Aqueous Precursor Research Articles

Mimicking Axons by Conductive Metal Lines Formed by Photocatalytically Grown Gold

Nanoionic memristive devices based on the field−driven migration of metal cations and oxygen vacancies have gathered high interest in the scientific community for their capability to technically mimic synaptic connections. Less attention has been given to long−range global plasticity in artificial neuronal networks. The aim of our research is to use light−stimulated growth of gold metal lines to technically mimic the growth of long−range axonal connections for neuromorphic computing architectures. For this purpose, we investigate the formation of metal lines by UV−light−stimulus−driven photocatalytic deposition of gold on titanium dioxide layers. In this study, we present a significant contribution that stems from our active involvement in CRC 1461- Neurotronics, a pivotal initiative funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation). Our research falls under Project-ID 434434223 – SFB 1461, within the broader context of Bio-inspired information pathways.0.8-mm wide photoactive titanium dioxide lines are defined by photolithography on a Sodalime glass substrate. We deposited a 70 nm thick titanium dioxide line on a 10 nm thick indium tin oxide adhesion layer by DC sputtering. The substrate was then heat treated for 90 minutes at 400°C and subsequently cooled on a metal plate to achieve the photocatalytically active anatase phase of titanium dioxide [1]. The growth process is conducted in a beaker by reduction from an aqueous gold chloride precursor solution (HAuCl4). In each step of the growth process, the substrate is placed in a beaker containing 15 ml of the precursor. The solution is obtained by dissolving 15 mg of HAuCl4 powder in 60 ml of deionized water. We utilize a UV LED with the peak wavelength of 365 nm and an approximate intensity of 1.8 - 2.7 mW/cm² to illuminate the sample in the beaker. The illumination time and UV intensity are crucial for this dynamic process. Here, we illuminated the sample for 12 hours and refreshed the solution every 2 hours. After each refreshment of the solution, the substrate is washed thoroughly with deionized (DI) water and is dried under nitrogen gas. We analyze the surface properties of grown gold utilizing scanning electron microscopy (SEM) and measure the conductance of the grown lines by applying voltage via the needles of a hard contact probe station.In the first experiments the growth of gold clusters on the surface is observed instead of the homogeneous gold coverage of the photolithographically defined titanium dioxide lines, which are needed for long-range electrical connections. Then, we coincidentally observed that the presence of a scratch on the titanium dioxide line led to the growth of continuous gold lines on the damaged area. Subsequently, deliberate scratches were introduced manually using tweezers, varying in both size and thickness. SEM images depict islands and covered areas, with notable growth observed on the scratched regions. Remarkably, wider scratches exhibit a proportionally increased width of the grown lines, and a uniform line devoid of any gaps is distinctly visible on broader scratches. We observed particle growth on thinner lines. However, unlike the uniform alignment observed in wider scratches, these particles did not coalesce into a continuous line. Instead, they remained separated from each other, exhibiting small gaps between individual particles. The morphological analysis of the grown gold line using SEM reveals a crystalline morphology of particles.As the primary objective of this research is to mimic axons with gold lines, ensuring conductivity is crucial for obtaining long−range electrical connections mimicking axons. To achieve this, voltage was applied using the needles of a hard contact probe station, and the resulting current was measured. The linear behavior observed in the I–V diagram of the wider line serves as a confirmation of its conductance (≈0.003 S).

(Invited) Optical Probes for Resonance-Enhanced Gold Growth on Nanooptical Substrates

