Acetylacetonate Precursors Research Articles

Fluidized Bed Chemical Vapor Deposition of Copper on Micronic Alumina Powders

AbstractUniformly coating micronic particles with metals is of main interest for a broad range of applications. This study demonstrates the feasibility of depositing pure copper on the surface of micronic alumina particles by the fluidized bed chemical vapor deposition process from the cheap and nontoxic copper acetylacetonate precursor. Thanks to the development of a preconditioning protocol, a complete fluidization of the particles organized as porous agglomerates was reached. The coating of the individual particles was favored by using conditions involving low deposition rates. The influence of key operating parameters on the process behavior and on the characteristics of the deposit was studied. The deposited copper was of cubic crystal structure without carbon nor oxide contamination.

New solvothermal flow synthesis of strontium titanate nanoparticles based on the use of acetylacetonate precursors in water/ethanol mixture

In this study, strontium titanate (SrTiO3) nanoparticles were obtained utilizing a one-step supercritical continuous solvothermal synthesis process involving acetylacetonate precursors for both strontium and titanium cations instead of the historical alkoxide ones. These precursors are expensive, difficult to access (especially for strontium isopropoxyde) and inadequately stable, forcing the use of a glove box and controlled atmospheres, which is not the case for acetylacetonates. Pure SrTiO3 nanoparticles with a crystallite size of roughly 20 nm were successfully synthesized. In addition to the cubic structure of SrTiO3, FTIR revealed surface functions that are typical of "wet" processes, while Raman spectroscopy showed the activation of non-centrosymmetric modes brought on by non-linear contributions. The nanoparticles show a faceted shape and are stable at elevated temperatures (up to 800 °C), according to in-situ high temperature XRD measurements. However, due to a chemical deficiency in strontium, titanium dioxide (TiO2) phases are formed at higher temperatures. In-situ high temperature HRTEM investigations showed the existence of two populations of particles, with a better stability for the bigger-sized particles after thermal treatment as well as the sintering and restructuring of the smallest ones. Also, the microscopy results suggest the possibility of a chemical inhomogeneity within the crystallites. Overall, this study offers important new knowledge on the physicochemical characteristics of the synthesized SrTiO3 nanoparticles and their thermal stability using a novel supercritical continuous solvothermal approach based on the use of acetylacetonate precursors.

Solvent‐Less Synthesis of Compositionally Tuned Mixed Metal (Ni−Zn) Ferrites for Enhanced Electrocatalytic Water Splitting and Supercapacitance

AbstractExploring efficient, abundant, economical and stable materials for sustainable energy applications, such as electrochemical water splitting and supercapacitance, is a challenging task. Mixed transition metal spinel ferrites can rationally be customized to attain these features and deliver enhanced electrochemical activity. The catalytic performance of spinels is remarkably influenced by tuning the cationic occupancy at the tetrahedral or octahedral position. Herein, a set of spinel Ni1‐xZnxFe2O4 (0≤x≤1) nanocomposites were obtained via a scalable solventless thermolysis of metal acetylacetonate precursors at relatively mild temperatures. A suite of techniques such as powder p‐XRD, EDX, SEM, TEM, HRTEM, and SAED were employed to confirm the formation of the Ni−Zn ferrite solid solutions. It was found that small amounts of Ni at tetrahedral sites were beneficial for charge storage and hydrogen evolution. For instance, Ni0.2Zn0.8Fe2O4 nanocomposite demonstrated superior HER activity with a much lower overpotential of 87 mV compared to the pristine NiFe2O4 (213 mV) or ZnFe2O4 (164 mV) catalysts. However, Ni‐occupied tetrahedral sites were not suitable for OER, whereby the pristine ZnFe2O4 displayed high catalytic activity with an overpotential of 330 mV, outperforming other electrode compositions. The study helps to identify suitable compositions and site tuning for HER, OER and supercapacitors.

Chemical engineering of cationic distribution in spinel ferrite nanoparticles: the effect on the magnetic properties.

