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Hazardous gases threaten human health and the environment due to their toxicity and flammability. Managing such risks requires reliable gas detection techniques. However, accurate detection of target environmental gases remains challenging. Recent advances in materials science have enabled the combination of molecular separation membranes with chemical sensors to achieve high selectivity in the detection of target gas molecules. Herein, we discuss the underlying gas separation mechanisms for different types of membrane overlayers, including graphene oxide, metal-organic frameworks, and metal oxides, as well as their integration with sensing materials. Furthermore, we discuss the relationship between sensing performance and surface chemistry, catalytic properties, and membrane nanostructure. We conclude by highlighting future directions for selective detection of environmental gas species.

The ability to fundamentally describe nanoparticle (NP) transport in the subsurface underpins environmental risk assessment and successful material applications, including advanced remediation and sensing technologies. Despite considerable progress, our understanding of NP deposition behavior remains incomplete as there are conflicting reports regarding the effect of fluid flow velocity on attachment efficiency. To directly address this and more accurately describe NP attachment behavior, we have developed a novel protocol using a quartz crystal microbalance with dissipation monitoring (QCM-D) to separate and individually observe deposition mechanisms (diffusion and sedimentation), providing in situ, real-time information about particle diffusion (from the bulk liquid to solid surface). Through this technique, we have verified that the approaching velocity of NPs via diffusion increases (0.8-6.7 μm/s) with increasing flow velocity (6.1-106.0 μm/s), leading to an increased NP kinetic energy, thus affecting deposition processes. Further, in the presence of a secondary energy minimum associated with organic surface coatings, secondary minimum deposition decreases and primary minimum deposition increases with the flow velocity. NPs deposited at the primary minimum are relatively more resistant to hydrodynamic energies (including detachment associated energies), resulting in an increase of observed attachment efficiencies. Taken together, this work not only describes a novel method to delineate and quantify physical processes underpinning particle behavior but also provides direct measurements regarding key factors defining the relationship(s) of flow velocity and particle attachment. Such insight is valuable for next-generation fate and transport model accuracy, especially under unfavorable attachment regimes, which is a current and critical need for subsurface material applications and implication paradigms.

Inorganic-organic nanocomposites, typically as an inorganic core with surface organic coating(s), have received interest as potential platform materials for sensor, catalyst, sorbent, and environmental applications, among others. Here, we describe the critical role of organic surface coatings with regard to the colloidal stability of engineered manganese oxide nanoparticles (MnxOy NPs). Specifically, we prepared libraries of monodisperse MnxOy NPs with a serial selection of surface coatings (stearic acid (SA), oleic acid (OA), poly(maleic anhydride-alt-1-octadecene) (PMAO), linear polyethyleneimine (LPEI), and multibranched polyethyleneimine (BPEI)), which were chosen based on comparable structure(s) and functional group(s). We systematically evaluated the role of surface organic coatings via critical coagulation concentrations (CCCs), which were compared with theoretical calculations (Schulze-Hardy rule). Through a newly developed light scattering protocol, we observed that the effective density of nanoclusters can exceed NPs' primary (bulk) density depending on the open space(s) within organic coatings. Interestingly, PMAO-coated NPs were more stable at the point of zero charge (PZC) than at neutral pH (pH 7), despite the loss of effective surface charge potential. CCC was 334 mM in NaCl and 1.5 mM in CaCl2 at pH 7, compared to CCC values of 807 mM in NaCl and 210 mM in CaCl2 at PZC. This increase in stability is due to polymer (re)configuration (at PZC), which was further confirmed with a quartz crystal microbalance-based technique to evaluate surface-based polymer dynamics. Taken together, this work quantifies the role of organic coating dynamics, including structure, grafting density, and configuration on the colloidal stability of organic-coated NPs.

Photoactive cetyltrimethylammonium bromide-oleic acid (CTAB-OA) bilayer coated iron oxide nanocrystals (IONCs) were precisely synthesized and demonstrated for photo-enhanced hexavalent chromium (Cr(VI)) treatment. For these materials, an outward facing, CTAB layer offers specific affinity for Cr(VI), while the core IONC (8 – 25 nm, as Fe3O4 single domain) surface participates in Fe(II)/Fe(III) redox cycling. Further, at the coating-particle interface, the OA layer alters material photoactive dynamics (near UV and visible light) via a ligand-to-metal charge transfer (LMCT) mechanism, significantly enhancing Cr(VI) reduction. To delineate process variables, we first quantified photo-catalytic Cr(VI) reduction rates under UVA irradiation (sunlight mimic intensities) as a function of IONC core size, which correlates with the amount of surface available ferrous ion (Fe(II)). It was observed that 25 nm CTAB functionalized IONC showed outstanding Cr(VI) sorption and photoreduction performance compared with other IONC explored and controls (i.e. TiO2 nanocrystals). We next systematically explored the photoreduction mechanism(s) through a matrix of control experiments, considering solution pH, dissolved gas (air, O2, and CO2), along with hydroxyl and superoxide radicals. Results indicate that Fe(II) (at the IONC interface) acts as the primary Cr(VI) reductant and that Fe(III) (oxidized from Fe(II)) (re)cycles via a photocatalyzed reaction. Taken together, this work presents a clear physical and mechanistic description of CTAB-OA bilayer IONCs which, when optimized, are highly effective for Cr(VI) treatment under UVA. In addition to potential broad application for other contaminant targets which are reactive with Fe(II), which are many, this work also highlights the need for precise interfacial understanding of nano composite materials towards process optimization.

