Polymer-confined synthesis of gram-scale high-entropy perovskite fluoride nanocubes for improved electrocatalytic reduction of nitrate to ammonia.

High-entropy perovskite fluoride (HEPF) has gradually attracted attention in the field of electrocatalysis due to its unique properties. Although traditional co-precipitation methods can efficiently produce HEPF, the resulting catalysts often lack regular morphology and tend to aggregate extensively. Here, nanocubic K(CuMgCoZnNi)F3 HEPF (HEPF-2) was successfully prepared on a gram-scale by a polyvinylpyrrolidone (PVP)-confined nucleation strategy. Benefiting from its large electrochemically active surface area and well-exposed active sites, the HEPF-2 demonstrates dramatically enhanced electrocatalytic activity in electrocatalytic nitrate reduction to ammonia, leading to an improved ammonia yield rate (7.031 mg h-1 mgcat.-1), a high faradaic efficiency (92.8%), and excellent long-term stability, outperforming the irregular HEPF nanoparticles (HEPF-0) prepared without the assistance of PVP. Our work presents an efficient and facile method to synthesize perovskite fluorides with a well-defined structure, showing great promise in the field of high-performance electrocatalysis.

An Aerosol-Assisted Chemical Vapor Deposition Route to Tin-Doped Gallium Oxide Thin Films with Optoelectronic Properties.

Gallium oxide is a wide-bandgap compound semiconductor material renowned for its diverse applications spanning gas sensors, liquid crystal displays, transparent electrodes, and ultraviolet detectors. This paper details the aerosol assisted chemical vapor deposition synthesis of tin doped gallium oxide thin films using gallium acetylacetonate and monobutyltin trichloride dissolved in methanol. It was observed that Sn doping resulted in a reduction in the transmittance of Ga2O3 films within the visible spectrum, while preserving the wide bandgap characteristics of 4.8 eV. Furthermore, Hall effect testing revealed a substantial decrease in the resistivity of Sn-doped Ga2O3 films, reducing it from 4.2 × 106 Ω cm to 2 × 105 Ω cm for the 2.5 at. % Sn:Ga2O3 compared to the nominally undoped Ga2O3.

Photobiocidal Activity of TiO2/UHMWPE Composite Activated by Reduced Graphene Oxide under White Light.

Herein, we introduce a photobiocidal surface activated by white light. The photobiocidal surface was produced through thermocompressing a mixture of titanium dioxide (TiO2), ultra-high-molecular-weight polyethylene (UHMWPE), and reduced graphene oxide (rGO) powders. A photobiocidal activity was not observed on UHMWPE-TiO2. However, UHMWPE-TiO2@rGO exhibited potent photobiocidal activity (>3-log reduction) against Staphylococcus epidermidis and Escherichia coli bacteria after a 12 h exposure to white light. The activity was even more potent against the phage phi 6 virus, a SARS-CoV-2 surrogate, with a >5-log reduction after 6 h exposure to white light. Our mechanistic studies showed that the UHMWPE-TiO2@rGO was activated only by UV light, which accounts for 0.31% of the light emitted by the white LED lamp, producing reactive oxygen species that are lethal to microbes. This indicates that adding rGO to UHMWPE-TiO2 triggered intense photobiocidal activity even at shallow UV flux levels.

Transparent Conductive Titanium and Fluorine Co-doped Zinc Oxide Films.

Aerosol-assisted chemical vapor deposition (AACVD) was used to deposit highly transparent and conductive titanium or fluorine-doped and titanium-fluorine co-doped ZnO thin films on glass substrate at 450 °C. All films were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), UV-Vis spectroscopy, scanning electron spectroscopy (SEM), and four-point probe. The films were 600-680 nm thick, crystalline, and highly transparent (80-87 %). The co-doped film consisted of 0.70 at % titanium and 1 at % fluorine, and displayed a charger carrier mobility, charge carrier concentration, and a minimum resistivity of 8.4 cm2 V-1 s-1, 3.97×1020 cm-3, and 1.69×10-3â€…Ω cm, respectively. A band gap of 3.6 eV was observed for the co-doped film. Compared to the undoped and singly doped films, the co-doped film displayed a notably higher structure morphology (more homogenous grains with well-defined boundaries) suitable for transparent conducting oxide applications.

