Monodisperse Polystyrene Spheres Research Articles

A Flexible and Free‐Standing Photonic Crystal‐Hydrogel Film for Enhanced Fluorescence from Nitrogen Doped Carbon Dots

AbstractEnhancement of fluorescence emission in a flexible and free‐standing fluorescing film is a key requirement for sensing platforms with augmented sensitivity. In this context, a study on the enhanced fluorescence emission from nitrogen‐doped carbon dots (NCDs) embedded on a flexible free‐standing photonic crystal hydrogel film prepared via photopolymerization, is presented. The composite structure utilizes the photonic crystal enhanced fluorescence (PCEF) technique and incorporates a self‐assembled 3D photonic crystal (3D PC) onto a photopolymerizable hydrogel matrix containing the NCDs. The 3D PC template is prepared through vertical deposition self‐assembly using monodisperse polystyrene (PS) spheres. By leveraging the enhanced excitation and extraction effect in a PC‐fluorophore composite, the authors’ structure exhibits a fourfold enhancement in fluorescence emission compared to the control sample. The relative positioning of the photonic stopband with the excitation and emission spectra of the fluorophore (NCDs) is thoroughly studied by selecting four different 3D PCs with varied lattice parameters. In addition, the hydrogel matrix offers improved photostability and enhanced lifetime for the NCDs. This structure can be further modified into an efficient sensor through appropriate functionalization.

Quantification of Very Low Concentrations of Colloids with Light Scattering Applied to Micro(Nano)Plastics in Seawater

The detection and quantification of micro(nano)plastics in the marine environment are essential requirements to understand the full impacts of plastic pollution on the ecosystem and human health. Here, static light scattering (SLS) and dynamic (DLS) light scattering techniques are assessed for their capacity to detect colloidal particles with diameters between d = 0.1 and 0.8 µm at very low concentrations in seawater. The detection limit of the apparatus was determined using model monodisperse spherical polystyrene latex particles with diameters of 0.2 µm and 0.5 µm. It is shown that the concentration and size of colloids can be determined down to about 10−6 g/L. Light scattering measurements on seawater obtained from different locations in Western Europe show that colloidal particles were detected with DLS in seawater filtered through 0.8 µm pore size filters. The concentration of these particles was not higher than 1 µg/L, with an average diameter of about 0.6 µm. We stress that these particles are not necessarily plastic. No particles were detected after filtration through 0.45 µm pore size filters.

Detection of Sub-20 μm Microplastic Particles by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy and Comparison with Raman Spectroscopy.

Microplastics are particulate water contaminants that are raising concerns regarding their environmental and health impacts. Optical spectroscopy is the gold standard for their detection; however, it has severe limitations such as tens of hours of analysis time and spatial resolution of more than 10 μm, when targeting the production of a 2D map of the microparticle population. In this work, through a single spectrum acquisition, we aim at quickly getting information about the whole population of identical particles, their chemical nature, and their size in a range below 20 μm. To this end, we built a compact setup enabling both attenuated total reflection Fourier transform infrared (ATR-FTIR) and Raman spectroscopy measurement on the same sample for comparison purposes. We used monodisperse polystyrene and poly(methyl methacrylate) microplastic spheres of sizes ranging between 6 and 20 μm, also measured collectively using a bench-top FTIR spectrometer in ATR mode. The ATR-FTIR technique appears to be more sensitive for the smallest particles of 6 μm, while the opposite trend is observed using Raman spectroscopy. We use theoretical modeling to simulate and explain the ripples observed in the measured spectra at the shortest wavelength (higher wavenumber) region, which appears as an indicator of the microparticle dimension. The latter finding opens new perspectives for ATR-FTIR for the identification and classification of populations of nearly identical micro-scale bodies, such as bacteria and other micro-organisms, where the same measured spectrum embeds dual information about the chemical nature and the size.