A set of ∼9 nm CoFe2O4 nanoparticles substituted with Zn2+ and Ni2+ was prepared by thermal decomposition of metallic acetylacetonate precursors to correlate the effects of replacement of Co2+ with the resulting magnetic properties. Due to the distinct selectivity of these cations for the spinel ferrite crystal sites, we show that it is possible to tailor the magnetic anisotropy, saturation magnetization, and interparticle interactions of the nanoparticles during the synthesis stage. This approach unlocks new possibilities for enhancing the performance of spinel ferrite nanoparticles in specific applications. Particularly, our study shows that the replacement of Co2+ by 48% of Zn2+ ions led to an increase in saturation magnetization of approximately 40% from ∼103 A m2 kg-1 to ∼143 A m2 kg-1, whereas the addition of Ni2+ at a similar percentage led to an ∼30% decrease in saturation magnetization to 68-72 A m2 kg-1. The results of calculations based on the two-sublattice Néel model of magnetization match the experimental findings, demonstrating the model's effectiveness in the strategic design of spinel ferrite nanoparticles with targeted magnetic properties through doping/inversion degree engineering.

Combinative solution processing and Li doping approach to develop p-type NiO thin films with enchanced electrical properties

The deposition of nickel oxide (NiOx) thin film from an acetylacetonate source using many solution-based techniques has been avoided owing to its poor solubility in alcohol solvents. From this perspective, this work provides a systematic investigation of the development of NiOx thin film, using a combinative approach of ultrasonic spray pyrolysis (USP) and Li dopant for the synthesis and optimization of structural and optoelectronic properties of the films. An in-depth comparative analysis of nickel acetylacetonate-based precursor, employing acetonitrile and methanol as solvents, is provided. It is demonstrated that USP from acetylacetonate precursor yielded uniform, well-compact, and transparent films, with polycrystalline cubic NiOx crystal structures. By screening the deposition temperature in the range of 300–450°C, a temperature of 400°C was identified as an optimal processing temperature leading to uniform, compact, highly transparent, and p-type conductive films. At optimized deposition conditions (400°C), lithium-doped NiOx (Li:NiOx) thin film was deposited. The shift of the main (200) XRD peak position from 43.48° (0-Li:NiOx) to 43.56° (60-Li:NiOx) indicated Li incorporation into the NiOx lattice. An X-ray photoelectron spectroscopy (XPS) study was employed to unravel the incorporation of Li into the deposited Li:NiOx thin films. With the deconvolution of the Ni 2p core level for the as-deposited (0, 60)-Li:NiOx films, the intensity of Ni3+ related peak was found to increase slightly with Li doping. Furthermore, all the deposited Li:NiOx thin films showed p-type conductivity behavior, and the resistivity was reduced from 104 Ωcm (0-Li:NiOx) to 102 Ωcm (60-Li:NiOx). Based on these results, the deposited NiOx and Li:NiOx thin films suggested that USP-deposited Li:NiOx is highly suitable for application in inverted structure solar cells as the hole transport layer.

BaTiO3/NixZn1−xFe2O4 (x = 0, 0.5, 1) Composites Synthesized by Thermal Decomposition: Magnetic, Dielectric and Ferroelectric Properties

To investigate the influence of spinel structure and sintering temperature on the functional properties of BaTiO3/NixZn1−xFe2O4 (x = 0, 0.5, 1), NiFe2O4, ZnFe2O4, and Ni0.5Zn0.5Fe2O4 were in situ prepared by thermal decomposition onto BaTiO3 surface from acetylacetonate precursors. As-prepared powders were additionally sintered at 1150 °C and 1300 °C. X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) coupled with electron dispersive spectroscopy (EDS) were used for the detailed examination of phase composition and morphology. The magnetic, dielectric, and ferroelectric properties were investigated. The optimal phase composition in the BaTiO3/NiFe2O4 composite, sintered at 1150 °C, resulted in a wide frequency range stability. Additionally, particular phase composition indicates favorable properties such as low conductivity and ideal-like hysteresis loop behavior. The favorable properties of BaTiO3/NiFe2O4 make this particular composite an ideal material choice for further studies on applications of multi-ferroic devices.