Modification of Commercial Polymer Coatings for Superhydrophobic Applications.

Superhydrophobic surfaces have been studied extensively over the past 25 years. However, many industries interested in the application of hydrophobic properties are yet to find a suitable solution to their needs. This paper looks at the rapid functionalization of nanoparticles and the fabrication of superhydrophobic surfaces with contact angles > 170°. This was achieved by simply mixing commercial products and applying the new formulation with scalable techniques. First, inexpensive and nontoxic superhydrophobic nanoparticles were made by functionalizing nanoparticles with fatty acids in under an hour. A similar methodology was then used to functionalize a commercial polymer coating to express superhydrophobic properties on it by lowering the coating's surface energy. The coating was then applied to a surface by the spray technique to allow for the formation of hierarchical surface structures. By combining the low surface energy with the necessary roughness, the surface was able to express superhydrophobic properties. Both the particles and the surfaces then underwent characterization and functional testing, which, among other things, allowed for clear differentiation between the functionalization properties of the zinc oxide (ZnO) and the silica (SiO2) nanoparticles. This paper shows that suitable superhydrophobic solutions may be found by simple additions to already optimized commercial products.

Visible-Light-Active Iodide-Doped BiOBr Coatings for Sustainable Infrastructure.

The search for efficient materials for sustainable infrastructure is an urgent challenge toward potential negative emission technologies and the global environmental crisis. Pleasant, efficient sunlight-activated coatings for applications in self-cleaning windows are sought in the glass industry, particularly those produced from scalable technologies. The current work presents visible-light-active iodide-doped BiOBr thin films fabricated using aerosol-assisted chemical vapor deposition. The impact of dopant concentration on the structural, morphological, and optical properties was studied systematically. The photocatalytic properties of the parent materials and as-deposited doped films were evaluated using the smart ink test. An optimized material was identified as containing 2.7 atom % iodide dopant. Insight into the photocatalytic behavior of these coatings was gathered from photoluminescence and photoelectrochemical studies. The optimum photocatalytic performance could be explained from a balance between photon absorption, charge generation, carrier separation, and charge transport properties under 450 nm irradiation. This optimized iodide-doped BiOBr coating is an excellent candidate for the photodegradation of volatile organic pollutants, with potential applications in self-cleaning windows and other surfaces.

A Single-Step Route to Robust and Fluorine-Free Superhydrophobic Coatings via Aerosol-Assisted Chemical Vapor Deposition.

Robust fluorine-free superhydrophobic films were produced from a mixture of two fatty acids (stearic acid and palmitic acid), SiO2 nanoparticles, and polydimethylsiloxane. These simple and nontoxic compounds were deposited via aerosol-assisted chemical vapor deposition to provide the rough topography required for superhydrophobicity, formed through island growth of the aggregates. The optimum conditions for well-adhered superhydrophobic films produced films with a highly textured morphology, which possessed a water contact angle of 162 ± 2° and a sliding angle of <5°. Superhydrophobicity was maintained after ultraviolet exposure (14 days at 365 nm), heat treatment (5 h at 300 °C and 5 h at 400 °C), 300 tape peel cycles, and exposure to ethanol and toluene (5 h each).

When It's Heavier: Interfacial and Solvation Chemistry of Isotopes in Aqueous Electrolytes for Zn-ion Batteries.

