Drop-Cast Hybrid Poly(styrene)-b-Poly(ethylene oxide) Metal Salt Films: Solvent Evaporation and Crystallinity-Dependent Evolution of Film Morphology.

Morphology templates of solution-based diblock copolymer (DBC) films with loading metal salts are widely applied in photocatalysts, photovoltaics, and sensors due to their adjustable characteristics based on surface (de-)wetting and microphase separation. The present work investigates the morphologies of drop-cast hybrid films based on poly(styrene)-b-poly(ethylene oxide) (PS-b-PEO) and the metal salts titanium isopropoxide (TTIP) and zinc acetate dehydrate (ZAD) in comparison to the pure DBC. By utilizing scanning electron microscopy, grazing-incidence small- and wide-angle X-ray scattering, and differential scanning calorimetry, we find that the resulting film morphologies depend not only on the presence of metal salts but also on solvent evaporation and crystalline formation. At 20 °C, additional TTIP and ZAD in the polymer template cause the morphology to change from packed globular structures to separated wormlike structures attributed to the changed polymer environment. Furthermore, additional tetrahydrofuran causes irregular structures at the precursor film part and the overlapped wormlike structures to transition into close-packed globular structures at the cap film parts of the pure DBC. In contrast, at 50 °C, the globular structures transit to fingerprint patterns due to the thermal behavior of the crystallizable PEO blocks, and the metal salt additives suppress crystalline structure formation in the PEO domains.

Honeycomb Cell Structures Formed in Drop-Casting CNT Films for Highly Efficient Solar Absorber Applications.

This study investigates the process of using multi-walled carbon nanotube (MWCNT) coatings to enhance lamp heating temperatures for solar thermal absorption applications. The primary focus is studying the effects of the self-organized honeycomb structures of CNTs formed on silicon substrates on different cell area ratios (CARs). The drop-casting process was used to develop honeycomb-structured MWCNT-coated absorbers with varying CAR values ranging from ~60% to 17%. The optical properties were investigated within the visible (400-800 nm) and near-infrared (934-1651 nm) wavelength ranges. Although fully coated MWCNT absorbers showed the lowest reflectance, honeycomb structures with a ~17% CAR achieved high-temperature absorption. These structures maintained 8.4% reflectance at 550 nm, but their infrared reflection dramatically increased to 80.5% at 1321 nm. The solar thermal performance was assessed throughout a range of irradiance intensities, from 0.04 W/cm2 to 0.39 W/cm2. The honeycomb structure with a ~17% CAR value consistently performed better than the other structures by reaching the highest absorption temperatures (ranging from 52.5 °C to 285.5 °C) across all measured intensities. A direct correlation was observed between the reflection ratio (visible: 550 nm/infrared: 1321 nm) and the temperature absorption efficiency, where lower reflection ratios were associated with higher temperature absorption. This study highlights the significant potential for the large-scale production of cost-effective solar thermal absorbers through the application of optimized honeycomb-structured absorbers coated with MWCNTs. These contributions enhance solar energy efficiency for applications in water heating and purification, thereby promoting sustainable development.

Comparative Study of Polymer-Modified Copper Oxide Electrochemical Sensors: Stability and Performance Analysis.

The effectiveness of copper oxide-modified electrochemical sensors using different polymers is being studied. The commercial powder was sonicated in an isopropyl alcohol solution and distilled water with 5 wt% polymers (chitosan, Nafion, PVP, HPC, α-terpineol). It was observed that the chitosan and Nafion caused degradation of CuO, but Nafion formed a stable mixture when diluted. The modified electrodes were drop-casted and analyzed using cyclic voltammetry in 0.1 M KCl + 3 mM [Fe(CN)6]3-/4- solution to determine the electrochemically active surface area (EASA). The results showed that α-terpineol formed agglomerates, while HPC created uneven distributions, resulting in poor stability. On the other hand, Nafion and PVP formed homogeneous layers, with PVP showing the highest EASA of 0.317 cm2. In phosphate-buffered saline (PBS), HPC and PVP demonstrated stable signals. Nafion remained the most stable in various electrolytes, making it suitable for sensing applications. Testing in 0.1 M NaOH revealed HPC instability, partial dissolution of PVP, and Cu ion reduction. The type of polymer used significantly impacts the performance of CuO sensors. Nafion and PVP show the most promise due to their stability and effective dispersion of CuO. Further optimization of polymer-CuO combinations is necessary for enhanced sensor functionality.

