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Polyelectrolyte-colloid (PEC) complexes, ubiquitous across diverse fields, exhibit remarkable phase transitions, mimicking intricate biological assemblies. While the role of electrostatic forces in the PEC complex assembly is undeniable, achieving a holistic comprehension remains an elusive goal. This study unveils a fascinating phenomenon: the formation of highly collapsed coacervate structures in PEC complexes at elevated polyelectrolyte concentrations, followed by the swelling of complexes at even higher concentrations. Employing anionic silica colloids and cationic chitosan as a model system, small-angle X-ray/neutron (SAXS/SANS) elucidates the transition from a bead-on-a-necklace-like phase to a dense packed coacervate state (with volume fraction ∼0.62) until 3 wt % concentration of the polyelectrolyte. However, beyond 3 wt %, swelling of the dense collapsed assembly is observed. This structural evolution of PEC complexes as a function of chitosan concentration is attributed to the interplay of electrostatically driven interactions and the Donnan effect. Notably, the critical concentration for coacervation, C s *, demonstrates a linear dependence on the initial colloid concentration. Interestingly, a complete expansion of the coacervate is observed at a high polyelectrolyte concentration, particularly for dilute colloid solutions (2 wt %). Furthermore, the addition of an electrolyte sheds light on the delicate interplay of forces. While a low electrolyte concentration partially screens charges, leading to a shift in phase diagram, higher concentrations trigger complete coacervate dissolution beyond the critical electrolyte concentration of 0.2 M, due to the complete screening of electrostatic charges.

Considering the low-level dose detection requirement for neutron and γ radiation in cancer therapy, synthesis and exploratory studies have been performed on a newly developed phosphor LiAlO 2 :Gd. Our results reveal that the presence of both Li and Gd makes it sensitive to both gamma and thermal neutrons. The applicability of LiAlO 2 :Gd for beta, gamma, and neutrons in both thermally stimulated and optically stimulated modes has been verified by extensive experiments followed by kinetic parametric evaluation with theoretical calculations. The current work confirms that LiAlO 2 :Gd is a highly sensitive phosphor with a minimum detectable dose of 5.7 μSv for gamma and 92 μSv for themral neutrons. The phosphor is found to show very high sensitivity at low energy and dose. Its ability for detection and discrimination of both gamma and thermal neutrons makes it a potential material to be used in medical dosimetry.

Evaporation is a ubiquitous phenomenon. Rapid evaporation of the continuous phase from micrometric colloidal droplets can be used to realize nanostructured microgranules, constituting the assembled nanoparticles. One of the important aspects of such nonequilibrium assembly is the nature of the packing of nanoparticles in the microgranules. The present work demonstrates the evidence of size stratification of the nanoparticles in such far-from-equilibrium configurations. Small-angle X-ray scattering, in combination with particle packing simulation, reveals the "large on top"-type stratification in such assembled microgranules, where the larger particles get concentrated at the outer shell of the granules while the smaller particles reside in the core region. It also reveals the presence of local clusters in such a rapid evaporative assembly in aerosolized colloidal droplets.

Understanding adsorption processes at the molecular level has transformed the discovery of engineered materials for maximizing gas storage capacity and kinetics in adsorption-based carbon capture applications. In this work, we studied the molecular mechanism of gas (CO 2 , H 2 , methane, and ethane) adsorption inside an interconnected porous network of carbon. This was achieved by synthesizing novel macro-meso-microporous carbon (M 3 C) nanospheres with interconnected pore structures. The M 3 Cs showed a CO 2 capture capacity of 5.3 mmol/g at atmospheric CO 2 pressure, with excellent kinetics. This was due to fast CO 2 adsorption within the interconnected hierarchical macro-meso-microporous M 3 C. In situ small-angle neutron scattering (SANS) under various CO 2 pressures indicated that the macro- and mesopores of M 3 C enable fast diffusion of CO 2 molecules inside the micropores, where adsorbed CO 2 molecules densify into a liquid-like state. This strong densification of CO 2 molecules causes fast CO 2 diffusion in the macro- and mesopores of M 3 C, restarting the adsorption cycle for fresh CO 2 molecules until all pores are completely filled. Notably, M 3 C also showed good capture capacities for hydrogen and various hydrocarbons, with excellent selectivity toward ethane over methane.