The electrochemical effect of isotope (EEI) of water is introduced in the Zn-ion batteries (ZIBs) electrolyte to deal with the challenge of severe side reactions and massive gas production. Due to the low diffusion and strong coordination of ions in D2 O, the possibility of side reactions is decreased, resulting in a broader electrochemically stable potential window, less pH change, and less zinc hydroxide sulfate (ZHS) generation during cycling. Moreover, we demonstrate that D2 O eliminates the different ZHS phases generated by the change of bound water during cycling because of the consistently low local ion and molecule concentration, resulting in a stable interface between the electrode and electrolyte. The full cells with D2 O-based electrolyte demonstrated more stable cycling performance which displayed ∼100 % reversible efficiencies after 1,000 cycles with a wide voltage window of 0.8-2.0 V and 3,000 cycles with a normal voltage window of 0.8-1.9 V at a current density of 2 A g-1 .

Transparent and conducting boron doped ZnO thin films grown by aerosol assisted chemical vapor deposition.

ZnO based transparent conducting oxides are important as they provide an alternative to the more expensive Sn : In2O3 that currently dominates the industry. Here, we investigate B-doped ZnO thin films grown via aerosol assisted chemical vapour deposition. B : ZnO films were produced from zinc acetate and triethylborane using either tetrahydrofuran or methanol (MeOH) as the solvent. The lowest resistivity of 5.1 × 10-3 Ω cm along with a visible light transmittance of ∼75-80% was achieved when using MeOH as the solvent. XRD analysis only detected the wurtzite phase of ZnO suggesting successful solid solution formation with B3+ substituting Zn2+ sites in the lattice. Refinement of the XRD patterns showed minimal distortion to the ZnO unit cell upon doping when MeOH was the solvent due to the immiscibility of the [BEt3] solution (1.0 M solution in hexane) in methanol that limited the amount of B going into the films, thus preventing excessive doping.

Robust and durable liquid-repellent surfaces.

Liquid-repellent surfaces, such as superhydrophobic surfaces, superoleophobic surfaces, and slippery liquid-infused surfaces, have drawn keen research interest from the communities engaged in chemical synthesis, interfacial chemistry, surface engineering, bionic manufacturing and micro-nano machining. This is due to their great potential applications in liquid-proofing, self-cleaning, chemical resistance, anti-icing, water/oil remediation, biomedicine, etc. However, poor robustness and durability that notably hinders the real-world applications of such surfaces remains their Achilles heel. The past few years have witnessed rapidly increasing publications that address the robustness and durability of liquid-repellent surfaces, and many breakthroughs have been achieved. This review provides an overview of the recent progress made towards robust and durable liquid-repellent surfaces. First, we discuss the wetting of solid surface and its generally-adopted characterisation methods, and introduce typical liquid-repellent surfaces. Second, we focus on various evaluation methods of the robustness and durability of liquid-repellent surfaces. Third, the recent advances in design and fabrication of robust and durable liquid-repellent surfaces are reviewed in detail. Fourth, we present the applications where these surfaces have been employed in fields like chemistry, engineering, biology and in daily life. Finally, we discuss the possible research perspectives in robust and durable liquid-repellent surfaces. By presenting such state-of-the-art of this significant and fast-developing area, we believe that this review will inspire multidisciplinary scientific communities and industrial circles to develop novel liquid-repellent surfaces that can meet the requirements of various real-world applications.

Production of an EP/PDMS/SA/AlZnO Coated Superhydrophobic Surface through an Aerosol-Assisted Chemical Vapor Deposition Process.

