions from the metal cores and repulsions between ligand shells to weaker entropic factors. The layer evolution is explored, starting with interfacial self-assembly upon solution spreading and domain and circular island formation, which subsequently merge into a complete monolayer and finally form multilayers or macroscopic wrinkles. Moreover, structural properties such as the core:ligand size ratio are investigated in the context of dispersive forces, whereby the nanoparticles with small cores and long ligands tend not to aggregate sufficiently to produce continuous films, those with large cores and short ligands were found to aggregate irreversibly, and those in between the two extremes were concluded to be…

Hydrogen and oxygen evolution via photocatalytic water splitting remains the quintessential alternative to fossil fuels. Photocatalysts must be sufficiently robust, competent, and productive toward harnessing sunlight in order to utilize the solar spectrum for maximal photocatalytic output. Herein, we have fabricated the MgIn 2 S 4 /UiO-66-NH 2 composite via a facile solvothermal route and have determined its efficacy toward light-induced H 2 and O 2 generation reactions through water splitting with the aid of different sacrificial agents. Initially, the formation of pristine and composite materials was ascertained by PXRD, FTIR, etc. Moreover, with the aid of sophisticated morphological characterization techniques (FESEM and HRTEM), the intricate interaction between MgIn 2 S 4 and UiO-66-NH 2 was revealed. Additionally, the XPS studies suggested the effective interaction between the individual components with binding energy shifting suggesting the transfer of electrons from Zr-MOF to MgIn 2 S 4 . The PL and electrochemical aspects supported the effective photogenerated charge…

The name of Herbert Freundlich is commonly associated with a power relationship for adsorbed amount of a substance ( C ads ) against the concentration in solution ( C sln ), such that C ads = K C sln n; this isotherm (together with the Langmuir isotherm) is considered to be the model of choice for correlating the experimental adsorption data of micropollutants or contaminants of emerging concern (pesticides, pharmaceuticals, and personal care products), but it also concerns the adsorption of gases on solids. However, Freundlich’s 1907 paper was a “sleeping beauty”, which only started to attract significant citations from the early 2000s onward; moreover, these citations were too often wrong. In this paper, the main steps in the historical developments of Freundlich isotherm are identified, along with a discussion of several theoretical points: (1) derivation of the Freundlich isotherm from an exponential distribution of energies, leading to a more general equation, based on the Gauss hypergeometric function, of which the power Freundlich equation is an approximation; (2) application…

Amino acid-capped gold nanoparticles (AuNPs) are a promising tool for various applications, including therapeutics and diagnostics. Most often, amino acids are used to cap AuNPs synthesized with other reducing agents. However, only a few studies have been dedicated to using α-amino acids as reducing and capping agents in AuNPs synthesis. Hence, there are still several gaps in understanding their role in reducing gold salts. Here, we used 20 proteinogenic α-amino acids and one non-proteinogenic α-amino acid in analogy to sodium citrate as reducing and capping agents in synthesizing AuNPs using the Turkevich method. Only four of the twenty-one investigated amino acids have not yielded gold nanoparticles. The shape, size distribution, stability, and optical properties of synthesized nanoparticles were characterized by scanning electron microscopy, differential centrifugal sedimentation, the phase analysis light scattering technique, and UV-vis spectroscopy. The physicochemical characteristics of synthesized AuNPs varied with the amino acid used for the reduction. We proposed that in…

Antifouling (AF) nanocoatings made of polydimethylsiloxane (PDMS) are more cost-efficient and eco-friendly substitutes for the already outlawed tributyltin-based coatings. Here, a catalytic hydrosilation approach was used to construct a design inspired by composite mosquito eyes from non-toxic PDMS nanocomposites filled with graphene oxide (GO) nanosheets decorated with magnetite nanospheres (GO–Fe 3 O 4 nanospheres). Various GO–Fe 3 O 4 hybrid nanofillers were dispersed into the PDMS resin through a solution casting method to evaluate the structure–property relationship. A simple coprecipitation procedure was used to fabricate magnetite nanospheres with an average diameter of 30–50 nm, a single crystal structure, and a predominant (311) lattice plane. The uniform bioinspired superhydrophobic PDMS/GO–Fe 3 O 4 nanocomposite surface produced had a micro-/nano-roughness, low surface-free energy (SFE), and high fouling release (FR) efficiency. It exhibited several advantages including simplicity, ease of large-area fabrication, and a simultaneous offering of dual micro-/nano-scale…