We investigate light-stimulated growth of gold metal lines to technically mimic the growth of long-range axonal connections for neuromorphic computing architectures. Photocatalytic gold growth from an aqueous gold chloride precursor solution (HAuCl4) on a photoactive titanium dioxide layer is used. It is known that local gold growth may be obtained by UV illumination through a shadow mask [1]. To obtain a wavelength and angle dependent growth of metal lines – and thus stimulus-dependent resistances – we suggest to employ a nanooptical template. Inspired by the typical number of 2 to 10 connections to a node found, e.g., in the neuronal system of the biological species Hydra, we decided on the implementation of a hexagonal design. The edges are formed by periodic grating nanostructures with 10 to 20 periods and a grating pitch of 170 nm to 210 nm for excitation in the UV. In order to investigate the resonant optical enhancement, we employ optical probes. It is well known that colloidal quantum dots show enhanced fluorescence emission on photonic crystal surfaces due to resonant excitation and resonant outcoupling [2]. In our initial experiments for investigation of the resonant enhancement, we use 4,4’-Bis(2,2-diphenylvinyl)-1,1’-biphenyl (DBVBi) as the emitter material. Its absorption maximum matches the excitation laser at 355 nm and fluorescence in the visible spectrum around 455 nm may be monitored with our camera and spectrometer setup.The nanostructure master was fabricated by electron-beam lithography (Kelvin Nanotechnology Ltd.) according to our design. We transfer the nanostructure pattern onto 1.1 mm thick soda-lime glass substrates by UV-nanoimprint lithography. Subsequently, a 100 nm titanium dioxide layer is deposited. The 150 nm emissive DBVBi layer is then added by thermal evaporation. The samples are characterized optically with a camera setup and magnifying optics on an in-plane rotatable xy-stage. We use a Cobolt Zouk 355 nm 10 mW laser to excite the emissive layer. The output power of the laser is set to 2 mW and its output beam is widened with a collimating lens setup to a diameter of approximately 1.5 mm². The widened beam is essential to obtain a homogeneous excitation. We observe the successful resonant excitation by the higher emission intensity of DPVBi in specific regions of the nanostructure at specific excitation angles. Already for 10 periods of the grating structure resonance effects are observed. A stronger enhancement is obtained for 20 periods. Further, the enhancement depends on the grating pitch as connections with nanograting pitches below 190 nm are no longer visible. They do not meet the criteria for resonant excitation.This method of using optical probes on the nanooptical template works well for initial characterization of the resonance enhancement at different excitation angles. Now the setup is ready for performing gold growth under different excitation conditions. Without the additional emissive layer, the waveguide thickness change needs to be compensated with an increased titanium dioxide layer thickness. For online monitoring of the resonant enhancement during growth optical probes may be employed below the photoactive titanium dioxide layer. It is expected that the resonance enhancement is reduced with the addition of gold due to the increased absorption and thus reduced quality factor as was previously studied in the context of nanostructured OLEDs [3].We acknowledge funding by the DFG (German Research Foundation) with the CRC 1461- Neurotronics (Project-ID 434434223 – SFB 1461).[1] S. Veziroglu et al. (2018). Photocatalytic growth of hierarchical au needle clusters on highly active TiO2 thin film. Advanced Materials Interfaces, 5(15), 1800465.[2] N. Ganesh et al. (2007). Enhanced fluorescence emission from quantum dots on a photonic crystal surface. Nature nanotechnology, 2(8), 515-520.[3] J. Buhl et al. (2023). Resonance‐Based Directional Light Emission from Organic Light‐Emitting Diodes: Comparing Integrated Nanopatterns and Color Conversion Waveguide Gratings. Advanced Photonics Research, 4(2), 2200143. Figure 1. (Left) Fluorescence image of optical probe layer on nanooptical substrate for 355 nm laser excitation. (Middle) Schematic of nanooptical substrate with grating pitch (in nm) and number of periods given. Same colors represent identical grating features. (Right) Field emission scanning electron microscopy (FESEM) image of one node with 6 connections. Figure 1

Electroless Deposition of Noble Metals on Rod-Shape Plant Viruses in Various Aqueous Metal Precursor Solutions.

The challenge of synthesizing noble metal nanostructures sustainably has encouraged researchers to explore biological routes for nanostructure production, such as biotemplating. Plant viruses with rod-shape morphology, such as tobacco mosaic virus (TMV) and barley stripe mosaic virus (BSMV), offer promising biotemplates to produce metal nanorods. TMV and BSMV can be incubated in aqueous metal precursor solutions to mineralize metals on the coat proteins (CPs) of the viruses. Previous studies have primarily examined palladium (Pd) mineralization on TMV and BSMV using Na2PdCl4 as the Pd precursor. There is limited scientific literature on the effect of using alternative Pd precursor solutions besides Na2PdCl4 such as K2PdCl4 and PdCl2 to mineralize Pd on TMV and BSMV. Past attempts at mineralizing other noble metals such as platinum (Pt) and gold (Au) required an initial layer of Pd to be deposited on the TMV and BSMV biotemplates. In this study, we aimed to expand the understanding of using alternative Pd precursor solutions to mineralize Pd on TMV and BSMV. Additionally, the deposition of Pt and Au onto TMV and BSMV without the need for an initial Pd mineralization layer was achieved using alternative Pt and Au precursors, including K2PtCl4 and AuCl3, respectively. Pd, Pt, and Au were successfully deposited on TMV and BSMV by incubation in aqueous solutions of Na2PdCl4, K2PdCl4, PdCl2, K2PtCl4, and AuCl3. Kinetic studies were also conducted using ultraviolet-visible (UV-vis) spectroscopy to examine the rates at which Pd, Pt, and Au precursor ions were reduced during the mineralization process, mimicking their adsorption onto TMV and BSMV CPs. BSMV adsorbed noble metal precursor ions faster than TMV as determined by UV-vis spectroscopy. While palladium nanorods (PdNRs) offer high electrical conductivity desirable for electronic applications, Pd-coated TMV and BSMV may face limitations due to their organic cores, potentially compromising conductivity. To address this, one approach is to convert the organic core into conductive amorphous carbon through thermal annealing. In this study, in situ transmission electron microscopy was utilized to thermally anneal Pd-TMV2Cys, thereby transforming them into PdNRs with amorphous carbon cores.