In this study, a superhydrophobic coating on glass has been prepared through a single-step aerosol-assisted chemical vapor deposition (AACVD) process. During the process, an aerosolized precursor containing polydimethylsiloxane, epoxy resin, and stearic acid functionalized Al-doped ZnO nanoparticles was deposited onto the glass at 350 °C. X-ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy showed that the precursor was successfully coated and formed a nano/microstructure (surface roughness: 378.0 ± 46.1 nm) on the glass surface. The coated surface had a water contact angle of 159.1 ± 1.2°, contact angle hysteresis of 2.2 ± 1.7°, and rolling off-angle of 1°, indicating that it was superhydrophobic. In the self-cleaning test of the coated surface at a tilted angle of 20°, it was shown that water droplets rolled and washed out dirt on the surface. The stability tests showed that the surface remained superhydrophobic after 120 h of exposure to ultraviolet (UV) irradiation and even after heat exposure at 350 °C. In addition, the surface was highly repellent to water solutions of pH 1-13. The results showed that the addition of the functionalized nanoparticles into the precursor allowed for the control of surface roughness and provided a simplified single-step fabrication process of the superhydrophobic surface. This provides valuable information for developing the manufacturing process for superhydrophobic surfaces.

Ethyl Zinc ß-Ketoiminates and ß-Amidoenoates: Influence of Precursor Design on the Properties of Highly Conductive Zinc Oxide Thin Films from Aerosol-Assisted Chemical Vapour Deposition.

Highly transparent (>85 %) and conductive (1.086×10-3 â€…Ω cm) zinc oxide thin films have been deposited from specifically selected precursors allowing us to establish a direct correlation between their molecular structure and the optoelectronic properties of the deposited films. Mono-ligated ethyl zinc compounds of varying steric bulk: [EtZn(OC(Me)CH(Me)N(i Pr))]2 (1), [EtZn(OC(OEt)CH(Me)N(i Pr))]2 (2) and [EtZn(OC(OEt)CH(CH3 )N(Dipp))]2 (3) were compared with the related bis-ligated zinc complexes [Zn(OC(Me)CH(Me)N(i Pr))2 ] (4), [Zn(OC(OEt)CH(Me)N(i Pr))2 ] (5) and [Zn(OC(OEt)CH(Me)N(Dipp))2 ] (6). In all cases bulkier ligands resulted in poorer electronic properties of deposited films, whilst all mono-ligated compounds were shown as superior precursors. All complexes were characterised by 1 H and 13 C{1 H} NMR and elemental analysis, with the structure of 6 determined by single crystal X-ray diffraction. Zinc oxide films were deposited from single and dual source (with methanol) reactions of these precursors, and analysed via XRD, XPS and EDX. Optoelectronic properties were investigated through UV/vis spectroscopy and Hall effect measurements, and morphology was examined via SEM. Tauc plots from UV/vis data indicated that Film A showed the lowest band gap of 3.31 eV. Varying the elemental composition of the precursors led to changes in the elemental composition of the resultant films, as well as changes in their structural and optoelectronic properties. Using this approach of precursor design, we have been able to tune single source precursors towards zinc oxide to deposit films with specific properties.

Exploring Equilibria between Aluminium(I) and Aluminium(III): The Formation of Dihydroalanes, Masked Dialumenes and Aluminium(I) Species.

The design of new reductive routes to low oxidation state aluminium (Al) compounds offers the opportunity to better understand redox processes at the metal centre and develop reactivity accordingly. Here, a monomeric AlI compound acts as a stoichiometric reducing agent towards a series of AlIII dihydrides, leading to the formation of new low oxidation state species including symmetric and asymmetric dihydrodialanes, and a masked dialumene. These compounds are formed by a series of equilibrium processes involving AlI , AlII and AlIII species and product formation can be manipulated by fine-tuning the reaction conditions. The transient formation of monomeric AlI compounds is proposed: this is shown to be energetically viable by computational (DFT) investigations and reactivity studies show support for the formation of AlI species. Importantly, despite the potential for the equilibrium mixtures to lead to ill-defined reactivity, controlled reactivity of these low oxidation state species is observed.

Investigations into the structure, reactivity, and AACVD of aluminium and gallium amidoenoate complexes.