A simple solvothermal method was used to synthesize a metal-organic framework (MOF) with an Al metal entity, viz., CAU-1 NH 2 . The synthesized MOF was characterized using different techniques like X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy (SEM), field emission SEM (FE-SEM), transmission electron microscopy, small-angle X-ray scattering, positron annihilation lifetime spectroscopy, and X-ray photoelectron spectroscopy. The radiation stability was evaluated by irradiating the material up to a cumulative dose of 2 MGy using 60 Co for the first time. The studies showed a remarkable gamma irradiation stability of the material up to 1 MGy. The porosity and surface area of the synthesized MOF were determined by Brunauer-Emmett-Teller, which showed a high specific surface area of 550 m 2 /g. The pH dependence study of Th uptake from an aqueous solution was performed from pH 2-8, followed by adsorption isotherm and adsorption kinetics studies. These results revealed that the Langmuir and pseudo-second-order kinetic models can be well adapted for understanding the Th uptake and kinetics, respectively. The synthesized MOF exhibited an ∼404 mg/g thorium adsorption capacity. Selectivity studies of adsorption of Th w.r.t. to U and different metal ions such as Cu, Co, Ni, and Fe showed that Th gets adsorbed preferentially as compared to other metal ions. In addition, the MOF could be used multiple times without much deterioration., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Lightweight and flexible gas sensors are essentially required for the fast detection of toxic gases to pass on the early warning to deter accident situations caused by gas leakage. In view of this, we have fabricated a thin paper-like free-standing, flexible, and sensitive carbon nanotube (CNT) aerogel gas sensor. The CNT aerogel film synthesized by the floating catalyst chemical vapor deposition method consists of a tiny network of long CNTs and ∼20% amorphous carbon. The pores and defect density of the CNT aerogel film were tuned by heating at 700 °C to obtain a sensor film, which showed excellent sensitivity for toxic NO 2 and methanol gas in the concentration range of 1-100 ppm with a remarkable limit of detection ∼90 ppb. This sensor has consistently responded to toxic gas even after bending and crumpling the film. Moreover, the film heat-treated at 900 °C showed a lower response with opposite sensing characteristics due to switching of the semiconductor nature of the CNT aerogel film to n-type from p-type. The annealing temperature-based adsorption switching can be related to a type of carbon defect in the CNT aerogel film. Therefore, the developed free-standing, highly sensitive, and flexible CNT aerogel sensor paves the way for a reliable, robust, and switchable toxic gas sensor., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Fine tuning of the pore architecture and flexibility of zeolitic imidazolate frameworks (ZIFs) is highly crucial for realizing their applications in molecular gas separation. Mixed ligand frameworks (ZIF-7-8) synthesized by mixing 2-methylimidazole (2meIm) and benzimidazole (bIm) ligands show enhanced gas separation performance, attributable to pore and flexibility tuning. In the present study, positron annihilation lifetime spectroscopy (PALS) measurements under CO 2 pressure have been used to experimentally investigate the tuning of the pore architecture and flexibility of mixed ligand frameworks ZIF-7-8 having a ZIF-8 structure and similar morphology with varying bIm content up to 18.2%. The aperture and cavity of frameworks begin to open up with an increasing bIm ligand content followed by a decrease at a higher content. On the contrary, flexibility of the frameworks indexed from PALS measurements carried out under CO 2 pressure shows a decreasing trend followed by an increase. The present study shows that mixed ligand frameworks having a larger aperture size are less flexible as a result of inherent open configurations of ligands in the framework lattice. On the other hand, frameworks having a comparatively smaller aperture size show higher flexibility as a result of a possibility of twisting of the ligands under CO 2 pressure, resulting in aperture opening. The pore-opening phenomenon as a result of lattice flexibility under CO 2 pressure is observed to be fully reversible for ZIF-7-8.

Understanding the deposition pattern formed by an evaporated colloidal drop is of fundamental and technological interest. Such an evaporative process is important in various applications starting from inkjet printing to disease diagnosis. In this work, it is shown that the deposit pattern on a porous membrane can be tuned by varying the colloidal viscosity and membrane pore size. We have used small-angle X-ray scattering (SAXS) in scanning mode for profiling of deposit morphology and also for estimation of the interparticle correlation. It is demonstrated that low viscosity and small pore size favor a centrally dipped pattern owing to the coffee ring effect, which can be modified to a contrasting centrally peaked pattern by increasing the viscosity and pore size. To comprehend the experimental observations, a computer model has been developed using a continuity equation that well corroborates the experimental observations on the final deposited pattern and also provides the time evolution of the pattern. The work provides a way to tune the pattern of colloidal stain on a porous substrate by controlling flow and absorption.