“Unveiling marigold assembled micro flowers of tungsten oxide towards solid-state flexible pouch and coin cell supercapacitors”

Marigold analogues micro flowers of tungsten oxide (WO3) have been grown in thin film form through simple and cost-effective solution chemistry approach on stainless steel substrate. Aqueous precursor involving WO4-2 ions agglomerated as self-sacrificing template growing initially into the nano-petal, followed by self-assembly; leading to marigold analogues micro flower surface architecture. This enthralling morphology motivated us not only to fabricate supercapacitive electrode but also to design complete solid-state supercapacitor devices in dual configurations: flexible pouch cell and coin cell. Interestingly, both devices even in symmetric configuration yields remarkable potential window of 1.82 V when sandwiched by gel inclusive of Li+ ions dispersed in non-conducting polyvinyl alcohol matrix. Solid-state flexible pouch cell and coin cell delivered specific capacitances of 103.98 ± 3.59 and 30.09 ± 1.03 F/g respectively at a scan rate of 5 mV/s. Assembled electrode, coin-cell and flexible pouch-cells have been well assessed in-depth through specific capacitances using cyclic voltammetry and galvanostatic charge discharge, diffusive and capacitive contributions, mechanical bending tests, electrochemical active surface area, and electrochemical impedance analysis. Practical applicability has been demonstrated for designed flexible pouch cell to run small fan and light emitting diode panel whereas coin cell to run light emitting diode panel.

Particle morphology of alkali metal chloride salts in induction heating based pulsed spray drier: Experimental analysis and ANN prediction

Hygroscopic nature of alkali metal chloride salts makes attaining mono-sized dried particles from their aqueous precursor solution an engineering challenge for conventional co-current or counter-current spray driers. Conventional spray driers offer better thermal utilization in either the spray zone or dried particle zone depending on their configuration viz. co-current or counter-current, respectively. In this work, an alternative prototype named induction heating based pulsed spray drier (IH-PSD) is proposed to obtain dry alkali metal chloride salt powders with narrow particle size distribution. Laser diffraction analysis is carried out for initial droplet size distribution whereas scanning electron microscopy and sieve shaker analysis is carried out for studying the particle morphology and particle size distribution of dried powder for all the selected salts. The resultant particle properties emphasized in the present work are the dried particle to initial droplet diameter ratio and the wet basis moisture content. It has been observed that the ratio of mean volume diameter of dried particle to sauter mean diameter of initial droplet lies in the range of 0.4–3.6 meanwhile the wet basis moisture content of dried powder lies in the range of 1.4–3.6 for the selected salts. Artificial neural network (ANN) model is applied for inferring the influence of IHPSD process parameters on the above mentioned dried particle properties and satisfactory convergence with experimental values has been achieved.

Integrating phase change materials and spontaneous emulsification: In-situ particle formation at oil–water interfaces

The properties of interfaces between two immiscible fluids, as engineered by interfacial materials, are crucial in various processes, including printing, coating, and multiphase flow in porous media. Interfacial materials, such as surface-active molecules and particles can be adsorbed from the bulk fluid phases to the interface or formed in-situ at the interface. In this study, we develop a methodology to form stiff silica-based particles in situ at the oil–water interface through coupling of phase change materials and spontaneous emulsification. This process is demonstrated by introducing a heptane micellar solution that spontaneously generates a microemulsion phase when in contact with an aqueous phase. Micron-sized droplets, consisting of an aqueous silicate precursor mixture, undergo a sol–gel reaction, leading to the generation of colloidal-sized particles. SEM micrographs and confocal images of dried samples, taken from the aqueous-heptane interface, reveal the formation of particles post-gelation. The in-situ formation of stiff particles can be characterized through the dynamics of evaporation, where a significant reduction in the heptane evaporation rate is observed. This particle generation method, utilizing phase change materials and emulsion templates, is spontaneous, energy-efficient, and enables particle formation at the interface at a predetermined time. Our findings offer valuable insights for the fabrication of interfacial materials with tailored properties and controlled timing.