Polystyrene spheres-templated mesoporous carbonous frameworks implanted with cobalt nanoparticles for highly efficient electrochemical nitrate reduction to ammonia

Electrocatalytic nitrate reduction reaction (eNO3RR) to ammonia (NH3) provides an intriguing approach for both environmental denitrification and sustainable NH3 synthesis. Herein, we report the fabrication of hierarchically mesoporous Co nanoparticles decorated N-doped carbon composites as a highly efficient electrocatalyst for eNO3RR by using monodispersed polystyrene spheres (PS) as sacrificial templates (MR Co-NC). By taking advantage of the large specific area of the pore-rich structures and the high intrinsic activity of metallic Co, the MR Co-NC shows remarkable activity toward eNO3RR, which achieves a partial current density of 268 mA cm−2 with a Faradaic efficiency (FE) of 95.35 ± 1.75 % and a generation rate of 1.25 ± 0.023 mmol h−1 cm−2 for NH3 production under the optimal conditions. The porous carbon skeleton was found to play a dual role by simultaneously protecting the active sites from oxidation and facilitating long-range charge and mass transfer. Theoretical calculations reveal a lower energy barrier of the rate-determining step (*NO2 + H2O + 2e- → *NO + 2OH-) on the metallic Co of MR Co-NC over β-Co(OH)2 formed by the reconstruction of carbon-free Co nanoparticles.

Screen-Printed Carbon Electrodes with Macroporous Copper Film for Enhanced Amperometric Sensing of Saccharides.

A porous layer of copper was formed on the surface of screen-printed carbon electrodes via the colloidal crystal templating technique. An aqueous suspension of monodisperse polystyrene spheres of 500 nm particle diameter was drop-casted on the carbon tracks printed on the substrate made of alumina ceramic. After evaporation, the electrode was carefully dipped in copper plating solution for a certain time to achieve a sufficient penetration of solution within the polystyrene spheres. The metal was then electrodeposited galvanostatically over the self-assembled colloidal crystal. Finally, the polystyrene template was dissolved in toluene to expose the porous structure of copper deposit. The morphology of porous structures was investigated using scanning electron microscopy. Electroanalytical properties of porous copper film electrodes were evaluated in amperometric detection of selected saccharides, namely glucose, fructose, sucrose, and galactose. Using hydrodynamic amperometry in stirred alkaline solution, a current response at +0.6 V vs. Ag/AgCl was recorded after addition of the selected saccharide. These saccharides could be quantified in two linear ranges (0.2–1.0 μmol L−1 and 4.0–100 μmol L−1) with detection limits of 0.1 μmol L−1 glucose, 0.03 μmol L−1 fructose, and 0.05 μmol L−1 sucrose or galactose. In addition, analytical performance of porous copper electrodes was ascertained and compared to that of copper film screen-printed carbon electrodes, prepared ex-situ by the galvanostatic deposition of metal in the plating solution. After calculating the current densities with respect to the geometric area of working electrodes, the porous electrodes exhibited much higher sensitivity to changes in concentration of analytes, presumably due to the larger surface of the porous copper deposit. In the future, they could be incorporated in detectors of flow injection systems due to their long-term mechanical stability.

Chemical Imaging of Single Anisotropic Polystyrene/Poly (Methacrylate) Microspheres with Complex Hierarchical Architecture.

Monodisperse polystyrene spheres are functional materials with interesting properties, such as high cohesion strength, strong adsorptivity, and surface reactivity. They have shown a high application value in biomedicine, information engineering, chromatographic fillers, supercapacitor electrode materials, and other fields. To fully understand and tailor particle synthesis, the methods for characterization of their complex 3D morphological features need to be further explored. Here we present a chemical imaging study based on three-dimensional confocal Raman microscopy (3D-CRM), scanning electron microscopy (SEM), focused ion beam (FIB), diffuse reflectance infrared Fourier transform (DRIFT), and nuclear magnetic resonance (NMR) spectroscopy for individual porous swollen polystyrene/poly (glycidyl methacrylate-co-ethylene di-methacrylate) particles. Polystyrene particles were synthesized with different co-existing chemical entities, which could be identified and assigned to distinct regions of the same particle. The porosity was studied by a combination of SEM and FIB. Images of milled particles indicated a comparable porosity on the surface and in the bulk. The combination of standard analytical techniques such as DRIFT and NMR spectroscopies yielded new insights into the inner structure and chemical composition of these particles. This knowledge supports the further development of particle synthesis and the design of new strategies to prepare particles with complex hierarchical architectures.