Ligand Decomposition during Nanoparticle Synthesis: Influence of Ligand Structure and Precursor Selection.

Aliphatic amine and carboxylic acid ligands are widely used as organic solvents during the bottom-up synthesis of inorganic nanoparticles (NPs). Although the ligands' ability to alter final NP properties has been widely studied, side reactivity of these ligands is emerging as an important mechanism to consider. In this work, we study the thermal decomposition of common ligands with varying functional groups (amines and carboxylic acids) and bond saturations (from saturated to polyunsaturated). Here, we investigate how these ligand properties influence decomposition in the absence and presence of precursors used in NP synthesis. We show that during the synthesis of inorganic chalcogenide NPs (Cu2ZnSnS4, Cu x S, and SnS x ) with metal acetylacetonate precursors and elemental sulfur, the ligand pyrolyzes, producing alkylated graphitic species. Additionally, there was less to no ligand decomposition observed during the sulfur-free synthesis of ZnO and CuO with metal acetylacetonate precursors. These results will help guide ligand selection for NP syntheses and improve reaction purity, an important factor in many applications.

In Situ Observation of ZnO Nanoparticle Formation by a Combination of Time-Resolved X-ray Absorption Spectroscopy and X-ray Diffraction.

The formation of ZnO nanomaterials from different Zn acetylacetonate precursor solutions was studied in situ by employing simultaneous, time-resolved X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS) at the Zn K-edge. The precursor solutions were heated from room temperature to the desired reaction temperatures in a hermetically sealed cell dedicated to X-ray experiments. In general, the first indications for the formation of hexagonal ZnO were found for elevated temperatures of about 80 °C both by XRD and EXAFS, and the contributions increase with temperature and time. However, no reaction intermediates could be proved in addition to the Zn precursors and the formed hexagonal ZnO materials. Furthermore, the results show that the efficiency of the reaction, i.e., the conversion of the precursor material to the ZnO product, strongly depends on the solvent used and the reaction temperature. ZnO formation is accelerated by an increased temperature of 165 °C and the use of 1-octanol, with a conversion to ZnO of more than 80% after only a ca. 35 min reaction time according to a detailed analysis of the EXAFS data. For comparison, an identical concentration of Zn acetylacetonate in water or dilute alkaline NaOH solutions and a reaction temperature of around 90 °C leads to a smaller conversion of approximately 50% only, even after several hours of reaction. The particle size determined from XRD for different orientations shows a preferred orientation along the c-direction of the hexagonal crystal system, as well in accordance with scanning electron microscopy. The LaMer model explained this highly non-uniform growth of needle-like ZnO crystallites.

Efficient sunlight promoted nitrogen fixation from air under room temperature and ambient pressure via Ti/Mo composites

Photocatalytic nitrogen fixation is an important pathway for carbon neutralization and sustainable development. Inspired by nitrogenase, the participation of molybdenum can effectively activate nitrogen. A novel Ti/Mo composites photocatalyst is designed by sintering the molybdenum acetylacetonate precursor with TiO2. The special carbon-coated hexagonal photocatalyst is obtained which photocatalytic nitrogen fixation performance is enhanced 16 times compared to pure TiO2 at room temperature and ambient pressure. The abundant surface defects in this composite were confirmed to be the key factor for nitrogen fixation. The 15N2 isotope labeling experiment was used to demonstrate the feasibility of nitrogen to ammonia conversion. Also, modelling on the interactions between light and the synthesized photocatalyst particle was examined for the light absorption. The optimum nitrogen fixation conditions have been examined, and the nitrogen fixation performance can reach up to 432 μg·gcat-1·h−1. Numerical simulations via the field-only surface integral method were also carried out to study the interactions between light and the photocatalytic particles to further confirm that it can be a useful material for photocatalyst. This newly developed Ti/Mo composites provide a simple and effective strategy for photocatalytic nitrogen fixation from air directly under ambient conditions.