Moldable Tissue-Sealant Hydrogels Composed of In Situ Cross-Linkable Polyethylene Glycol via Thiol-Michael Addition and Carbomers.

Moldable tissue-sealant hydrogels were developed herein by combining the yield stress fluidity of a Carbomer and in situ cross-linking of 3-arm PEG-thiol (PEG-SH) and 4-arm PEG-acrylate (PEG-AC). The Carbomer was mixed with each PEG oligomer to form two aqueous precursors: Carbomer/PEG-SH and Carbomer/PEG-AC. The two hydrogel precursors exhibited sufficient yield stress (>100 Pa) to prevent dripping from their placement on the tissue surface. Moreover, these hydrogel precursors exhibited rapid restructuring when the shear strain was repeatedly changed. These rheological properties contribute to the moldability of these hydrogel precursors. After mixing these two precursors, they were converted from yield-stress fluids to chemically cross-linked hydrogels, Carbomer/PEG hydrogel, via thiol-Michael addition. The gelation time was 5.0 and 11.2 min at 37 and 25 °C, respectively. In addition, the Carbomer/PEG hydrogels exhibited higher cellular viability than the pure Carbomer. They also showed stable adhesiveness and burst pressure resistance to various tissues, such as the skin, stomach, colon, and cecum of pigs. The hydrogels showed excellent tissue sealing in a cecum ligation and puncture model in mice and improved the survival rate due to their tissue adhesiveness and biocompatibility. The Carbomer/PEG hydrogel is a potential biocompatible tissue sealant that surgeons can mold. It was revealed that the combination of in situ cross-linkable PEG oligomers and yield stress fluid such as Carbomer is effective for developing the moldable tissue sealant without dripping of its hydrogel precursors.

Strength Increase of Alumina Foams by a Sodium Aluminosilicate Glass Coating with Subsequent Na+ ↔ K+ Ion Exchange (Gorilla Glass Coating)

Reticulated alumina ceramic foams manufactured by the Schwartzwalder technique are coated with a sodium aluminosilicate glass using an aqueous precursor containing alumina particles and sodium silicate. After a heat treatment, a well‐adhering glass layer with a thickness between 10 and 120 μm is obtained. Besides the strut surface, the glass phase also penetrates the hollow strut cavities as well as strut cracks. The total porosity of the glass‐coated foams is between 88% and 90%, and the open cellular structure is not negatively affected by the glass coating. The compressive strength increases by a factor of two under consideration of the decrease in total porosity; a compressive strength in the order of magnitude of 2 MPa is feasible. An ion exchange of Na+ by K+ into the glass coating layer (chemical strengthening) is successfully demonstrated, but does not result in an additional improvement of the compressive strength.

Fabrication of conductive Nb-doped anatase TiO2 thin films by mist chemical vapor deposition using aqueous solutions of water-soluble Ti and Nb compounds

Electrically conductive Nb-doped anatase TiO2 (Ti1−x Nb x O2: TNO) films can be fabricated through mist CVD using aqueous precursor solutions of water-soluble oxo-peroxo-glycolato titanium complex and ammonium niobium oxalate. Post-deposition annealing in vacuum crystallizes the as-deposited amorphous films into a conductive anatase phase, leading to the fabrication of conductive TNO films. Notably, the addition of H2O2 to the precursor solutions enhances both the crystallinity and conductivity of the annealed TNO films. A Ti0.77N0.23O2 film, annealed at 700 °C, exhibits a resistivity of 2.0 × 10−2 Ω cm at ambient temperature. In general, the solution-based fabrication of TiO2 films relies on organic solvents, which are sometimes toxic and explosive. Here, we demonstrate for the first time that conductive TNO films can be prepared from less toxic and nonflammable aqueous solutions. These findings mark a significant advancement towards a more environmentally compatible process for fabricating TNO films with sufficient conductivity.

The Chemistry of Spinel Ferrite Nanoparticle Nucleation, Crystallization, and Growth.