The packing of particles is ubiquitous, and it is of fundamental importance, particularly in materials science in the nanometric length scale. It becomes more intriguing when constituent particles deviate from spherical symmetry owing to the inherent complexity in quantifying their positional and rotational correlation. For quantitative estimation of packing fraction, it requires a thorough analysis of the positional correlation of jammed particles. This article adopts a novel approach for determination of the packing fraction of strongly correlated nano-ellipsoids in a microsphere using small-angle scattering. The method has been elucidated through a quantitative analysis of structural correlation of nano-hematite ellipsoids in 3D micrometric granules, which are realized using rapid evaporative assembly. Owing to the deviation from spherical symmetry, the conventional analysis of scattering data fails to interpret the actual packing fraction of the anisotropic particles. The structural correlation gets smeared out because of orientation distribution among the packed anisotropic particles, which leads to an anomaly in the estimation of packing fraction using the conventional analysis approach. It is illustrated that consideration of an interparticle distance distribution function of the correlated nano-ellipsoids becomes indispensable in determining their packing fraction.

The discovery of dendritic fibrous nanosilica (DFNS) has attracted great attention to the field of catalysis, CO 2 capture, drug delivery due to its distinct morphology, and pore size distribution. Despite extensive research, the understanding of the DFNS formation process and its internal structure remains incomplete as microscopy and gas sorption techniques were not able to provide necessary in-depth structural information due to their inherent limitations. In the current work, we present a structural model of DFNS derived using small-angle X-ray scattering (SAXS) supported by 129 Xe nuclear magnetic resonance (NMR), which provided intricate details of DFNS and its internal structure. Mechanistic understanding of the DFNS formation and growth process was achieved by performing time-resolved SAXS measurements during the synthesis of DFNS, which unveils the evolution of two levels of a bicontinuous microemulsion structure responsible for intricate DFNS morphology. The validity and the accuracy of the SAXS method and the model were successfully established through a direct correlation among the functionality of the DFNS scattering profile and its pore size distribution, as well as results obtained from the 129 Xe NMR studies. It has been established that the DFNS structure originates from direct modulation of the bicontinuous structure controlled by a surfactant, a co-surfactant, and the silicate species formed during hydrolysis and the condensation reaction of the silica precursor.

Photoelectrochemical performance of bismuth vanadate (BiVO 4 ) photoanode is limited by poor charge separation and transport properties. The roles of carbon nanotube, reduced graphene oxide, or graphitic carbon nitride in BiVO 4 composite photoanode were investigated toward enhancing light absorption and reducing overall impedance during photoelectrochemical water oxidation process. X-ray diffraction and Tauc analysis showed that BiVO 4 retains its monoclinic phase, n-type semiconductor nature, and band gap in all carbon nanomaterials-incorporated composite photoanodes. It was observed that the carbon nanomaterials incorporation in BiVO 4 film increases its surface porosity, ultimately leading to enhanced light absorption. The BiVO 4 photoanode with reduced graphene oxide and graphitic carbon nitride showed same bulk charge separation efficiency, whereas the latter showed better charge transfer. It was found that the graphitic carbon nitride formed composite with BiVO 4 to provide enhanced light absorption efficiency, i.e., 89% in 350-505 nm range. The BiVO 4 with graphitic carbon nitride photoanode showed the best performance with a photocurrent of 2.2 mA cm -2 , charge separation efficiency of 67%, and photocurrent of 4.0 mA cm -2 with cobalt-phosphate surface catalyst at 1.23 V RHE for water oxidation under 1 sun illumination. The Mott-Schottky and impedance measurements confirmed the shift of conduction band position toward hydrogen reduction potential and reduction in film resistance, respectively, with carbon nanomaterials addition, and the shift was most significant for graphitic carbon nitride. It is concluded that by concomitant formation of junction during photoanode fabrication between carbon nanomaterials, BiVO 4 , and fluorine-doped tin oxide glass substrate, better charge separation, transport, and light absorption can be achieved.

Shale is an increasingly viable source of natural gas and a potential candidate for geologic CO 2 sequestration. Understanding the gas adsorption behavior on shale is necessary for the design of optimal gas recovery and sequestration projects. In the present study neutron diffraction and small-angle neutron scattering measurements of adsorbed CO 2 in Marcellus Shale samples were conducted on the Near and InterMediate Range Order Diffractometer (NIMROD) at the ISIS Pulsed Neutron and Muon Source, STFC Rutherford Appleton Laboratory along an adsorption isotherm of 22 °C and pressures of 25 and 40 bar. Additional measurements were conducted at approximately 22 and 60 °C at the same pressures on the General-Purpose Small-Angle Neutron Scattering (GP-SANS) instrument at Oak Ridge National Laboratory. The structures investigated (pores) for CO 2 adsorption range in size from Å level to ∼50 nm. The results indicate that, using the conditions investigated densification or condensation effects occurred in all accessible pores. The data suggest that at 22 °C the CO 2 has liquid-like properties when confined in pores of around 1 nm radius at pressures as low as 25 bar. Many of the 2.5 nm pores, 70% of 2 nm pores, most of the <1 nm pores, and all pores <0.25 nm, are inaccessible or closed to CO 2 , suggesting that despite the vast numbers of micropores in shale, the micropores will be unavailable for storage for geologic CO 2 sequestration.