During electrocatalytic water splitting, the management of bubbles possesses great importance to reduce the overpotential and improve the stability of the electrode. Bubble evolution is accomplished by nucleation, growth, and detachment. The expanding nucleation sites, decreasing bubble size, and timely detachment of bubbles from the electrode surface are key factors in bubble management. Recently, the surface engineering of electrodes has emerged as a promising strategy for bubble management in practical water splitting due to its reliability and efficiency. In this review, we start with a discussion of the bubble behavior on the electrodes during water splitting. Then we summarize recent progress in the management of bubbles from the perspective of surface physical (electrocatalytic surface morphology) and surface chemical (surface composition) considerations, focusing on the surface texture design, three-dimensional construction, wettability coating technology, and functional group modification. Finally, we present the principles of bubble management, followed by an insightful…

Exploring a covalent organic framework (COF) material as an efficient metal-free photocatalyst and as an adsorbent for the removal of pollutants from contaminated water is very challenging in the context of sustainable chemistry. Herein, we report a new porous crystalline COF, C 6 -TRZ-TPA COF, via segregation of donor–acceptor moieties through the extended Schiff base condensation between tris(4-formylphenyl)amine and 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)trianiline. This COF displayed a Brunauer–Emmett–Teller (BET) surface area of 1058 m 2 g –1 with a pore volume of 0.73 cc g –1 . Again, extended π-conjugation, the presence of heteroatoms throughout the framework, and a narrow band gap of 2.2 eV, all these features collectively work for the environmental remediation in two different perspectives: it could harness solar energy for environmental clean-up, where the COF has been explored as a robust metal-free photocatalyst for wastewater treatment and as an adsorbent for iodine capture. In our endeavor of wastewater treatment, we have conducted the photodegradation of rose bengal (RB)…

Density functional theory (DFT) calculation was used to study the adsorption and sensing performances of a transition metal atom (TMA) doped MoTe 2 monolayer for two industrial toxic and harmful gases, SO 2 and NH 3, in this study. The adsorption structure, molecular orbital, density of state, charge transfer, and energy band structure were applied to investigate the interaction between the gas and MoTe 2 monolayer substrate. The conductivity of the MoTe 2 monolayer film doped with TMA (Ni, Pt, Pd) is significantly improved. The original MoTe 2 monolayer has poor adsorptive ability for SO 2 and NH 3, which is physisorption, while for the TMA-doped MoTe 2 monolayer, it is significantly enhanced and the adsorption process is chemisorption. All results provide a trustworthy theoretical basis for sensors based on MoTe 2 to detect toxic and harmful gases SO 2 and NH 3 . Additionally, it also provides guidance for further research on the transition metal cluster doped MoTe 2 monolayer for gas detection.

Green synthesis of metal–organic frameworks (MOFs) in aqueous solutions under ambient conditions with reduced production costs and environmental effects is an efficient technique to transfer lab-scale production to industrial large scale. Hence, this work proposes a green, low-cost, sustainable, rapid, and innovative synthetic strategy to produce cerium-based (Ce-UiO-66) MOFs under ambient conditions in the presence of water as a green solvent. This synthetic strategy exhibits great potential compared to conventional solvothermal synthetic techniques, and it does not need external activation energy and organic solvents, which can achieve the standards of green chemistry. Ce-UiO-66 MOF was synthesized successfully and utilized as a green adsorbent to efficiently eliminate anionic Congo Red (CR) dye from dye-containing wastewater. The experimental adsorption results were well matched to the pseudo-second-order kinetic and Langmuir isotherm models, in which the maximum CR adsorption capacity was measured to be about 285.71 mg/g. To evidence the applicability of Ce-UiO-66 MOFs in CR…