Photoluminescence variations in organic fluorescent crystals by changing the surface energy of the substrate.

Organic fluorescent crystals were obtained using single-benzene-based diethyl 2,5-dihydroxyterephthalate (DDT) molecules through crystallization from a droplet of the DDT solution on an Au substrate. To control the size of the DDT crystals, the surface energy of the Au substrate was modified with air plasma treatment, producing a hydrophilic surface and a hydrophobic self-assembled monolayer (SAM) coating. The size of DDT crystals increased as the surface energy of the substrate decreased. The averaged cross-section area of the DDT crystals on the Au substrates increased in the order of the air-plasma-treated substrate (∼23.43 µm2) < pristine substrate (∼225.6 µm2) < hydrophobic SAM-coated substrate (∼2240 µm2). On the other hand, the main emission of the DDT crystals redshifted from blue to green as the crystal size increased, which is related to the aggregation of the DDT crystals. Moreover, the coffee-ring effect during the DDT crystallization was hindered by controlling the solvent evaporation conditions. As examples of the application of the proposed technique, patterned DDT crystals were obtained using selectively patterned hydrophobic and hydrophilic substrates.

Indispensable Nafion Ionomer for High-Efficiency and Stable Oxygen Evolution Reaction in Alkaline Media.

Addressing the challenge of sluggish kinetics and limited stability in alkaline oxygen evolution reactions, recent exploration of novel electrochemical catalysts offers improved prospects. To expedite the assessment of these catalysts, a half-cell rotating disk electrode is often favored for its simplicity. However, the actual catalyst performance strongly depends on the fabricated catalyst layers, which encounter mass transport overpotentials. We systematically investigate the role and sequence of electrode drop-casting methods onto a glassy carbon electrode regarding the efficiency of the oxygen evolution reaction. The catalyst layer without Nafion experiences nearly 50% activity loss post stability test, while those with Nafion exhibit less than 5% activity loss. Additionally, the sequence of application of the catalyst and Nafion also shows a significant effect on catalyst stability. The catalyst activity increases by roughly 20% after the stability test when the catalyst layer is coated first with an ionomer layer, followed by drop-casting the catalysts. Based on the half-cell results, the Nafion ionomer not only acts as a binder in the catalyst layer but also enhances the interfacial interaction between the catalyst and electrolyte, promoting performance and stability. This study provides new insights into the efficient and accurate evaluation of electrocatalyst performance and stability as well as the role of Nafion ionomer in the catalyst layer.

Influence of Solvents and Adsorption of Organic Molecules on the Properties of CVD Synthesized 2D MoS2.

We present a simple method for modification of 2D materials by drop-casting of the organic molecule in solution on the 2D material under ambient conditions. Specifically, we investigated the adsorption of 6-(4,5-Dihydro-1H-imidazol-3-ium-2-yl)-2-(naphthalene-2-yl)benzothiazole methanesulfonate (L63MS) organic molecule on 2D MoS2. To better understand the effect of the organic molecule on the 2D material, we also investigated the impact of solvents alone on the materials' properties. The MoS2 samples were synthesized using ambient pressure chemical vapor deposition. Atomic force microscopy, Raman spectroscopy, photoluminescence spectroscopy and optical microscopy were used to characterize the samples. The measurements were performed after synthesis, after the drop-casting of solvents and after the drop-casting of organic molecule solutions. Our results indicate that the used organic molecule effectively adsorbs on and prompts discernible changes in the (opto)electronic properties of the 2D material. These changes encompass variations in the Raman spectra shape, alterations in the photoluminescence (PL) signal characteristics and modifications in excitonic properties. Such alterations can be linked to various phenomena including doping, bandgap modifications, introduction or healing of defects and that the solvent plays a crucial role in the process. Our study provides insights into the modification of 2D materials under ambient conditions and highlights the importance of solvent selection in the process.