In-situ scanning small-angle X-ray scattering (SAXS) experiments have been performed to probe the drying of a single suspended droplet of silica colloids. It has been demonstrated that the formation of a nanoparticle shell during drying can be confirmed just by measuring the temporal evolution of the spatial transmission profile across the drying droplet. The shrinkage of the droplet stops once the shell is formed. The temporal dependence of the shell thickness and droplet radius has been estimated by quantitative analysis of the functionality of the transmission profiles. It is revealed that the position of the correlation peak originating from interactions between silica nanoparticles evolves linearly during the initial stage of drying and exhibits sigmoidal growth behavior in later stages. The interaction between colloidal particles in different drying stages has been investigated. We provide experimental confirmation of the transition from repulsive interaction to a capillary-driven short-range attraction during shell formation. The present work demonstrates that in-situ scanning SAXS on a suspended droplet is an invaluable technique for monitoring the dynamic self-organization of colloids as it probes the drying of complex fluids without the interference of a substrate.

The structure of deterministically nanopatterned surfaces created using a combination of electron beam lithography and reactive ion etching was evaluated using small-angle neutron scattering (SANS). Samples exhibit 2D neutron scattering patterns that confirm the presence of ordered nanoscale cavities consistent with the targeted morphologies as well as with SEM data analysis. Comparison of SANS intensities obtained from samples in air and in contact with an aqueous phase (pure deuterium oxide, D2O, or a contrast matched mixture of D2O + H2O) reveals formation of stable gaseous nanobubbles trapped inside the cavities. The relative volume of nanobubbles depends strongly on the hydrophobicity of the cavity walls. In the case of hydrophobic surfaces, nanobubbles occupy up to 87% of the total cavity volume. The results demonstrate the high degree of sensitivity of SANS measurements for detecting and characterizing nano- and mesoscale bubbles with the volume fraction as low as ∼10(-6).

The evaporation-induced self-assembly of mixed colloids has been employed to synthesize microspheres of TiO(2)/SiO(2) nanocomposites. Small-angle neutron/X-ray scattering and scanning electron microscopy experiments reveal the hierarchical morphology of the microspheres. Although the internal structure of the microspheres, consisting of solely silica nanoparticles, gets significantly modified with time because of the reduction in the high specific surface area by internal coalescence, the same for the composite microspheres remains stable over an aging time of 1 year. Such temporal stability of the composite microspheres is attributed to the inhibition of coalescence of the silica nanoparticles in the presence of titania nanoparticles. X-ray diffraction and thermogravimetric results show the improved thermal stability of the composite grains against the anatase-to-rutile phase transition. Such thermal stability is attributed to the suppression of the growth of titania nanoparticles in the presence of silica nanoparticles. The UV-vis results indicate the confinement effect of the TiO(2) nanoparticles in the silica matrix. A plausible mechanism has been elucidated for the formation of microspheres with different morphology during self-assembly.

Micrometric grains of anisotropic morphology have been achieved by evaporation-induced self-assembly of silica nanoparticles. The roles of polymer concentration and its molecular weight in controlling the buckling behavior of drying droplets during assembly have been investigated. Buckled doughnut grains have been observed in the case of only silica colloid. Such buckling of the drying droplet could be arrested by attaching poly(ethylene glycol) on the silica surface. The nature of buckling in the case of only silica as well as modified silica colloids has been explained in terms of theory of homogeneous elastic shell under capillary pressure. However, it has been observed that colloids, modified by polymer with relatively large molecular weight, gives rise to buckyball-type grains at higher concentration and could not be explained by the above theory. It has been demonstrated that the shell formed during drying of colloidal droplet in the presence of polymer becomes inhomogeneous due to the presence of soft polymer rich zones on the shell that act as buckling centers, resulting in buckyball-type grains.

The origin of the buckling of micrometer-sized colloidal droplets during evaporation-induced self-assembly (EISA) has been elucidated using electron microscopy and small-angle neutron scattering. Doughnut-like assembled grains with varying aspect ratios are formed during EISA at different physicochemical conditions. It has been revealed that this phenomenon is better explained by an existing hypothesis based on the formation of a viscoelastic shell of nanoparticles during drying than by other existing hypotheses based on the inertial instability of the initial droplets and hydrodynamic instability due to thermocapillary forces. This conclusion was further supported by the arrest of buckling through modification of the colloidal interaction in the initial dispersion., (© 2011 American Chemical Society)