Superhydrophilic Coating of Pine Wood by Plasma Functionalization of Self-Assembled Polystyrene Spheres

Self-assembling films typically used for colloidal lithography have been applied to pine wood substrates to change the surface wettability. Therefore, monodisperse polystyrene (PS) spheres have been deposited onto a rough pine wood substrate via dip coating. The resulting PS sphere film resembled a polycrystalline face centered cubic (FCC)-like structure with typical domain sizes of 5–15 single spheres. This self-assembled coating was further functionalized via an O2 plasma. This plasma treatment strongly influenced the particle sizes in the outermost layer, and hydroxyl as well as carbonyl groups were introduced to the PS spheres’ surfaces, thus generating a superhydrophilic behavior.

Anionic/nonionic surfactants for controlled synthesis of highly concentrated sub-50 nm polystyrene spheres.

Polystyrene nanospheres are of great importance in 3D hard templating along with many other fields like pharmaceuticals and coatings. Therefore, it is important to be able to prepare polystyrene beads with different sphere sizes that suit each application. In this work, the emulsion polymerization method was used to prepare monodispersed polystyrene (PS) spheres with an average size of 50 nm, using styrene monomer, sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP) as surfactants, and potassium persulfate (KPS) as the initiator. The average size and size distribution of the PS spheres were controlled by optimizing the synthesis parameters such as the concentration of the monomer, initiator, and surfactant, the type of surfactant, and the time and temperature of polymerization. The shape, size, and size distribution of the prepared PS spheres were characterized using dynamic light scattering (DLS) and scanning electron microscopy (SEM). The preparation of perfectly spherical PS spheres as small as 50 nm with a narrow size distribution is obtained using 8% styrene with (5% SDS and 2% KPS of the styrene amount) at 90 °C, with the monomer and surfactant molar ratio and concentration and the polymerization temperature being the dominating factors that affect the PS bead size.

Reversibly compressible and freestanding monolithic carbon spherogels

We present a versatile strategy to tailor the nanostructure of monolithic carbon aerogels. By use of an aqueous colloidal solution of polystyrene in the sol-gel processing of resorcinol-formaldehyde gels, we can prepare, after supercritical drying and successive carbonization, freestanding monolithic carbon aerogels, solely composed of interconnected and uniformly sized hollow spheres, which we name carbon spherogels. Each sphere is enclosed by a microporous carbon wall whose thickness can be adjusted by the polystyrene concentration, which affects the pore texture as well as the mechanical properties of the aerogel monolith. In this study, we used monodisperse polystyrene spheres of approximately 250 nm diameter, which result in an inner diameter of the final hollow carbon spheres of approximately 200 ± 5 nm due to shrinkage during the carbonization process. The excellent homogeneity of the samples, as well as uniform sphere geometries, are confirmed by small- and angle X-ray scattering. The presence of macropores between the hollow spheres creates a monolithic network with the benefit of being reversibly compressible up to 10% linear strain without destruction. Electrochemical tests demonstrate the applicability of ground and CO2 activated carbon spherogels as electrode materials.

Paper-based porous graphene/single-walled carbon nanotubes supported Pt nanoparticles as freestanding catalyst for electro-oxidation of methanol

In this paper, we designed a facile strategy to prepare a freestanding 3D interconnected embossed graphene (e-RGO)-single wall carbon nanotubes (SWCNTs) paper supported Pt nanoparticles (Pt/e-RGO-SWCNT) without binder, which can be used as a flexible and robust electrode for methanol oxidation. The 3D porous e-RGO was prepared by using monodispersed polystyrene (PS) spheres as sacrificial templates to suppress the re-stacking of RGO sheets. Meanwhile, the SWCNTs penetrated through the e-RGO, and thus weaved them into a scalable film to provide an integrative conductive framework. Benefited from their high surface area, 3D porous interconnected architecture, and good electrical conductivity, the Pt/e-RGO-SWCNT catalyst exhibited much higher electrocatalytic activity and durability for methanol oxidation than Pt/e-RGO and Pt/RGO catalysts. More importantly, the Pt/e-RGO-SWCNT is demonstrated to be outstanding flexible electrocatalysts, and the electrocatalytic performances under the different distorted situation (such as folded and rolled states) are almost the same as the normal state.