Developing aerogel surfaces via switchable-hydrophilicity tertiary amidine coating for improved oil recovery.

Blanket aerogels (i.e., Cabot™ Thermal Wrap® (TW) and Aspen™ Spaceloft® (SL)) with surfaces that have controllable wettability are promising advanced materials for oil recovery applications, where high oil uptake during deployment could be coupled with high oil release to enable reusability of recovered oil. The study presented here details the preparation of CO2-switchable aerogel surfaces through the application of switchable tertiary amidine (i.e., tributylpentanamidine (TBPA)) onto aerogel surfaces using drop casting, dip coating, and physical vapor deposition techniques. TBPA is synthesized via two step processes: (1) synthesis of N, N-dibutylpentanamide, (2) synthesis of N, N-tributylpentanamidine. The deposition of TBPA is confirmed by X-ray photoelectron spectroscopy. Our experiments revealed that surface coating of TBPA onto aerogel blankets was partially successful within limited set of process conditions (e.g., 290 ppm CO2 and 5500 ppm humidity for PVD, 106 ppm CO2 and 700 ppm humidity for drop casting and dip coating), but that the post-aerogel modification strategies yielded poor, heterogeneous reproducibility. Overall, more than 40 samples were tested for their switchability in the presence of CO2 and water vapor, respectively, and the success rate was 6.25 %, 11.7 % and 18 % for PVD, drop casting, and dip coating, respectively. The most likely reasons for unsuccessful coating onto aerogel surfaces are: (1) the heterogeneous fiber structure of the aerogel blankets, (2) poor distribution of the TBPA over the aerogel blanket surface.

Drop-casted Photosystem I/cytochrome c multilayer films for biohybrid solar energy conversion.

One of the main barriers to making efficient Photosystem I-based biohybrid solar cells is the need for an electrochemical pathway to facilitate electron transfer between the P700 reaction center of Photosystem I and an electrode. To this end, nature provides inspiration in the form of cytochrome c6, a natural electron donor to the P700 site. Its natural ability to access the P700 binding pocket and reduce the reaction center can be mimicked by employing cytochrome c, which has a similar protein structure and redox chemistry while also being compatible with a variety of electrode surfaces. Previous research has incorporated cytochrome c to improve the photocurrent generation of Photosystem I using time consuming and/or specialized electrode preparation. While those methods lead to high protein areal density, in this work we use the quick and facile vacuum-assisted drop-casting technique to construct a Photosystem I/cytochrome c photoactive composite film with micron-scale thickness. We demonstrate that this simple fabrication technique can result in high cytochrome c loading and improvement in cathodic photocurrent over a drop-casted Photosystem I film without cytochrome c. In addition, we analyze the behavior of the cytochrome c/Photosystem I system at varying applied potentials to show that the improvement in performance can be attributed to enhancement of the electron transfer rate to P700 sites and therefore the PSI turnover rate within the composite film.

Palladium/Graphene Oxide Nanocomposite for Hydrogen Gas Sensing Applications Based on Tapered Optical Fiber.

Gaseous pollutants such as hydrogen gas (H2) are emitted in daily human activities. They have been massively studied owing to their high explosivity and widespread usage in many domains. The current research is designed to analyse optical fiber-based H2 gas sensors by incorporating palladium/graphene oxide (Pd/GO) nanocomposite coating as sensing layers. The fabricated multimode silica fiber (MMF) sensors were used as a transducing platform. The tapering process is essential to improve the sensitivity to the environment through the interaction of the evanescent field over the area of the tapered surface area. Several characterization methods including FESEM, EDX, AFM, and XRD were adopted to examine the structure properties of the materials and achieve more understandable facts about their functional performance of the optical sensor. Characterisation results demonstrated structures with a higher surface for analyte gas reaction to the optical sensor performance. Results indicated an observed increment in the Pd/GO nanocomposite-based sensor responses subjected to the H2 concentrations increased from 0.125% to 2.00%. The achieved sensitivities were 33.22/vol% with a response time of 48 s and recovery time of 7 min. The developed optical fiber sensors achieved excellent selectivity and stability toward H2 gas upon exposure to other gases such as ammonia and methane.