The nucleation, crystallization, and growth mechanisms of MnFe2O4, CoFe2O4, NiFe2O4, and ZnFe2O4 nanocrystallites prepared from coprecipitated transition metal (TM) hydroxide precursors treated at sub-, near-, and supercritical hydrothermal conditions have been studied by in situ X-ray total scattering (TS) with pair distribution function (PDF) analysis, and in situ synchrotron powder X-ray diffraction (PXRD) with Rietveld analysis. The in situ TS experiments were carried out on 0.6 M TM hydroxide precursors prepared from aqueous metal chloride solutions using 24.5% NH4OH as the precipitating base. The PDF analysis reveals equivalent nucleation processes for the four spinel ferrite compounds under the studied hydrothermal conditions, where the TMs form edge-sharing octahedrally coordinated hydroxide units (monomers/dimers and in some cases trimers) in the aqueous precursor, which upon hydrothermal treatment nucleate through linking by tetrahedrally coordinated TMs. The in situ PXRD experiments were carried out on 1.2 M TM hydroxide precursors prepared from aqueous metal nitrate solutions using 16 M NaOH as the precipitating base. The crystallization and growth of the nanocrystallites were found to progress via different processes depending on the specific TMs and synthesis temperatures. The PXRD data show that MnFe2O4 and CoFe2O4 nanocrystallites rapidly grow (typically <1 min) to equilibrium sizes of 20-25 nm and 10-12 nm, respectively, regardless of applied temperature in the 170-420 °C range, indicating limited possibility of targeted size control. However, varying the reaction time (0-30 min) and temperature (150-400 °C) allows different sizes to be obtained for NiFe2O4 (3-30 nm) and ZnFe2O4 (3-12 nm) nanocrystallites. The mechanisms controlling the crystallization and growth (nucleation, growth by diffusion, Ostwald ripening, etc.) were examined by qualitative analysis of the evolution in refined scale factor (proportional to extent of crystallization) and mean crystallite volume (proportional to extent of growth). Interestingly, lower kinetic barriers are observed for the formation of the mixed spinels (MnFe2O4 and CoFe2O4) compared to the inverse (NiFe2O4) and normal (ZnFe2O4) spinel structured compounds, suggesting that the energy barrier for formation may be lowered when the TMs have no site preference.

Copper-Enriched Nanostructured Conductive Thermoelectric Copper(I) Iodide Films Obtained by Chemical Solution Deposition on Flexible Substrates

The objects of our research are flexible thin-film thermoelectric materials with nanostructured CuI layers 0.5–1.0 μm thick, fabricated by the chemical solution method Successive Ionic Layer Adsorption and Reaction (SILAR) on flexible polyethylene terephthalate and polyimide substrates. These cubic γ-CuI films differ from films obtained by other chemical solution methods, such as spin-coating, sputtering, and inject printing, in their low resistivity due to acceptor impurities of sulfur and oxygen introduced into CuI from aqueous precursor solutions during SILAR deposition. Energy barriers at the boundaries of 18–22 nm CuI nanograins and a large number of charge carriers inside the nanograins determine the transport properties in the temperature interval 295–340 K characterized by transitions from semiconductor to metallic behavior with increasing temperature, which are typical of nanostructured degenerate semiconductors. Due to the resistivity of about 0.8 mΩ· m at 310 K and the Seebeck coefficient 101 μV/K, the thermoelectric power factor of the CuI film 1.0 μm thick on the polyimide substrate is 12.3 μW/(m · K2), which corresponds to modern thin-film p-type thermoelectric materials. It confirms the suitability of CuI films obtained by the SILAR method for the fabrication of promising inexpensive non-toxic flexible thermoelectric materials.

Exploration of anion effects in solvothermal synthesis using in situ X-ray diffraction.

Solvothermal synthesis presents a facile and highly flexible approach to chemical processing and it is widely used for preparation of micro- and nanosized inorganic materials. The large number of synthesis parameters in combination with the richness of inorganic chemistry means that it is difficult to predict or design synthesis outcomes, and it is demanding to uncover the effect of different parameters due to the sealed and complex nature of solvothermal reactors along with the time demands related to reactor cleaning, sample purification, and characterization. This study explores the effect on formation of crystalline products of six common anions in solvothermal treatment of aqueous and ethanolic precursors. Three different cations are included in the study (Mn2+, Co2+, Cu2+) representing chemical affinities towards different regions of the periodic table with respect to the hard soft acid base (HSAB) classification and the Goldschmidt classification. They additionally belong to the commonly used 3d transition metals and display a suitable variety in solvothermal chemistry to highlight anion effects. The results of the solvothermal in situ experiments demonstrate a clear effect of the precursor anions, with respect to whether crystallization occurs or not and the characteristics of the formed phases. Additionally, some of the anions are shown to be redox active and to influence the formation temperature of certain phases which in turn relates to the observed average crystallite sizes.