Film growth mechanism of mist-chemical-vapor-deposited magnetite

Crystal growth techniques using mist precursors, such as mist chemical vapor deposition (mist CVD), are useful for growing epitaxial thin films of various functional oxides under non-vacuum conditions and at relatively low temperatures. Their growth mechanism remains elusive, however, so we developed a home-made reaction chamber for mist CVD and investigated the epitaxial growth mechanism of magnetite Fe3O4 using alcoholic mists of iron acetylacetonate precursors. We show here that grown epitaxial films’ structural and physical properties depend on mist flow rates (or N2 carrier gas flow rates). Increasing the mist flow and promoting mists’ reactions on substrate surfaces produce Fe3O4 epitaxial films having larger magnetizations and lower electrical resistivities and exhibiting the Verwey transition. We also show that films’ properties are modified by changing either water additive concentrations in alcoholic mist solutions or the distance (the joint pipe length) between the mist bottle and the reaction chamber. Our results highlight the significance of the mist-flow-induced reactions for mist CVD epitaxial growth, providing new insight into the mechanism of epitaxial growth by mist CVD.

SIMULTANEOUS SOLAR PHOTO-DEGRADATION OF PVC-FE-DOPED ZNO-NANOCOMPOSITE FLAKES AND METHYLENE BLUE DYE IN WATER

Simultaneous solar photocatalytic decolorization of Methlene Blue (MB) dye and degradation of polymer nanocomposite film in water has been attempted in the present work. The film immobilized iron (Fe)-doped zinc oxide (ZnO) nanoparticles (NPs) in polyvinyl chloride (PVC) matrix. This reduced the cost of separation of nanoparticles from treated water. Doped NPs were prepared sonochemically using zinc acetylacetonate (0.95 mmol) and ferric acetylacetonate (0.05 mmol) precursors in aqueous ethanol medium. XRD, UV-vis spectroscopy, FESEM and EDX were used for characterizing nanoparticles whereas the film was characterized by SEM. During the process, the film also reduced in weight. Degradation of both the dye and the polymer followed pseudo-first order kinetics. About 28% of the initial concentration of dye and about 5.04% of the initial weight of the PVC-film were decreased in the process after a run time of 3 h 45 minutes.

In situ formed ultrafine metallic Ni from nickel (II) acetylacetonate precursor to realize an exceptional hydrogen storage performance of MgH2[sbnd]Ni-EG nanocomposite

It has been well known that doping nano-scale catalysts can significantly improve both the kinetics and reversible hydrogen storage capacity of MgH2. However, so far it is still a challenge to directly synthesize ultrafine catalysts (e.g., < 5 nm), mainly because of the complicated chemical reaction processes. Here, a facile one-step high-energy ball milling process is developed to in situ form ultrafine Ni nanoparticles from the nickel acetylacetonate precursor in the MgH2 matrix. With the combined action of ultrafine metallic Ni and expanded graphite (EG), the formed MgH2Ni-EG nanocomposite with the optimized doping amounts of Ni and EG can still release 7.03 wt.% H2 within 8.5 min at 300 °C after 10 cycles. At a temperature close to room temperature (50 °C), it can also absorb 2.42 wt.% H2 within 1 h. It can be confirmed from the microstructural characterization analysis that the in situ formed ultrafine metallic Ni is transformed into Mg2Ni/Mg2NiH4 in the subsequent hydrogen absorption and desorption cycles. It is calculated that the dehydrogenation activation energy of the MgH2Ni-EG nanocomposite is also reduced obviously in comparison with the pure MgH2. Our work provides a methodology to significantly improve the hydrogen storage performance of MgH2 by combining the in situ formed and uniformly dispersed ultrafine metallic catalyst from the precursor and EG.

Sol–gel synthesis of manganese-doped ceria from acetylacetonate precursors

Sol–gel synthesis of manganese-doped ceria from acetylacetonate precursors

Colloidal synthesis of nanoparticles: from bimetallic to high entropy alloys.