Mechanical formation of micro- and nano-plastic materials for environmental studies in agricultural ecosystems

Release of microplastics (MPs) and nanoplastics (NPs) into agricultural fields is of great concern due to their reported ecotoxicity to organisms that provide beneficial service to the soil such as earthworms, and the potential ability of MPs and NPs to enter the food chain. Most fundamental studies of the fate and transport of plastic particulates in terrestrial environments employ idealized MP materials as models, such as monodisperse polystyrene spheres. In contrast, plastics that reside in agricultural soils consist of polydisperse fragments resulting from degraded films employed in agriculture. There exists a need for more representative materials in fundamental studies of the fate, transport, and ecotoxicity of MPs and NPs in soil ecosystems. The objective of this study was therefore to develop a procedure to produce MPs and NPs from agricultural plastics (a mulch film prepared biodegradable polymer polybutyrate adipate-co-terephthalate (PBAT) and low-density PE [LDPE]), and to characterize the resultant materials. Soaking of PBAT films under cryogenic conditions promoted embrittlement, similar to what occurs through environmental weathering. LDPE and cryogenically-treated PBAT underwent mechanical milling followed by sieve fractionation into MP fractions of 840 μm, 250 μm, 106 μm, and 45 μm. The 106 μm fraction was subjected to wet grinding to produce NPs of average particle size 366.0 nm and 389.4 nm for PBAT and LDPE, respectively. A two-parameter Weibull model described the MPs' particle size distributions, while NPs possessed bimodal distributions. Size reduction did not produce any changes in the chemical properties of the plastics, except for slight depolymerization and an increase of crystallinity resulting from cryogenic treatment. This study suggests that MPs form from cutting and high-impact mechanical degradation as would occur during the tillage into soil, and that NPs form from the MP fragments in regions of relative weakness that possess lower molecular weight polymers and crystallinity.

The Structural Colors of Photonic Glasses

AbstractThe color of materials usually originates from a combination of wavelength‐dependent absorption and scattering. Controlling the color without the use of absorbing dyes is of practical interest, not only because of undesired bleaching properties of dyes but also regarding minimization of environmental and health issues. Color control without dyes can be achieved by tuning the material's scattering properties in controlling size and spatial arrangement of scatterers. Herein, calibrated photonic glasses (PGs), which are isotropic materials made by random aggregation of nonabsorbing, monodisperse colloidal polystyrene spheres, are used to generate a wide spectral range of purely structural, angular‐independent colors. Experimental reflectance spectra for different sized spheres compare well with a recent theoretical model, which establishes the latter as a tool for color mapping in PGs. It allows to determine the range of visible colors accessible in PGs as function of size, packing fraction, and refractive index of scatterers. It also predicts color saturation on top of the white reflectance as function of the sample's optical thickness. Blue, green, and red are obtained even with low index, while saturated green, cyan, yellow, and magenta can be reached in higher index PGs over several orders of magnitude of sample thickness.

Preparation of monodisperse polystyrene spheres by physical method

The preparation of monodisperse polystyrene spheres was carried out by physical method, i.e. milling and gamma irradiation processes, which used the solid commercial polystyrene. The solid polystyrene was dissolved by ethyl acetate at a concentration of 10%. The monodisperse particle arrangement was obtained by milling process which in this research the time duration varied by 8 and 60 minutes. Whereas the spherical particle structure was achieved by gamma irradiation at a dose varied by 5 KGy or 15 KGy. The yielded solution was characterized using Particle Size Analyser (PSA) and Scanning Electron Microscopy (SEM). The results showed that the optimum monodisperse polystyrene spheres solutions were produced by dissolving the solid polystyrene using ethyl acetate and milling the solution for 8 minutes and radiating the solution using gamma radiation at a dose of 15 KGy. The resulting solution has a particle diameter range of 23-57.8 nm and a span of 0.49-0.59.