High Resolution Image Download MS PowerPoint Slide Hydrogen (H 2 ) underground storage has attracted considerable attention as a potentially efficient strategy for the large-scale storage of H 2 . Nevertheless, successful execution and long-term storage and withdrawal of H 2 necessitate a thorough understanding of the physical and chemical properties of H 2 in contact with the resident fluids. As capillary forces control H 2 migration and trapping in a subsurface environment, quantifying the interfacial tension (IFT) between H 2 and the resident fluids in the subsurface is important. In this study, molecular dynamics (MD) simulation was employed to develop a data set for the IFT of H 2 –brine systems under a wide range of thermodynamic conditions (298–373 K temperatures and 1–30 MPa pressures) and NaCl salinities (0–5.02 mol·kg –1 ). For the first time to our knowledge, a comprehensive assessment was carried out to introduce the most accurate force field combination for H 2 –brine systems in predicting interfacial properties with an absolute relative deviation (ARD) of less than 3%…

NH 3 gas in human exhaled breath contains abundant physiological information related to human health, especially chronic kidney disease (CKD). Unfortunately, up to now, most wearable NH 3 sensors show inevitable defects (low sensitivity, easy to be interfered by the environment, etc.), which may lead to misdiagnosis of CKD. To solve the above dilemma, a nanoporous, heterogeneous, and dual-signal (optical and electrical) wearable NH 3 sensor mask is developed successfully. More specifically, a polyacrylonitrile/bromocresol green (PAN/BCG) nanofiber film as a visual NH 3 sensor and a polyacrylonitrile/polyaniline/reduced graphene oxide (PAN/PANI/rGO) nanofiber film as a resistive NH 3 sensor are constructed. Due to the high specific surface area and abundant NH 3 binding sites of these two nanofiber films, they exhibit good NH 3 sensing performance. However, although the visual NH 3 sensor (PAN/BCG nanofiber film) is simple without the need of any detecting facilities and quite stable when temperature and humidity change, it shows poor sensitivity and resolution. In comparison, the…

MXenes are 2D nanomaterials with a wide array of possible compositions; they feature a unique combination of properties such as high electrical conductivity, hydrophilicity, and colloidal stability which makes them attractive for a variety of applications. However, the shelf life and industrial utility of MXenes face challenges due to their tendency to oxidize and disintegrate, particularly in dispersions. Thus, it is crucial to find effective ways to ensure the degradation stability of MXenes. This feature article reviews the key factors affecting the degradation of MXenes such as pH, concentration of the dispersion, humidity, and storage temperature. In addition, we review our group’s progress in mitigating the degradation of MXenes such as low-temperature storage, the use of antioxidants, and thermal annealing, particularly for Ti 3 C 2 T z . These simple approaches may allow for applications of MXenes on a commercial scale.

Cesium lead halide (CsPbX 3, X = Cl, Br, and I) perovskite nanocrystals (NCs) possess great potential in light-emitting diode applications because of their high brightness, low cost, tunable luminescence, and facile synthesis nature. However, these NCs are often disadvantaged by their instability in nonsolvent environment that hinders the practical applications of the material. In order to solve these issues, cesium lead halide NCs prepared using a solvent environment can be placed on substrates to retain the high stability and expand the applicability of the material. This Review focuses on the transfer of the all-inorganic cesium lead halide NCs (synthesized in solutions) onto matrix materials and their direct synthesis on these bases, including the inert shell growth (inorganic and organic shell), embedment in matrixes (e.g., metal organic frameworks, porous SiO 2, glass, ZrO 2, Al 2 O 3, and AlOOH), and direct synthesis in substrates. In particular, the strategies for stability and PL property improvement of the materials are also summarized. The purpose of this Review is to…

Condensing atmospheric water vapor on surfaces is a sustainable approach to addressing the potable water crisis. However, despite extensive research, a key question remains: what is the optimal combination of the mode and mechanism of condensation as well as the surface wettability for the best possible water harvesting efficacy? Here, we show how various modes of condensation fare differently in a humid air environment. During condensation from humid air, it is important to note that the thermal resistance across the condensate is nondominant, and the energy transfer is controlled by vapor diffusion across the boundary layer and condensate drainage from the condenser surface. This implies that, unlike condensation from pure steam, filmwise condensation from humid air would exhibit the highest water collection efficiency on superhydrophilic surfaces. To demonstrate this, we measured the condensation rates on different sets of superhydrophilic and superhydrophobic surfaces that were cooled below the dew points using a Peltier cooler. Experiments were performed over a wide range of…