At the nanoscale, the synthesis of a random alloy (i.e. without phase segregation, whatever the composition) by chemical synthesis remains a difficult task, even for simple binary type systems. In this context, a unique approach based on the colloidal route is proposed enabling the synthesis of face-centred cubic and monodisperse bimetallic, trimetallic, tetrametallic and pentametallic nanoparticles with diameters around 5 nm as solid solutions. The Fe-Co-Ni-Pt-Ru alloy (and its subsets) is considered a challenging task as each element has fairly different physico-chemical properties. Particles are prepared by temperature-assisted co-reduction of metal acetylacetonate precursors in the presence of surfactants. It is highlighted how the correlation between precursors' degradation temperatures and reduction potential values of the metal cations is the driving force to achieve a homogeneous distribution of all elements within the nanoparticles.

Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production.

A method for facile synthesis of nanostructured catalysts supported on carbon nanotubes with atomically dispersed cobalt and nitrogen dopant is presented herein. The novel strategy is based on a facile one-pot pyrolysis treatment of cobalt (II) acetylacetonate and nitrogen-rich organic precursors under Ar atmosphere at 800 °C, resulting in the formation of Co- and N- co-doped carbon nanotube with earthworm-like morphology. The obtained catalyst was found to have a high density of defect sites, as confirmed by Raman spectroscopy. Here, cobalt (II) nanoparticles were stabilized on the atomically dispersed cobalt- and nitrogen-doped carbon nanotubes. The catalyst was confirmed to be effective in the catalytic hydrolysis of ammonia borane, in which the turnover frequency was 5.87 mol H2·molCo-1·min-1, and the specific hydrogen generation rate was determined to be 2447 mL H2·gCo-1·min-1. A synergistic function between the Co nanoparticle and the doped carbon nanotubes was proposed for the first time in the catalytic hydrolysis of ammonia borane reaction under a mild condition. The resulting hydrogen production with its high energy density and minimal refueling time could be suitable for future development as energy sources for mobile and stationary applications such as road trucks and forklifts in transport and logistics.

Chemical vapor deposition of CoFe2O4 micropillar arrays with enhanced magnetic properties

Single-step thermal chemical vapor deposition was optimized at 400 °C for the growth of CoFe2O4 spinel thin films starting from the corresponding metal acetylacetonate precursors. Enhanced magnetization was observed for conditions leading to a columnar growth with a preferred (100) orientation. The implemented liquid precursor delivery secured a reliable films’ composition control and a straightforward dosage of acetylacetone, as a molecular growth inhibitor, to enhance the film conformality on structured surfaces. The optimized conditions enabled an efficient micro-pore filling, and the fabricated ordered micropillar arrays feature a coercivity of 1.8 kOe and a saturation magnetization of 350 emu/cm3. The implemented state-of-the-art up-scalable microfabrication technology, the reasonable thermal budget and the resulting high magnetic performance pave the way towards the development of innovative magnetoelectric devices.

Microwave Irradiation Assisted Synthesis of Gallium Aluminum Oxide Using Metal Acetylacetonate Precursors, Peculiar Observations and Safety Guidelines for Young Scientists

Microwave-assisted nano-particle synthesis has seen a boom in recent decade. Different variants are being tested all over the world, be it microwave-irradiation-assisted solvothermal synthesis, thin-film deposition using microwave plasma-assisted CVD, microwave-assisted combustion synthesis, or mist CVD. This technology induces self-catalysis, faster reaction time, less energy and is considered safer from other purely chemical variants. Gallium-Aluminum Oxide is an oxide of vital importance. Gallium Oxide in its most stable form, β-Ga2O3, has a band-gap of ∼4.8 eV and cannot be used for deep ultra-violet (UV) applications (i.e., below 250 nm). Aluminum oxide is a wide band-gap material. The ionic radius of Aluminum ions is similar to that of Gallium ions. Therefore, according to Hume-Rothery rule, Aluminum ion can substitute Gallium in its lattice structure and vice-versa. This gives the possibility of band-gap engineering from 4.6 eV (band-gap, β-Gallium Oxide) to 8.8 eV (band-gap, α-Aluminum Oxide), extending the application of Gallium Oxide to deep UV applications. In present work, three different compositions of Gallium-Aluminum Oxide thin films (varied by mass) are deposited, using microwave-irradiation-assisted solvothermal thin-film deposition technique and metal acetylacetonate precursors. A stoichiometric ratio of ∼5:1 is obtained for 90:100 variation. For 50:50 and 10:90, the stoichiometric ratio remained close to 5:5 and 1:9, respectively, showing good agreement with the Gallium to Aluminum ratio in precursor solution. The investigation is done by using energy dispersive X-Ray analysis. A particle variation from 5 nm to 500 nm was obtained as calculated from Field Emission Scanning Electron Microscopy (FESEM) results. In second part of the work, the corresponding author wants to strongly argue that “Microwave in kitchen is not same as microwave in lab” and report some of the observations from lab to pave a way towards a truly Green or safer technology.