Gold nanoparticle decorated blu-ray digital versatile disc as a highly reproducible surface-enhanced Raman scattering substrate for detection and analysis of rotavirus RNA in laboratory environment.

Detection and estimation of various biomolecular samples are often required in research and clinical laboratory applications. Present work demonstrates the functioning of a surface-enhanced Raman scattering (SERS) substrate that has been obtained by drop-casting of citrate-reduced gold nanoparticles (AuNPs) of average dimension of 23 nm on a bare blu-ray digital versatile disc (BR-DVD) substrate. The performance of the proposed SERS substrate has been initially evaluated with standard Raman active samples, namely malachite green (MG) and 1,2-bis(4-pyridyl)ethylene (BPE). The designed SERS substrate yields an average enhancement factor of 3.2 × 106 while maintaining reproducibility characteristics as good as 94% over the sensing region of the substrate. The usability of the designed SERS substrate has been demonstrated through the detection and analysis of purified rotavirus double-stranded RNA (dsRNA) samples in the laboratory environment condition. Rotavirus RNA concentrations as low as 10 ng/µL could be detected with the proposed sensing scheme.

High-Sensitivity and Environmentally Friendly Humidity Sensors Deposited with Recyclable Green Microspheres for Wireless Monitoring.

The reliable, high-sensitive, wireless, and affordable requirements for humidity sensors are needed in high-precision measurement fields. Quartz crystal microbalance (QCM) based on the piezoelectric effect can accurately detect the mass changes at the nanogram level. However, water-capture materials deposited on the surface of QCM generally show disadvantages in either cost, sensitivity, or recyclability. Herein, novel QCM-based humidity sensors (NQHSs) are developed by uniformly depositing green microspheres (GMs) of natural polymers prepared by the chemical synthesis of the emulsification/inner gel method on QCM as humidity-sensitive materials. The NQHSs demonstrate high accuracy and sensitivity (27.1 Hz/% RH) owing to the various hydrophilic groups and porous nano-3D deposition structure. Compared with the devices deposited with a smooth film, the frequency of the NQHSs shows almost no changes during the cyclic test and exhibits long-term stability. The NQHSs have been successfully applied to non-contact sensing human activities and remote real-time humidity monitoring via Bluetooth transmission. In addition, the deposited humidity-sensitive GMs and QCM substrate are fully recycled and reused (72% of the original value). This work has provided an innovative idea to construct environmental-friendly, high-sensitivity, and wireless humidity sensors.

Effect of Humidity and Temperature on the Impedances and Voltage of Al/Gr-Jelly/Cu-Rubber Composite-Based Flexible Electrochemical Sensors.

Here we present the fabrication of graphene and jelly (superabsorbent polymer) electrolyte composite-based shockproof flexible electrochemical sensors (Al/Gr-Jelly/Cu) and their properties under the effect of humidity and temperature. A layer of graphene mixed in jelly electrolyte was drop-casted onto porous rubber substrates between preliminary fixed aluminum (Al) and copper (Cu) electrodes followed by rubbing-in. It was observed that the graphene and jelly mixture was mechanically soft and flexible, similar to jelly. Electrically, this mixture (graphene and jelly) behaved as a flexible electrolyte. It was observed that under the effect of humidity ranging from 47 to 98%, the impedances of the sensors decreased by 2.0 times on average. Under the effect of temperatures ranging from 21 to 41 °C the impedances decreased by 2.4 times. The average temperature coefficient of impedances was equal to -0.03 °C-1. The electrochemical voltage generated by the flexible jelly electrolyte sensors was also investigated. It was found that the initial open-circuit voltages were equal to 201 mV and increased slightly, by 5-10% under the effect of humidity and temperature as well. The short-circuit currents under the effect of humidity and temperature increased by 2-3 times. The Al/Gr-Jelly/Cu electrochemical sensors may be used as prototypes for the development of the jelly electronic-based devices.

Freestanding and Sandwich MXene-Based Cathode with Suppressed Lithium Polysulfides Shuttle for Flexible Lithium-Sulfur Batteries.