Access to and use of energy resources are now crucial components of modern human existence thanks to the exponential growth of technology. Traditional energy sources provide significant challenges, such as pollution, scarcity, and excessive prices. As a result, there is more need than ever before to replace depleting resources with brand-new, reliable, and environmentally friendly ones. With the aid of reverse electrodialysis, the salinity gradient between rivers and seawater as a clean supply with easy and infinite availability is a viable choice for energy generation. The development of nanofluidic-based reverse electrodialysis (NRED) as a novel high-efficiency technology is attributable to the progress of nanoscience. However, understanding the predominant mechanisms of this process at the nanoscale is necessary to develop and disseminate this technology. One viable option to gain insight into these systems while saving expenses is to employ simulation tools. In this study, we looked at how a layer-by-layer (LBL) soft layer influences ion transport and energy production in…

Peptides are versatile building blocks for the fabrication of various nanostructures that result in the formation of hydrogels and nanoparticles. Precise chemical functionalization promotes discrete structure formation, causing controlled bioactivity and physical properties for functional materials development. The conjugation of small molecules on amino acid side chains determines their intermolecular interactions in addition to their intrinsic peptide characteristics. Molecular information affects the peptide structure, formation, and activity. In this Perspective, peptide building blocks, nanostructure formation mechanisms, and the properties of these peptide materials are discussed with the results of recent publications. Bioinstructive and stimuli-responsive peptide materials have immense impacts on the nanomedicine field including drug delivery, cellular engineering, regenerative medicine, and biomedicine.

Cultural heritage is a crucial resource to increase our society's resilience. However, degradation processes, enhanced by environmental and anthropic risks, inevitably affect works of art, hindering their accessibility and socioeconomic value. In response, interfacial and colloidal chemistry has proposed valuable solutions over the past decades, overcoming the limitations of traditional restoration materials and granting cost- and time-effective remedial conservation of the endangered artifacts. Ranging from inorganic nanoparticles to hybrid composites and soft condensed matter (gels, microemulsions), a wide palette of colloidal systems has been made available to conservators worldwide, targeting the consolidation, cleaning, and protection of works of art. The effectiveness and versatility of the proposed solutions allow the safe and effective treatment of masterpieces belonging to different cultural and artistic productions, spanning from classic ages to the Renaissance and modern/contemporary art. Despite these advancements, the formulation of materials for the preservation of…

Spatial charge separation and migration are the critical shortcomings dominating the core energy conversion corridors of photocatalytic systems. Here, a biomimetic multi-interfacial architecture providing strong coupled interaction and rapid charge transmission for photostable and competent photocatalytic H 2 O 2 production and H 2 evolution is proposed. The triple-hybrid all-solid-state Z-scheme system was formed with the (001) facet exposed TiO 2 nanosheets derived from MXene layers and B- g -C 3 N 4 nanosheets (M/(001)TiO 2 @BCN) through an electrostatic self-assembly strategy with intimate electronic interaction due to Ti orbital modulation and proper stacking among the hybrids. The metallic and highly conductive MXene layers act as solid state electron mediators in the Z-scheme heterojunction that promote electron–hole separation and migration efficiency. Specifically, the MTBCN-12.5 composite provides optimum yield of H 2 O 2 up to 1480.1 μmol h –1 g –1 and a H 2 evolution rate of 408.4 μmol h –1 (with ACE 6.7%), which are 4 and 20 fold greater than the pristine BCN,…

Herein, we report the synthesis of the CeO 2 /CuO composite as a bifunctional oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) electrocatalyst in a basic medium. The electrocatalyst with an optimum 1:1 CeO 2 /CuO shows low OER and HER overpotentials of 410 and 245 mV, respectively. The Tafel slopes of 60.2 and 108.4 mV/dec are measured for OER and HER, respectively. More importantly, the 1:1 CeO 2 /CuO composite electrocatalyst requires only a 1.61 V cell voltage to split water to achieve 10 mA/cm 2 in a two-electrode cell. The role of oxygen vacancies and the cooperative redox activity at the interface of the CeO 2 and CuO phases is explained in the light of Raman and XPS studies, which play the determining factor for the enhanced bifunctional activity of the 1:1 CeO 2 /CuO composite. This work provides guidance for the optimization and design of a low-cost alternative electrocatalyst to replace the expensive noble-metal-based electrocatalyst for overall water splitting.