Low hysteresis zwitterionic supramolecular polymer ion-conductive elastomers with anti-freezing properties, high stretchability, and self-adhesion for flexible electronic devices.

The fabrication of stretchable ionic conductors with low hysteresis and anti-freezing properties to enhance the durability and reliability of flexible electronics even at low temperatures remains an unmet challenge. Here, we report a facile strategy to fabricate low hysteresis, high stretchability, self-adhesion and anti-freezing zwitterionic supramolecular polymer ion-conductive elastomers (ICEs) by photoinitiated polymerization of aqueous precursor solutions containing a newly designed zwitterionic monomer carboxybetaine ureido acrylate (CBUIA) followed by solvent evaporation. The resultant poly(carboxybetaine ureido acrylate) (PCBUIA) ICEs are highly stretchable and self-adhesive owing to the presence of strong hydrogen bonds between ureido groups and dipole-dipole interactions of zwitterions. The zwitterion groups on the polymer side chains and loaded-lithium chloride endow PCBUIA ICEs with excellent anti-freezing properties, demonstrating mechanical flexibility and ionic transport properties even at a low temperature (-20 °C). Remarkably, the PCBUIA ICEs demonstrate a low hysteresis (≈10%) during cyclic mechanical loading-unloading (≤500%), and are successfully applied as wearable strain sensors and triboelectric nanogenerators (TENGs) for energy harvesting and human motion monitoring. In addition, the PCBUIA ICE-based TENG was used as a wireless sensing terminal for Internet of Things smart devices to enable wireless sensing of finger motion state detection.

Aqueous Solution-Gel Deposition of Copper-Based Photo-Electrodes for Multipurpose Photo-Electrochemical Systems

Efficient valorization of solar energy is expected to contribute significantly to a sustainable supply of energy and fuel sources, as well as the reduction of atmospheric pollution. To this end, photo-electrochemical systems show encouraging potential by converting light into chemical energy. These devices rely on semiconducting photoanodes and/or -cathodes that absorb light efficiently and generate electron-hole pairs with sufficient energy for initiating redox reactions. Several copper-based oxides exhibit appropriate band edges for both photo-electrochemical water splitting and CO2 reduction [1]. This, in combination with their bandgap values, low toxicity, and earth-abundance, has recently increased the attention for copper-based photo-electrodes for multipurpose photo-electrochemical systems. Substantial photocorrosion of CuO and Cu2O is the main issue restricting their application as functional photo-electrodes. In contrast, copper-based ternary oxides are found to be significantly less susceptible to photocorrosion. The citrate-based aqueous solution-gel method has proven to be a versatile approach for the formulation of stable aqueous metal ion precursor solutions, and the subsequent synthesis of (doped) multi-metal oxides by this method has been demonstrated numerously. [2,3] Still, due to the flexible redox chemistry of copper, the solution-gel synthesis of phase-pure copper-based ternary oxides remains challenging. This work describes the synthesis of copper-based photo-electrode materials by focusing on copper ferrite (CFO), copper tungstate (CWO), copper niobate (CNO), and copper bismuth oxide (CBO). The formulation of the respective precursor solutions is described, and their thermal decomposition is investigated. Thin-film photo-electrodes are deposited on transparent conductive substrates by spin coating. The phase purity of the resulting copper-based oxides is determined by X-ray diffraction and Raman spectroscopy. Using UV-Vis spectroscopy, the optical bandgap of the oxide semiconductors is calculated. Furthermore, the photo-electrodes are subjected to linear sweep voltammetry in dark and under illumination to evaluate their photo-electrochemical performance. [1] Wang et al. “Insights into the development of Cu-based photocathodes for carbon dioxide conversion” Green Chem. (2021) 23, 3207[2] Van den Rul et al. “Aqueous Solution-Based Synthesis of Nanostructured Metal Oxides” in “Handbook of Nanoceramics and Their Based Nanodevices” (2009) Ed. T-Y Tseng and H. S. Nalwa[3] Marchal et al. “Precursor Design Strategies for the Low-Temperature Synthesis of Functional Oxides: It’s All in the Chemistry” Chem. Eur. J. (2020) 26, 9070 This work has received funding from the Belgian federal government through the ETF project T-REX and from the VLAIO network “Flanders Innovation & Entrepreneurship” through the Catalisti Moonshot project SYN-CAT. Part of this work was financially supported by TNO in the framework of the “Energy Conversion and Storage” Early Research Program.