Exploring the influence of nickel precursors on constructing efficient Ni-based CO2 methanation catalysts assisted with in-situ technologies

In this work, a series of Ni-based CO2 methanation catalysts were prepared with different nickel salt precursors. The Ni-AA catalyst with nickel acetylacetonate precursor displayed the highest activity among these catalysts. The in-situ diffused reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS) and the online-tandem thermogravimetric mass spectrometry (TG-MS) were performed to investigate the intermediates of the catalyst calcination process. The superior performance of the Ni-AA catalyst could be derived from its special coordinating anion. Furthermore, the rapid deactivation of the Ni-S catalyst with nickel sulfate precursor was attributed to the generation of the Ni3S2 after reduction pretreatment. As for the Ni-Cl catalyst with nickel chloride precursor, its negligible activity could be owing to poisoning effect of the Cl− by the coverage of the catalyst surface. Therefore, the significant role of the metal salt precursor should be preferentially considered when designing the Ni-based catalysts and even other metal based heterogeneous catalysts.

The Influence of the Thickness of Compact TiO2 Electron Transport Layer on the Performance of Planar CH3NH3PbI3 Perovskite Solar Cells.

In recent years, lead halide perovskites have attracted considerable attention from the scientific community due to their exceptional properties and fast-growing enhancement for solar energy harvesting efficiency. One of the fundamental aspects of the architecture of perovskite-based solar cells (PSCs) is the electron transport layer (ETL), which also acts as a barrier for holes. In this work, the influence of compact TiO2 ETL on the performance of planar heterojunction solar cells based on CH3NH3PbI3 perovskite was investigated. ETLs were deposited on fluorine-doped tin oxide (FTO) substrates from a titanium diisopropoxide bis(acetylacetonate) precursor solution using the spin-coating method with changing precursor concentration and centrifugation speed. It was found that the thickness and continuity of ETLs, investigated between 0 and 124 nm, strongly affect the photovoltaic performance of PSCs, in particular short-circuit current density (JSC). Optical and topographic properties of the compact TiO2 layers were investigated as well.

Substrate Effects on Crystal Phase in Atomic Layer Deposition of Tin Monosulfide

Obtaining single-phase tin monosulfide (SnS) films at low temperatures is challenging since cubic (π-SnS) and orthorhombic (α-SnS) polymorphs have similar energies of formation and grow under similar conditions. Here, we show that in atomic layer deposition (ALD) of polycrystalline SnS using tin(II) acetylacetonate and H2S precursors, the substrate surface greatly influences the SnS phase evolution. For example, a silicon (100) substrate, with a highly hydroxylated surface, favors the growth of α-SnS. Meanwhile, ozone treatment or preannealing of the same substrate leads to mainly π-SnS. Just a few ALD cycles of another oxide or sulfide can even more substantially alter the outcome. Substrates that favor α-SnS growth typically produce initially enhanced growth rates, while those promoting π-SnS are partially surface-poisoned by the acetylacetonate precursor ligands. Growth of either polymorph is self-sustained after its initiation, and the sustaining factor appears to be the surface–ligand interaction; π-SnS preferentially evolves on substrates and π-SnS surfaces that are rich in highly reactive dangling bonds, while chemically inert substrates and α-SnS surfaces promote α-SnS. While lattice matching is less central, the role of ligand bonding in SnS ALD also helps explain the previously reported phase dependence on growth temperature and H2S precursor dose and shows promise for area-selective ALD of SnS.