Amidoenoate (AME = {ethyl-3-(R-amido)but-2-enoate}) complexes of aluminium and gallium, of the type: [AlCl2(AMER)] R = iPr (1-Al); [AlCl(AMER)2] R = iPr (2-Al), Dip (3-Al); [GaCl2(AMER)] R = iPr (1-Ga) and [GaCl(AMER)2] R = iPr (2-Ga), Dip (3-Ga), have been synthesised (iPr = isopropyl, Dip = 2,6-diisopropylphenyl). The coordination chemistry of these complexes has been studied in relation to precursor suitability. Investigations into the reactivity of the aluminium and gallium amidoenoate complexes involved reactions with hydride sources including alkali metal hydride salts, alkylsilanes, and magnesium hydride species and magnesium(I) dimers. The isolation of alkyl metal amidoenoate precursors including an aluminium hydride amidoenoate, [AlH(AMEDip)2] (4-Al) and dimethyl gallium amidoenoates [GaMe2(AMEDip)] (4-Ga), [GaMe2(AMEiPr)] (5-Ga) concluded the synthetic studies. A selection of the isolated complexes were used as precursors for aerosol assisted chemical vapour deposition (AACVD) at 500 °C. Thin films of either amorphous Al2O3 or Ga2O3 were deposited and subsequently annealed at 1000 °C to improve the materials' crystallinity. The films were characterised by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-visible (UV-vis) spectroscopy and energy dispersive X-ray analysis (EDXA).

Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes via ethyl and amide zinc thioureides.

Ethyl and amide zinc thioureides [L1ZnEt]2 (1), [L1*ZnEt]2 (2) and [L1Zn(N(SiMe3)2)]2 (3) have been synthesised from the equimolar reaction of thiourea ligands (HL1 = iPrN(H)CSNMe2 and HL1* = PhN(H)CSNMe2) with diethyl zinc and zinc bis[bis(trimethylsilyl)amide] respectively. New routes towards heteroleptic complexes have been investigated through reactions of 1, 2 and 3 with ß-ketoiminates (HL2 = [(Me)CN(H){iPr}-CHC(Me)[double bond, length as m-dash]O]), bulky aryl substituted ß-diiminates (HL3 = [(Me)CN(H){Dipp}-CHC(Me)[double bond, length as m-dash]N{Dipp}] (Dipp = diisopropylphenyl) and HL3* = [(Me)CN(H){Dep}-CHC(Me)[double bond, length as m-dash]N{Dep}] (Dep = diethylphenyl)) and donor-functionalised alcohols (HL4 = Et2N(CH2)3OH and HL4* = Me2N(CH2)3OH) and have led to the formation of the heteroleptic complexes [L1*ZnL3*] (5), [L1ZnL4]2 (6), [L1ZnL4*]2 (7), [L1*ZnL4] (8) and [L1*ZnL4*] (9). All complexes have been characterised by 1H and 13C NMR, elemental analysis, and the X-ray structures of HL1*, 1, 2, 6 and 7 have been determined via single crystal X-ray diffraction. Variable temperature 1H, COSY and NOESY NMR experiments investigating the dynamic behaviour of 5, 6 and 7 have shown these molecules to be fluxional. On the basis of solution state fluxionality and thermogravimetric analysis (TGA), alkoxyzinc thioureides 6 and 7 were investigated as single-source precursors for the deposition of the ternary material zinc oxysulfide, Zn(O,S), a buffer layer used in thin film photovoltaic devices. The aerosol-assisted chemical vapour deposition (AACVD) reaction of 7 at 400 °C led to the deposition of the heterodichalcogenide material Zn(O,S), which was confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX), with optical properties investigated using UV/vis spectroscopy, and surface morphology and film thickness examined using scanning electron microscopy (SEM).

Aluminum Amidinates: Insights into Alkyne Hydroboration.