Solution-Processed Non-Crystalline Solid Electrolytes for Advanced Energy Storage

Advanced batteries containing a Li metal anode (LMA) are needed to enable the clean economy and meet ambitious climate targets. Currently, LMA batteries are limited by dendrite propagation due to the non-uniform plating and stripping of Li, which is detrimental to cell performance. The non-crystalline solid electrolyte (SE), lithium phosphorus oxynitride (LiPON) is unique in demonstrating stable Li plating/stripping at appreciable rates, but its synthesis requires costly and slow vacuum deposition methods. We use aqueous precursor solutions which are rapidly condensed during spin coating and gently annealed to produce dense, flat, Li metal oxide films without long-range order. However, such solution-processed SEs typically exhibit ionic conductivities (σ ion ) too low for energy storage applications (~10-8 S cm-1) and far lower than vacuum-deposited LiPON (~10-6 S cm-1).We will discuss various approaches to increase the σion of these materials, including compositional engineering and controlled processing conditions. Structure-property relationships have been elucidated using modelling of the local structure and interphase formation against Li evaluated by time-dependent electrochemical impedance spectroscopy and in situ X-ray photoelectron spectroscopy. Electrochemical testing of these films deposited onto a current collector in an anode-free cell will be used to evaluate their ability to facilitate stable deposition and stripping of Li.Initial exploration of processing parameters have yielded σion values > 10-7 S cm-1 [1] and the presence of medium-range order (nanocrystalline domains) in some cases. Beyond Li, new non-crystalline SEs for other ions will be discussed. As only limited chemical compositions and processing conditions of these materials have been reported, with no corresponding structural studies, our work provides insight to enable the optimisation and discovery of scalable non-crystalline SEs for advanced batteries.1. P. Vadhva, T. Gill, J. H. Cruddos, S. Said, M. Siniscalchi, S. Narayanan, M. Pasta, T.S. Miller, A.J.E. Rettie. Engineering solution-processed non-crystalline solid electrolytes for Li metal batteries. Chemistry of Materials, 2022, 35, 3, 1168–1176.

Growth and Dispersion Control of SnO2 Nanocrystals Employing an Amino Acid Ester Hydrochloride in Solution Synthesis: Microstructures and Photovoltaic Applications.

Tin oxide (SnO2) is a technologically important semiconductor with versatile applications. In particular, attention is being paid to nanostructured SnO2 materials for use as a part of the constituents in perovskite solar cells (PSCs), an emerging renewable energy technology. This is mainly because SnO2 has high electron mobility, making it favorable for use in the electron transport layer (ETL) in these devices, in which SnO2 thin films play a role in extracting electrons from the adjacent light-absorber, i.e., lead halide perovskite compounds. Investigation of SnO2 solution synthesis under diverse reaction conditions is crucial in order to lay the foundation for the cost-effective production of PSCs. This research focuses on the facile catalyst-free synthesis of single-nanometer-scale SnO2 nanocrystals employing an aromatic organic ligand (as the structure-directing agent) and Sn(IV) salt in an aqueous solution. Most notably, the use of an aromatic amino acid ester hydrochloride salt-i.e., phenylalanine methyl ester hydrochloride (denoted as L hereafter)-allowed us to obtain an aqueous precursor solution containing a higher concentration of ligand L, in addition to facilitating the growth of SnO2 nanoparticles as small as 3 nm with a narrow size distribution, which were analyzed by means of high-resolution transmission electron microscopy (HR-TEM). Moreover, the nanoparticles were proved to be crystallized and uniformly dispersed in the reaction mixture. The environmentally benign, ethanol-based SnO2 nanofluids stabilized with the capping agent L for the Sn(IV) ions were also successfully obtained and spin-coated to produce a SnO2 nanoparticle film to serve as an ETL for PSCs. Several SnO2 ETLs that were created by varying the temperature of nanoparticle synthesis were examined to gain insight into the performance of PSCs. It is thought that reaction conditions that utilize high concentrations of ligand L to control the growth and dispersion of SnO2 nanoparticles could serve as useful criteria for designing SnO2 ETLs, since hydrochloride salt L can offer significant potential as a functional compound by controlling the microstructures of individual SnO2 nanoparticles and the self-assembly process to form nanostructured SnO2 thin films.