In addition to the band gap of a semiconducting photocatalyst, its band edges are important because they play a crucial role in the analysis of charge transfer and possible pathways of the photocatalytic reaction. The Mott–Schottky method using electrochemical impedance spectroscopy is the most common experimental technique for the determination of the electron potential in photocatalysts. This method is well suited for large crystals, but in the case of nanocatalysts, when the thickness of the charged layer is comparable with the size of the nanocrystals, the capacitance of the Helmholtz layer can substantially affect the measured potential. A contact between the electrolyte and the substrate, used for deposition of the photocatalyst, also affects the impedance. Application of other photoelectrochemical methods may help to avoid concerns in the interpretation of impedance data and improve the reliability of measurements. In this study, we have successfully prepared five visible-light active photocatalysts (i.e., N-doped TiO 2, WO 3, Bi 2 WO 6, CoO, and g-C 3 N 4 ) and measured…

Surfactants are used in many fields of the chemical industry in a wide range of applications. Generally, surfactants on water/oil interfaces reduce interfacial tension, enabling the formation of emulsions or providing greater stability to the emulsion formed. Although molecular dynamics has been extensively used and has achieved remarkable success in describing thermodynamic and molecular properties of systems with surface-active compounds, the traditional molecular simulation force fields considerably constrain the system size and the time scale of simulations. Here, we propose a coarse-grained model of polysorbate 80, a nonionic surfactant commercially known as Tween-80. Based on the proposed coarse-grained model, we evaluate the influence of the more internal ethylene oxide chain on the properties of the water/Tween-80/decane system. We verify with the simulation results that the model can reproduce the expected decrease in interfacial tension as the surfactant quantity increases in the simulations. Furthermore, we observe changes in the surfactant orientation as their quantity…

In the past decades, remarkable progress has been made in the field of human-machine interaction. The need for accurate sensing devices with satisfactory user experiences has propelled the development of flexible, stretchable, biocompatible, and imperceptible hydrogel-based interfaces. These innovative interfaces facilitate direct interactions between humans and machines while receiving detected input signals from sensors and giving output commands to controllers, thus motivating accurate real-time responsiveness. This Perspective discusses the sensing mechanisms for the two categories of hydrogel-based sensors and summarizes the recent progress in the development of different representations of human-machine interactions, including intelligent identification, information secrecy, interactive control, and virtual reality and augmented reality technologies. The advantages of hydrogel-based systems over conventionally used rigid electrical components are explicitly discussed. The conclusion provides a perspective on current challenges and outlines a future roadmap for the realization…

The hydroxylamine method involves the synthesis of a new hydroxamic acid collector, i.e., phenylpropyl hydroxamic acid (PHA), from methyl cinnamic hydroxamic acid. Flotation test results show that PHA exhibits good selective collection ability. The adsorption mechanism of PHA is investigated using the zeta potential, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results show that PHA formed a new Ca–O bond with Ca 2+ on the fluorite surface via chemical adsorption. A new five-element chelated hydroxamate group may have formed in Ca on the fluorite surface. The PHA selectivity is fully explained via density functional theory (DFT) calculations, and an adsorption model is established.

The broad application potential of superhydrophobic coatings is limited by the usage of environment-threatening materials and poor durability. The nature-inspired design and fabrication of self-healing coatings is a promising approach for addressing these issues. In this study, we report a fluorine-free and biocompatible superhydrophobic coating that can be thermally healed after abrasion. The coating is composed of silica nanoparticles and carnauba wax, and the self-healing is based on surface enrichment of wax in analogy to the wax secretion in plant leaves. The coating not only exhibits fast self-healing, just in 1 min under moderate heating, but also displays increased water repellency and thermal stability after healing. The rapid self-healing ability of the coating is attributed to the relatively low melting point of carnauba wax and its migration to the surface of the hydrophilic silica nanoparticles. The dependence of self-healing on the size and loading of particles provides insights into the process. Furthermore, the coating exhibits high levels of biocompatibility where…