Oxidative desulfurization of fuels at room temperature using ordered meso/macroporous H3PW12O40/SiO2 catalyst with high specific surface areas

Ordered meso/macroporous H3PW12O40/SiO2 nanocomposites with high specific surface areas were prepared using cationic surfactant and monodispersed polystyrene spheres (PS) as dual-template. The characterization results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption, and small-angle XRD patterns confirmed the existence of ordered meso/macroporous structure and the wide-angle XRD patterns, Fourier transform infrared spectroscopy (FTIR), X-ray photoemission spectroscopy (XPS) measurements suggested the high dispersivity of the Keggin-type heteropolyacid (HPA) on silica matrix. There was an optimum value of cationic surfactant usage and proper calcination temperature of ordered meso/macroporous H3PW12O40/SiO2 catalyst leading to ultra-high specific surface areas. Furthermore, the ordered meso/macroporous H3PW12O40/SiO2 catalyst was evaluated for ultra-deep oxidative desulfurization (ODS) of cyclic sulphur-containing compounds using hydrogen peroxide (H2O2) as oxidant. Under optimum reaction conditions, dibenzothiophene (DBT) could be removed within 100 min at 30 °C by meso/macroporous H3PW12O40/SiO2 catalyst. The excellent catalytic activity should be attributed to the combination of ordered meso/macroporous architecture and high surface area of H3PW12O40/SiO2 catalyst which promoted the mass transport of reactants and products in the pore channel and provided more accessible catalytic active sites. In addition, the meso/macroporous H3PW12O40/SiO2 catalyst showed good stability with only 1.9% efficiency decreased after 6 cycles.

Highly efficient deep desulfurization of fuels by meso/macroporous H3PW12O40/TiO2 at room temperature

This paper described the synthesis of meso/macroporous phosphotungstic acid (HPW) /TiO2 catalyst with quaternary ammonium bromide and monodispersed polystyrene spheres (PS) as dual-template. The synthetic parameters, such as concentration of the templates and the alky chain length of quaternary ammonium bromide was studied carefully and optimized to generate catalyst with regulated porous features. The chemical properties of the catalyst was also investigated, X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) measurements confirmed the Keggin-type HPW were highly dispersed on the TiO2 framework. The optimal meso/macroporous HPW/TiO2 catalyst exhibited excellent catalytic activity in the oxidation of refractory sulphur compounds such as benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT). DBT was removed within 2 h at 30 °C under selected reaction conditions and the apparent activation energy for DBT oxidation was calculated to be 45.7 kJ/mol. The high ODS reaction rate of catalyst could be attributed to the combination of unique meso/macroporous architecture allowing for efficient mass transport of reactants and products in pore channel and its high surface area, large mesoporous size, and pore volume enabling sufficient exposure of catalytic active sites. Moreover, the meso/macroporous HPW/TiO2 catalyst also exhibited excellent reusability with no obviously degradation even after eight cycles.

Surface-enhanced Raman spectroscopy substrate based on Ag-coated self-assembled polystyrene spheres

The silver (Ag) films were deposited on the monodispersed polystyrene spheres that were drop-coated on hydrophilic glass substrates in order to form a self-assembled 2D monolayer. Thus prepared Ag films over polystyrene nanospheres (AgFONs) were used to record the surface-enhanced Raman scattering (SERS) spectra of rhodamine 6G (R6G) and pyridine (λex = 514.5 nm). AgFONs were prepared by depositing 120, 180 and 240 nm thick Ag layer on the 1000 nm polystyrene spheres and 80, 120, 160 and 200 nm thick Ag layer on the 350 nm spheres as well as on their mixture (350 + 1000 nm). The silver was deposited by electron beam evaporation technique. The best enhancement of the Raman signal for both test molecules was obtained using 180 nm Ag film deposited on the 1000 nm spheres and using 80 nm Ag film deposited on the 350 nm polystyrene spheres. The lowest detectable concentrations of R6G and pyridine were 10−9 mol L−1 and 1.2 × 10−3 mol L−1, respectively. This study has shown that AgFONs could be regarded as good and reproducible SERS substrate for analytical detection of various organic molecules.