CuO/ZnO catalysts in chitosan film for CO2 reduction

In this work, ZnO of 1.1 and 10.2 nm sizes, respectively, were synthesized by irradiating femtosecond pulse laser in aqueous Zn ion precursor solutions at pH 5.5 and 10.2 in comparison with ZnO of 18.1 nm size prepared by hydrothermal procedure in an alkaline condition. The 12.8 nm CuO synthesized by precipitation method was physically mixed with ZnO, and the nanocomposites were embedded in chitosan (CS) film. Based on the catalytic activity of CuO/ZnO nanocomposite in CS film, the photocatalysis was performed for CO2 gas adsorbed on amine group in CS acting as a CO2 absorber. On the photocatalytic reaction under UV irradiation, the production of methanol was quantified using a chromogenic reagent, sodium nitroprusside. The highest catalytic activity (5642 μmol/g(catalyst)) for the CO2 conversion was achieved on CuO/ZnO/CS film, where ZnO was synthesized at pH 10.2 by femtosecond laser irradiation. The energy level alignment profile proposed the best hole transition from ZnO to CuO on CuO/ZnO/CS film in consistence with the best catalytic activity. Then the ecofriendly film-type system consisting of CS will be focused as promising biocompatible reactors because of facile production procedure and easy catalytic treatment.

PARTICLE MORPHOLOGY AND PHASE COMPOSITIONS OF COPT AND COPD NANOSTRUCTURED SYSTEMS IN THE REGIONS RICH IN PRECIOUS METALS

The morphology of nanoparticles, structural-phase properties, and phase transformations that occur during heating in the nanostructured CoPt and CoPd systems rich in precious metals, obtained by co-reduction of aqueous precursor solutions by hydrazine hydrate, were studied by X-ray diffraction and X-ray structural analysis, small-angle X-ray scattering, and high-resolution transmission electron microscopy. The results obtained are of interest for the development of the fundamentals of materials science of bimetallic nanoalloys, and provide a key to understand the processes of the formation of FePt, CoPt and FePd nanoalloys while heating intermetallic compounds with a highly ordered structure L10, which possess record-setting magnetic and magneto-optical properties.

Photoinitiated chemical vapor deposition (piCVD) of composition tunable, ionically conductive hydrogels on diverse substrates

Ionically conductive hydrogels are finding prominence in a wide range of emerging devices and applications, including biopotential sensors, organic field effect transistors, biomedicine, and soft robotics. Traditionally, these gels are synthesized through solution-phase polymerization or solvent based swelling of a polymer network and then cast in place or adhered to an intended substrate after synthesis. These fabrication approaches place artificial limitations on the accessible chemical composition and ionic conductivity of the gels, and limit deployment of ionically conductive hydrogels in complex platforms. Here we present a modular method to create ionically conductive hydrogels on a variety of rigid, flexible, or filamentary substrates through a photoinitiated chemical vapor deposition (piCVD) process. First, a viscosity tunable precursor mixture of desired ionic composition and strength is created and coated onto a target substrate. Next, an acrylate film is grown directly on these coated substrates via piCVD. Since both the monomer and photoinitiator used during the piCVD process are miscible in the aqueous precursor mixture, polymerization occurs at both the surface of and within the precursor layer. Using this two-step strategy, we isolate a robust composite hydrogel with independently tunable ionic properties and physical structure. This method is compatible with most substrates and results in a conformal, persistent gel coating with excellent rehydration properties. Gels containing a variety of biocompatible salts can be accessed, without concomitant changes in physical structure and morphology. Ionic conductivities can be tuned between 1 × 10−5–0.03 S cm−1 by changing the ionic strength of the precursor mixture. Additionally, we show that the material retains its ion concentration and conductivity after washing. Finally, we deploy this material onto several different substrates and show that through this method the same gel can be manufactured in-place regardless of the intended substrate.

Highly nonlinear optic nucleic acid thin-solid film to generate short pulse laser

Using aqueous precursors, we report successfully fabricating thin-solid films of two nucleic acids, ribonucleic acid (RNA) and deoxyribonucleic acid (DNA). We investigated the potential of these films deposited on a fiber optic platform as all-fiber integrated saturable absorbers (SAs) for ultrafast nonlinear optics. RNA-SA performances were comparable to those of DNA-SA in terms of its nonlinear transmission, modulation depth, and saturation intensity. Upon insertion of these devices into an Erbium-doped fiber ring-laser cavity, both RNA and DNA SAs enabled efficient passive Q-switching operation. RNA-SA application further facilitated robust mode-locking and generated a transform-limited soliton pulse, exhibiting a pulse duration of 633 femtoseconds. A detailed analysis of these pulsed laser characteristics compared RNA and DNA fiber optic SAs with other nonlinear optic materials. The findings of this research establish the feasibility of utilizing RNA as a saturable absorber in ultrafast laser systems with an equal or higher potential as DNA, which presents novel possibilities for the nonlinear photonic applications of nucleic acid thin solid films.