In this study, NaNbO 3 microcubes were introduced during the preparation of Bi 2 O 2 CO 3 nanosheets to construct a series of NaNbO 3 /Bi 2 O 2 CO 3 heterojunctions with varying NaNbO 3 content. Their photoactivities for N 2 fixation were examined and compared. Results demonstrated that 7.5% NaNbO 3 /Bi 2 O 2 CO 3 had the highest photoactivity. The NH 3 production rate under simulated solar light is 453.1 μmol L –1 g –1 h –1, representing 2.0 and 3.8-fold increases compared to those of Bi 2 O 2 CO 3 and NaNbO 3, respectively. A comprehensive investigation encompassing the physical and chemical properties of the NaNbO 3 /Bi 2 O 2 CO 3 photocatalyst was conducted. Bi 2 O 2 CO 3 nanosheets were discovered to be distributed on the NaNbO 3 microcubes surface. The addition of NaNbO 3 exhibited nearly no effect on the photoabsorption performance and specific surface area of the Bi 2 O 2 CO 3 . However, the tight contact between NaNbO 3 and Bi 2 O 2 CO 3 and their appropriate band positions led to the formation of a heterojunction structure between them. The electron drift occurring in the…

High Resolution Image Download MS PowerPoint Slide Reactive molecular dynamics simulations have been used to simulate the chemical mechanical polishing (CMP) process of silica glass surfaces with the ceria (111) and (100) surfaces, which are predominantly found in ceria nanoparticles. Since it is known that an alteration layer is formed at the glass surface as a consequence of the chemical interactions with the slurry solutions used for polishing, we have created several glass surface models with different degrees of hydroxylation and porosity for investigating their morphology and chemistry after the interaction with acidic, neutral, and basic water solutions and the ceria surfaces. Both the chemical and mechanical effects under different pressure and temperature conditions have been studied and clarified. According to the simulation results, we have found that the silica slab with a higher degree of hydroxylation (thicker alteration layer) is more reactive, suggesting that proper chemical treatment is fundamental to augment the polishing efficiency. The reactivity between the…

Adsorption separation is considered one of the most commonly used gas purification methods. At present, the most widely used adsorption methods are mainly pressure swing adsorption (PSA) and temperature swing adsorption (TSA). In both adsorption methods, a comprehensive understanding of the equilibrium data and the adsorption capacity of the adsorbent is essential for process design and optimization, and the adsorption isotherm can provide a powerful aid in this regard. In this study, through mathematical analysis of the Langmuir isotherm model, the optimal cyclic adsorption conditions and the optimal thermodynamic parameters (entropy change and enthalpy change) under PSA and TSA were obtained. In addition, the isotherm model can be used to predict the isobaric adsorption capacity, and the objective function was established according to the cyclic adsorption capacity and the regeneration sensible heat consumption per unit adsorption capacity to calculate the optimal adsorption/desorption temperatures and optimal cyclic adsorption capacity of various adsorbents.

High Resolution Image Download MS PowerPoint Slide With recent advances and anticipated proliferation of lipid nanoparticle (LNP)-delivered vaccines and therapeutics, there is a need for the availability of internationally recognized reference materials of LNP systems. Accordingly, we developed six LNP and liposome (anionic, neutral, and cationic each) candidate reference material formulations and thoroughly characterized by dynamic light scattering their particle hydrodynamic size (Z-avr) and polydispersity. We also evaluated the particle size homogeneity and long-term −70 °C and 4 °C storage stability using multiple large sets of randomly selected vials for each formulation. The formulations stored at −70 °C remained stable and homogeneous for a minimum of 9 months. The Z-avr relative combined uncertainty and the long-term variability were both <1.3% for liposome formulations and anionic LNPs, (3.9% and 1.7%) for neutral LNPs, and (6.7% and 4.4%) for cationic LNPs. An inadvertent few-hour-long storage temperature increase to −35 °C due to a freezer malfunction resulted in a small…