Developments in nanoscale engineering now allow for molecular scale optimization of reactivity, sorption, and magnetism, among other properties, for advanced, material-based environmental applications, including sorption, separation, and sensing of radionuclides. Herein, we describe novel, monodisperse nanoscale manganese ferrite crystals (MnFe2O4) for ultra-high capacity environmental sorption and subsequent separation of uranyl in water. System optimization was explored as a function of nanocrystal (core) composition, surface coating(s), and water chemistry. 11 nm MnFe2O4 nanocrystals, which were colloidally stabilized via engineered oleyl-based surface bilayers, demonstrate extreme, yet specific, uranium binding capacities while remaining monomerically stable under environmentally relevant conditions (water chemistries), which are key for application. In particular, MnFe2O4 cores with oleyl phosphate (as the outer facing layer) bilayers demonstrate preferential uranium binding of >150% (uranium weight)/(particle system weight) while being highly water stable in elevated ionic strengths/types and pH (up to 235.4 ppm (10.24 mM) of NaCl and 51.3 ppm (1.28 mM) of CaCl2, in addition to 60 ppm of uranyl, pH 5–9). Further, when normalized for size and surface coatings, MnFe2O4 nanocrystals had significantly enhanced sorption capacities compared to Mn2FeO4, Fe3O4 and manganese oxide core analogs. Mechanistically, we demonstrate that observed uranium sorption enhancement is due not only to thermodynamically favorable interfacial interactions (for both particle and selected bilayer coatings), but also due to significant uranyl reduction at the particle interface itself. Uranium sorption capacities for optimized systems described are the highest of any material reported to date.

Engineered, superparamagnetic, iron oxide nanoparticles (IONPs) have significant potential as platform materials for environmental sensing, imaging and remediation due to their unique size, physicochemical and magnetic properties. To this end, controlling the size and surface chemistry of the materials is crucial for such applications in the aqueous phase, and in particular, for porous matrixes with particle-surface interaction considerations. In this study, superparamagnetic, highly monodispersed 8 nm IONPs were synthesized and transferred into water as stable suspensions (remaining monodispersed) by way of an interfacial oleic acid bilayer surface. Once stabilized and characterized, particle-particle and model surface interactions (deposition and release) were quantitatively investigated and described systematically as a function of ionic strength (IS) and type with time-resolved dynamic light scattering (DLS), zeta potential, and real-time quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The critical coagulation concentration (CCC) for oleic acid bilayer coated iron oxide nanoparticles (OA-IONPs) were determined to be 710 mM for NaCl (matching DLVO predictions) and 10.6 mM for CaCl2, respectively. For all conditions tested, surface deposition kinetics showed stronger, more favorable interactions between OA-IONPs and polystyrene surfaces compared to silica, which is hypothesized to be due to increased particle-surface hydrophobic interactions (when compared to silica surfaces).

Neutron reflectometry (NR) was employed to study the interaction of nanosized silica particles with a flat silica surface in aqueous solutions. Unlike other experimental tools that are used to study surface interactions, NR can provide information on the particle density profile in the solution near the interface. Two types of silica particles (25 and 100 nm) were suspended in aqueous solutions of varying ionic strength. Theoretical calculations of the surface interaction potential between a particle and a flat silica surface using the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory were compared to the experimental data. The theory predicts that the potential energy is highly dependent on the ionic strength. In high ionic strength solutions, NR reveals a high concentration of particles near the flat silica surface. Under the same conditions, theoretical calculations show an attractive force between a particle and a flat surface. For low ionic strength solutions, the particle concentration near the surface obtained from NR is the same as the bulk concentration, while depletion of particles near the surface is expected because of the repulsion predicted by the DLVO theory.

Soft phase magnetic Fe-B nanoparticles were prepared by coprecipitation and the hard phase magnetic Nd-Fe-B nanoparticles were obtained from mechanical ball mill of the bulk Nd-Fe-B with a shaker mill. Also mechanical ball mill technique was applied to the mixture of Nd-Fe-B and Fe-B nanoparticles to build up an exchange-coupled nanocomposite magnet. It was loaded in electronic furnace and annealed under a flow of hydrogen at 953 K for 30 min. The exchange coupled interaction of isotropic magnets was characterized by smooth hysteresis loop with a high value of remanence (Mr/Ms > 0.5).

High temperature solution phase decomposition of Fe(CO)5 and reduction of Pt(acac)2 in the presence of stabilizers of oleic acid and oleyl amine are employed to produce Fe1–xPtx alloy nanoparticles. The Fe and Pt composition of the nanosized materials can be tuned by adjusting the molar ratio of Fe(CO)5 to Pt(acac)2, and the compositions ranging from Fe40Pt60 to Fe80Pt20 are obtained. This study is to investigate the influence of the composition on Curie temperature (Tc) of Fe1–xPtx nanoparticles monitored by thermomagnetic analysis (TMA).