The mechanism of the aluminum-mediated hydroboration of terminal alkynes was investigated using a series of novel aluminum amidinate hydride and alkyl complexes bearing symmetric and asymmetric ligands. The new aluminum complexes were fully characterized and found to facilitate the formation of the (E)-vinylboronate hydroboration product, with rates and orders of reaction linked to complex size and stability. Kinetic analysis and stoichiometric reactions were used to elucidate the mechanism, which we propose to proceed via the initial formation of an Al-borane adduct. Additionally, the most unstable complex was found to promote decomposition of the pinacolborane substrate to borane (BH3), which can then proceed to catalyze the reaction. This mechanism is in contrast to previously reported aluminum hydride-catalyzed hydroboration reactions, which are proposed to proceed via the initial formation of an aluminum acetylide, or by hydroalumination to form a vinylboronate ester as the first step in the catalytic cycle.

Synthetic and Structural Studies of Ethyl Zinc ß-Amidoenoates and ß-Ketoiminates.

A set of heteroleptic ethyl zinc ß-amidoenoates (1, 2) and ß-ketoiminates (3) of the form [LZnEt]2 with varying steric bulk have been synthesised via the reaction of diethylzinc with ß-aminoenoate ligands HL1 and HL2 and ß-ketoimine HL3. These complexes have been characterised via 1H and 13C NMR, mass spectrometry and single-crystal X-ray diffraction, which unambiguously determined all three structures as dimeric species in the solid state. We observe the unusual dimerisation of 1 and 2 through coordination of the central zinc atom to the methine carbon of the second monomer, which gives these complexes high reactivity. The thermal properties of complex 3 are explored via thermal gravimetric analysis (TGA), to investigate their potential as single-source precursors to zinc oxide, which shows that 3 has a significantly lower decomposition temperature as compared to its bis-ligated counterpart [Zn(L3)2], which gives 3 promise as a single-source precursor to zinc oxide.

Applying the Crystalline Sponge Method to Agrochemicals: Obtaining X-ray Structures of the Fungicide Metalaxyl-M and Herbicide S-Metolachlor.

The crystalline sponge method is a technique that provides the ability to elucidate the absolute structure of noncrystalline or hard to crystallize compounds through single-crystal X-ray diffraction by removing the need to obtain crystals of the target compound. In this study the crystalline sponges {[(ZnX2)3(2,4,6-tris(4-pyridyl)-1,3,5-trazine)2].x(solvent)} n (X = I, Br) were used to obtain X-ray structures of the agrochemical active ingredients metalaxyl-M and S-metolachlor. The effect of the temperature used during guest uptake and the influence of changing the host framework ZnX2 nodes on guest encapsulation were investigated. Additionally, three compounds containing chemical fragments similar to those of metalaxyl-M and S-metolachlor (phenylacetaldehyde, N-ethyl-o-toluidine, and methyl phenylacetate) were also encapsulated. This allowed for the effect of guest size on the position that guests occupy within the host frameworks to be examined. The disorder experienced by the guest compounds was documented, and an analysis of the intermolecular host-guest interactions (CH···π and π ···π) used for guest ordering within the host frameworks was also undertaken in this study.

Electrochemical Investigation of Phenethylammonium Bismuth Iodide as Anode in Aqueous Zn2+ Electrolytes.

Despite the high potential impact of aqueous battery systems, fundamental characteristics such as cost, safety, and stability make them less feasible for large-scale energy storage systems. One of the main barriers encountered in the commercialization of aqueous batteries is the development of large-scale electrodes with high reversibility, high rate capability, and extended cycle stability at low operational and maintenance costs. To overcome some of these issues, the current research work is focused on a new class of material based on phenethylammonium bismuth iodide on fluorine doped SnO2-precoated glass substrate via aerosol-assisted chemical vapor deposition, a technology that is industrially competitive. The anode materials were electrochemically investigated in Zn2+ aqueous electrolytes as a proof of concept, which presented a specific capacity of 220 mAh g-1 at 0.4 A g-1 with excellent stability after 50 scans and capacity retention of almost 100%.