Flexible lithium-sulfur (Li-S) batteries with high mechanical compliance and energy density are highly desired. This manuscript reported that large-area freestanding MXene (Ti3C2Tx) film has been obtained through a scalable drop-casting method, significantly improving adhesion to the sulfur layer under the continuously bent. Titanium oxide anchored on holey Ti3C2Tx (TiO2/H-Ti3C2Tx) was also produced by the well-controlled oxidation of few-layer Ti3C2Tx, which greatly facilitates lithium ion transport as well as prevents the shuttling of lithium polysulfides. Therefore, the obtained sandwich electrode has demonstrated a high capacity of 740 mAh g-1 at 2 C and a high capacity retention of 81% at 1 C after 500 cycles. Flexible Li-S batteries based on this sandwich electrode have a capacity retention as high as 95% after bending 500 times. This work provides effective design strategies of MXene for flexible batteries and wearable electronics.

Drop-Casting Method to Screen Ruddlesden-Popper Perovskite Formulations for Use in Solar Cells.

Small-area metal-halide perovskite solar cells (PSCs) having power-conversion efficiencies (PCEs) of greater than 25% can be prepared by using a spin-coated perovskite layer, but this technique is not readily transferrable to large-scale manufacturing. Drop-casting is a simple alternative method for film formation that is more closely aligned to industry-relevant coating processes. In the present work, drop-casting was used to prepare films for screening two-dimensional Ruddlesden-Popper (2DRP) metal-halide perovskite formulations for potential utility in PSCs, without additional processing steps such as inert-gas blowing or application of antisolvent. The composition of the 2DRP formulation used for drop-casting was found to have a profound effect on optical, spectroscopic, morphological, and phase-distribution properties of the films as well as the photovoltaic performance of related PSC devices. This facile method for screening film quality greatly assists in speeding up the identification of perovskite formulations of interest. The optimal 2DRP perovskite formulation identified from screening was utilized for industry-relevant one-step roll-to-roll slot-die coating on a flexible plastic substrate, producing PSCs having PCEs of up to 8.8%. A mechanism describing film formation and phase distribution in the films is also proposed.

Ink-jet printing and drop-casting deposition of 2H-phase SnSe2and WSe2nanoflake assemblies for thermoelectric applications.

The development of simple, scalable, and cost-effective methods to prepare Van der Waals materials for thermoelectric applications is a timely research field, whose potential and possibilities are still largely unexplored. In this work, we present a systematic study of ink-jet printing and drop-casting deposition of 2H phase SnSe2and WSe2nanoflake assemblies, obtained by liquid phase exfoliation, and their characterization in terms of electronic and thermoelectric properties. The choice of optimal annealing temperature and time is crucial for preserving phase purity and stoichiometry and for removing dry residues of ink solvents at inter-flake boundaries, while maximizing the sintering of nanoflakes. An additional pressing is beneficial to improve nanoflake orientation and packing, thus enhancing electric conductivity. In nanoflake assemblies deposited by drop casting and pressed at 1 GPa, we obtained thermoelectric power factors at room temperature up to 2.2 × 10-4mW m-1K-2for SnSe2and up to 3.0 × 10-4mW m-1K-2for WSe2.

Photothermal Effects and Heat Conduction in Nanogranular Silicon Films.

We present results on the photothermal (PT) and heat conductive properties of nanogranular silicon (Si) films synthesized by evaporation of colloidal droplets (drop-casting) of 100 ± 50 nm-sized crystalline Si nanoparticles (NP) deposited on glass substrates. Simulations of the absorbed light intensity and photo-induced temperature distribution across the Si NP films were carried out by using the Finite difference time domain (FDTD) and finite element mesh (FEM) modeling and the obtained data were compared with the local temperatures measured by micro-Raman spectroscopy and then was used for determining the heat conductivities k in the films of various thicknesses. The cubic-to-hexagonal phase transition in Si NP films caused by laser-induced heating was found to be heavily influenced by the film thickness and heat-conductive properties of glass substrate, on which the films were deposited. The k values in drop-casted Si nanogranular films were found to be in the range of lowest k of other types of nanostructurely voided Si films due to enhanced phonon scattering across inherently voided topology, weak NP-NP and NP-substrate interface bonding within nanogranular Si films.