Ice accretion always brings much inconvenience in the field of production and life. How to anti-ice or de-ice easily on solid surfaces becomes research focus in the engineering material fields. In this work, a kind of photo-thermal superhydrophobic polyurethane sponge (PSP-SPONGE) was developed by depositing Fe 3 O 4 nanoparticles and polydopamine and simple fluorination treatment to realize anti-icing and de-icing fast under faint sunlight irradiation. Utilizing the thermal insulation of porous PSP-SPONGE, the photo-thermal energy was located at the sunlight irradiation area, which heated PSP-SPONGE surface rapidly under sunlight irradiation in cold surroundings. Water droplets on PSP-SPONGE surface would never freeze under faint 0.3 kW/m 2 (“0.3 sun”) sunlight illumination in −30 °C damp surroundings, and the ice melts entirely within 18 min under “1 sun” illumination. Furthermore, PSP-SPONGE has excellent self-cleaning and self-healing properties that can cope with the complex and volatile natural environment to guarantee durable anti-icing and de-icing performances. The…

Liposomes, which consist of bilayer lipids surrounding interior aqueous compartment(s), were first characterized nearly 60 years ago. Remarkably, many fundamental properties of liposomes and their micellar-like "solid core" counterparts (a lipid monolayer surrounding a hydrophobic core) and transitions between these structures remain poorly understood. In this work, we examine the effects of basic variables on the morphology adopted by lipid-based systems produced by rapid mixing of lipids in ethanol with aqueous media. We show that, for lipids such as distearolyphosphatidylcholine (DSPC)-cholesterol mixtures that form bilayer vesicles on hydration, osmotic stress can induce regions of high positive membrane curvature, leading to fusion between unilamellar vesicles to produce bilamellar vesicles. Addition of lyso PC, an "inverted cone"-shaped lipid that supports regions of high positive curvature, can inhibit the formation of these bilamellar vesicles by stabilizing a hemifused intermediate structure. Conversely, the presence of "cone"-shaped lipids such as…

Surface modification to improve the oxidation stability and dispersibility of MXene in diverse organic media is a facile strategy for broadening its application. Among the various ligands that can be grafted on the MXene surface, oleylamine (OAm), with amine functionalities, is an advantageous candidate owing to its strong interactions and commercial viability. OAms are grafted onto MXene through covalent bonds induced by nucleophilic reactions and H bonds in liquid interface reactions at room temperature. In addition, this grafting behavior of the ligand was characterized by a reduction in the slope with an increase in the ligand concentration ( C l ), confirming that the OAms were grafted via Langmuir-like behavior, and the monolayer of OAms was developed via two distinct steps (I: lying-down phase; II: ordered monolayer). MXene nanosheets modified by OAm (OAm-MX) are highly dispersible in a wide range of organic solvents owing to the alkyl chain of the OAms, which induces hydrophobic properties on the surface of MXene. The OAm-MX dispersion exhibits outstanding oxidation and…

Emulsification is a crucial technique for mixing immiscible liquids into droplets in various industries, such as food, cosmetics, biomedicine, agrochemistry, and petrochemistry. Quantitative analysis of the stability is pivotal before the utilization of these emulsions. Differences in X-ray attenuation for emulsion components and surface relaxation of the droplets may contribute to X-ray CT imaging and low-field NMR spectroscopy as viable techniques to quantify emulsion stability. In this study, Pickering (stabilized solely by nanoparticles) and Classical (stabilized solely by low molecular weight polymers) nanoemulsions were prepared with a high-energy method. NMR and X-ray CT were employed to constantly monitor the two types of nanoemulsions until phase separation. The creaming rates calculated from NMR match well with the results obtained from X-ray CT. Furthermore, we show that Stokes' law coupled with the classical Lifshitz-Slyozov-Wagner theory underestimates the creaming rate of the nanoemulsions compared to the experimental results from NMR and X-ray CT imaging. A new theory…

High Resolution Image Download MS PowerPoint Slide Organic–inorganic hybrid nanoflowers (NFs) consisting of horseradish peroxidase (HRP) and copper II (Cu 2+ ) are successfully synthesized with the involvement of carbon nanotubes (CNTs) by in situ and post-modification methods. Catalytic activities of in situ synthesized [email protected] ( [email protected] ) and post-modification-synthesized [email protected] ( [email protected] ) are systematically examined. The 30 mg CNTs incorporated [email protected] ( [email protected] ) exhibits greatly increased catalytic activity and stability toward 3,3′,5,5′-tetramethylbenzidine (TMB), thanks to the synergistic effect between HRP-NF and CNTs and the peroxidase-like activity of CNTs in the presence of hydrogen peroxide (H 2 O 2 ). While [email protected] retains almost 85% of its initial activity even after 10 cycles, HRP-NF (without CNTs) loses half of its initial activity at the same experimental conditions. We study how two experimental parameters, the pH values and temperatures, influence the catalytic activity of [email protected],…