Tailoring Size and Coverage Density of Silver Nanoparticles on Monodispersed Polymer Spheres as Highly Sensitive SERS Substrates.

Silver nanoparticles (AgNPs) were deposited onto the monodispersed carboxylic polystyrene (CPS) spheres by an improved in situ reduction method. The size and coverage density of the AgNPs on the surface of CPS spheres could be easily tailored by tuning the concentrations of carboxylic functional groups and silver precursor. The morphologies and structures of the resulting CPS/Ag hybrid particles were studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-Vis-NIR spectrometer and X-ray photoelectron spectroscopy (XPS), etc. The surface enhanced Raman scattering (SERS) performances of the resulting uniform CPS/Ag hybrid particles were investigated using 4-aminobenzenethiol (4-ABT) as the probe molecule. The optimized CPS/Ag hybrid particles show high enhancement factor (EF) of 2.71×10(7) , low limit of detection (LOD) of 10(-10) m and good reproducibility with relative standard deviation (RSD) of 9.64 %. The good SERS improvement properties demonstrate these hybrid particles could be employed as simple and effective substrates in the SERS spectroscopy.

Co-templating synthesis of mesoporous hollow silica spheres and their application in catalytic oxidation with low Pt loading

Mesoporous hollow silica spheres (MHSS) with uniform size were successfully prepared by introducing monodispersed polystyrene (PS) spheres as hard template and selected surfactant as soft template in acid condition. With assistance of different surfactants, a series of mesoporous shells were created and the used surfactants have a significant effect on the structural properties of MHSS. The highest surface area was 690.3m2g−1 on the MHSS which was achieved by using P123 as a soft template. The MHSS was further used for loading active Pt through the reaction between chloroplatinic acid or and sodium borohydride. The as-prepared Pt/MHSS catalyst exhibited high activity for VOCs' deep oxidation.

Enhanced structural and phase stability of titania inverse opals

The applications and processing of nanostructured materials at high temperatures require stability of their morphology. However, in such environments (>1000°C), these structures are prone to significant undesired microstructural changes that result in a loss of functional properties. The thermal stability of titania inverse opal films, prepared from self-assembled templates of monodisperse polystyrene spheres by infiltration utilizing atomic layer deposition and subsequent calcination, was assessed. Resistance to grain growth and a shift in the anatase-to-rutile transformation to higher temperatures was observed, with dramatic stability under vacuum. Vacuum annealed samples retained the anatase phase and exhibited minimal grain growth even after 3h at 1300°C. Photonic properties were retained until the transformation onset. The remarkable resistance was attributed to inhibition of surface diffusion and structure-substrate constraints. In addition to being technologically enabling, the results provide further insight into the titania system and its phase transformation mechanism.

Study on a Photonic Crystal Hydrogel Material for Chemical Sensing

There is intense interest in the applications of photonic crystal hydrogel materials for the detection of glucose, metal ions, organophosphates and so on. In this paper, monodisperse polystyrene spheres with diameters between 100 ~ 440 nm were synthesized by emulsion polymerization. Highly charged polystyrene spheres readily self-assembled into crystalline colloidal array because of electrostatic interactions. Photonic crystal hydrogel materials were formed by polymerization of acrylamide hydrogel around the crystalline colloidal arrays of polystyrene spheres. After chemical modification of hydrogel backbone with carboxyl groups, our photonic crystals hydrogel materials are demonstrated to be excellent in response to pH and ionic strength changes.