Ordered Ti-doped FeVO4 nanoblock photoanode with improved charge properties for efficient solar water splitting.

Highly photoactive FeVO4 photoanodes with ordered nanoblock morphology and uniform Ti-doping were prepared by drop-casting mixed Ti and V precursors onto FeOOH nanorod films and following an annealing process. The results indicate that Ti4+ is uniformly doped into the FeVO4 lattice by substituting V5+ and provides an increased number of O2- vacancies. The optimized film thickness and doping level are 620 nm and 0.3%, respectively. Compared to the undoped sample, the Ti-doped photoanode showed ~ 219% enhancement in photocurrent at 1.0 V vs Ag/AgCl under back illumination of AM 1.5, reaching a state-of-the-art value of ~ 1.47 mA cm-2, and also achieved stable and efficient overall water splitting activity with evolution rates of 28.3 and 14.1 µmol cm-2h-1 for H2 and O2, respectively. The excellent PEC performance could be attributed to the remarkably enhanced charge carrier concentration and conductivity, and the facilitated charge transfer kinetics across the semiconductor/electrolyte interface, as a result of Ti-doping.

Chemosensitive Thin Films Active to Ammonia Vapours.

The paper presents various dispersive systems developed for sensing toxic substance-ammonia. Polycarbonate dissolved in methylene chloride was used as a polymer matrix, which was enriched with: multi-walled carbon nanotubes (MWCNs), reduced graphene oxide (rGO) and conductive polymer (polyaniline-PANi). Dispersive systems were applied to the prefabricated substrates with comb electrodes by two methods: spraying and drop-casting, forming an active chemosensitive to ammonia vapours films. The spraying method involved applying the dispersion to the substrate by an aerograph for a specific time, whereas drop-casting involves depositing of the produced dispersive systems using a precision automatic pipette. The electrical responses of the obtained films were examined for nominal concentrations of ammonia vapours. Different types of dispersions with various composition were tested, the relationships between individual compounds and ammonia were analysed and the most promising dispersions were selected. Sensor containing rGO deposited by drop-casting revealed the highest change in the resistance (14.21%).

Drop-casted Platinum Nanocube Catalysts for Hydrogen Evolution Reaction with Ultrahigh Mass Activity.

Platinum hydrogen evolution reaction (HER) electrocatalysts in the form of nanocubes (NCs) were synthesized at 50 °C by aqueous-based colloidal synthesis and were applied to electrochemical (EC) and photoelectrochemical (PEC) systems by a fast and simple drop-casting method. A remarkable Pt mass activity of 1.77 A mg-1 at -100 mV was achieved in EC systems (fluorine-doped tin oxide/Pt NC cathode) with neutral electrolyte while maintaining low overpotential and Tafel slope. In the Cu(In,Ga)(S,Se)2 (CIGS)-based PEC system, a carefully chosen amount of Pt NC loading to achieve a compromise between the catalytic activity (more Pt NCs) and better light transmittance (fewer Pt NCs) led to a maximum onset potential of 0.678 V against the reference hydrogen electrode. The photoelectrodes with Pt NCs also exhibited good long-term operational stability over 9.5 h with negligible degradation of the photocurrent. This study presents an effective strategy to greatly reduce the use of expensive Pt without compromising the catalytic performance because the drop-casting of Pt NC solutions to form electrocatalysts is expected to waste less raw material than vacuum deposition.

Drop-Casting to Make Efficient Perovskite Solar Cells under High Humidity.

Drop-casting was used to make MAPbI3 films for solar cells. The crystal growth in drop-cast MAPbI3 films was regulated by adjusting temperature. A mechanism for the formation of different morphology was proposed by combining in situ crystal-growth study with XRD measurements. The crystals in the films made at low temperature (60 °C) and high temperature (≥120 °C) are (110) and (200) oriented, respectively. The different crystal growth mode leads to quite different film morphology. Compared with spin-coating, drop-casting shows much better tolerance to humidity. MAPbI3 solar cells made under 88 % humidity delivered a PCE of 18.17 %, which is the highest PCE for perovskite solar cells made under >70 % humidity without antisolvent assistance.