Porous electrodes with high specific surface areas have been commonly employed for alkaline water electrolysis. The gas bubbles generated in electrodes due to water electrolysis, however, can screen the reaction sites and hinder reactant transport, thereby deteriorating the performance of electrodes. Hence, an in-depth understanding of the behavior of bubbles in porous electrodes is of great importance. Nevertheless, since porous electrodes are opaque, direct observation of bubbles therein is still a challenge. In this work, we have successfully captured the behavior of bubbles in the pores at the side surfaces of nickel-based porous electrodes. Two types of porous electrodes are employed: the ones with straight pores along the gravitational direction and the ones with tortuous pores. In the porous electrodes with tortuous pores, the moving bubbles are prone to collide with the solid matrix, thereby leading to the accumulation of bubbles in the pores and hence bubble trapping. By contrast, in the porous electrodes with straight pores, bubbles are seldom trapped; and when two bubbles…

Cation-π interaction is one of the most important noncovalent interactions identified in biosystems, which has been proven to play an essential role in the strong adhesion of marine mussels. In addition to the well-known catecholic amino acid, l-3,4-dihydroxyphenylalanine, mussel foot proteins are rich in various aromatic moieties (e.g., tyrosine, phenylalanine, and tryptophan) and cationic residues (e.g., lysine, arginine, and histidine), which favor a series of short-range cation-π interactions with adjustable strengths, serving as a prototype for the development of high-performance underwater adhesives. This work highlights our recent advances in understanding and utilizing cation-π interactions in underwater adhesives, focusing on three aspects: (1) the investigation of the cation-π interaction mechanisms in mussel foot proteins via force-measuring techniques; (2) the modulation of cation-π interactions in mussel mimetic polymers with the variation of cations, anions, and aromatic groups; (3) the design of wet adhesives based on these revealed principles, leading to functional…

Developing efficient adsorbent materials for iodine scavenging is essential to mitigate the threat of radioactive iodine causing adverse effects on human health and the environment. In this context, we explored N-rich two-dimensional covalent organic frameworks (COFs) with diverse functionalities for iodine capture. The pyridyl-hydroxyl-functionalized triazine-based novel 5,5′,5″-(1,3,5-triazine-2,4,6-triyl)tris(pyridine-2-amine) (TTPA)-COF possesses high crystallinity (crystalline domain size: 24.4 ± 0.6 nm) and high porosity (specific BET surface area: 1000 ± 90 m 2 g –1 ). TTPA-COF exhibits superior vapor-phase iodine adsorption (4.43 ± 0.01 g g –1 ) compared to analogous COF devoid of pyridinic moieties, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT)-COF. The high iodine capture by TTPA-COF is due to the enhanced binding affinity conferred by the extra pyridinic active sites. Furthermore, the crucial role of long-range order in porous adsorbents has been experimentally evidenced by comparing the performance of iodine vapor capture of TTPA-COF with an amorphous network polymer…

Deposition and spread of aqueous droplets on hydrophobic/superhydrophobic surfaces are of great significance in many practical applications, such as spraying, coating, and printing, and particularly in improving pesticide utilization efficiency because the intrinsic hydrophobicity/superhydrophobicity of most plant leaves results in serious loss of water-based pesticides during spraying. It has been found that proper surfactants can promote the droplet spread on such surfaces. However, most reports involved the effects of surfactants on the spread of the gently released droplets over hydrophobic or highly hydrophobic substrates, while the situation on superhydrophobic substrates has rarely been explored. Moreover, high-speed impact makes it extremely difficult to deposit and spread the aqueous droplets on superhydrophobic surfaces; thus, the deposition and spread have just been achieved by surfactants in recent years. Here, we give an overview concerning the influence factors on the deposition and spreading performance of gently released and high-speed impacted droplets on…