Precursor Composition Research Articles

Alkaline activation via in-situ caustification of one-part binders of composite precursors of waste glass and limestone

Mixtures of powders of waste glass (WG), limestone (LS), Na2CO3 and CaO were used to formulate novel one-part in situ alkali-activated cement (WG-AAC). The in-situ interaction Na2CO3-CaO-H2O promoted the formation of CaCO3 and NaOH, which promoted the WG and LS dissolution and influenced the micro- and molecular features of the resulting cementitious products. Pastes and mortars developed 1-year strengths of up to 29 MPa and were stable underwater. Characterization by XRD, SEM, EDS, and 29Si-NMR indicated that a Na2CO3:CaO ratio close to 1:1 resulted in polymerized C-S-H, CaCO3, silica gel, and Ca-modified silica gel, which were intimately intermixed and possibly crosslinked through Q3 bonds. Such phases interacted synergistically improving the underwater stability of the WG-AAC, indicating that in-situ caustification is a suitable and practical alkaline activation for SiO2-rich precursors.

High-responsivity photoelectrochemical ultraviolet photodetector based on SnO2 nanosheets-Ga2O3

Abstract Tin oxide (SnO2) has garnered significant attention for its high spectral selectivity when used as an ultraviolet photodetector. In this study, SnO2 nanosheets (NSs) were synthesized via a hydrothermal method, followed by spin-coating a layer of Ga2O3 thin film to construct a heterojunction photoelectrochemical ultraviolet photodetector (PEC UV PD). Initially, we investigated the effect of precursor composition on the properties of the Ga2O3 thin films. It was observed that the thickness of the films increased with higher precursor concentrations, while the optical bandgap decreased. Based on these findings, we successfully fabricated the SnO2 NSs-Ga2O3 PEC UV PD. Electrochemical analysis revealed that as the precursor concentration used for spin-coating Ga2O3 increased, the device's responsivity and detectivity initially increased and then decreased. After optimization, the device prepared with a 0.2M Ga(NO3)3 solution spin-coated on SnO2 exhibited excellent spectral selectivity (R 265nm/R 420nm ~ 4472), a responsivity of 4.86 mA W-1, and a detectivity of 2.72×109 Jones. This study demonstrates that coating Ga2O3 is an effective approach to constructing high-performance SnO2-based UV PDs.

Thin Film Deposition and Optical Properties of Cs-Cu-I System Via Mist Deposition with Various Precursor Compositions

Thin Film Deposition and Optical Properties of Cs-Cu-I System Via Mist Deposition with Various Precursor Compositions

Oxidation Behaviour of TiC/TiN Coatings Deposited by Chemical Vapor Deposition (CVD): Mechanisms, Structures, and Properties

This review explores the oxidation behavior of Titanium Carbide (TiC) and Titanium Nitride (TiN) coatings deposited by Chemical Vapor Deposition (CVD), with a focus on their industrial applications as wear-resistant coatings for cutting tools. It examines effect of process parameters—such as temperature, pressure, precursor composition, and substrate preparation—on formation and performance of TiC/TiN coatings. The review evaluates the microstructural characteristics of these coatings, including crystal structure, using X-ray diffraction analysis. Also, estimates the mechanical properties such as hardness, wear resistance, and adhesion strength. Additionally, the review covers the thermal stability of TiC/TiN coatings, emphasizing their ability to maintain structural integrity at high temperatures, which is essential for the performance of cutting tools and other industrial components. A major focus is the oxidation behavior of TiC/TiN coatings, including the impact of coating composition, deposition methods, and environmental conditions. The review details oxidation kinetics and mechanisms, revealing various stages of oxidation at different temperatures. It also examines oxide scale morphology and its effect on coating properties. Finally, this review reveals the importance of alloying elements, like silicon, in improving oxidation resistance. Composite coatings such as TiSiN and TiSiCN are shown to offer better high-temperature stability compared to traditional TiN coatings. The effects of coating thickness and the benefits of multilayer coatings for enhanced oxidation resistance are also discussed.

Insights into the mechanism of enhancing resistance of MnAlOx-Str NH3-SCR catalyst derived from streptomycin waste residue and LDHs

Streptomycin waste residue composited with Layered double hydroxides (LDHs) derived Mn1Al1Ox-Str-2 catalyst was proposed for NH3 selective catalytic reduction (NH3-SCR) denitration technology, which improved the overall catalytic performance. In the wide temperature range of 150-300℃, the preferred Mn1Al1Ox-Str-2 catalyst had Nitrogen oxides (NOx) conversion of exceeded 96%, which was higher than that of the control Mn1Al1Ox and Mn/Al2O3 catalysts. In addition, Mn1Al1Ox-Str-2 catalyst had better resistance to SO2 and/or H2O, as well as good regeneration ability. Various analytical techniques had confirmed that the Mn1Al1Ox-Str-2 catalyst derived from streptomycin residue composite LDHs precursor had better surface properties with more active species, abundant surface oxygen, higher reduction capacity and better adsorption of NOx and NH3. Analytical techniques revealed that the Lewis acid site on the surface of Mn1Al1Ox-Str-2 catalyst was involved in SCR reaction and both the Eley-Rideal mechanism and Langmuir-Hinshelwood mechanism existed simultaneously in the NH3-SCR reaction, and SO2 had a weak effect on the adsorption of reactants with fewer sulfate species formation. This work provided feasible strategies for efficient and stable SCR technology and efficient utilization of streptomycin residue waste resources, which was significant for the design and application of SCR technology in the future.

Unveiling the generation of mesoporous MFI zeolites with one-dimensional fins in the assistance from small quaternary ammonium cation and its application in propane aromatization

In this work, a kind of ZSM-5 zeolite with one-dimensional fins growing along the [010] direction has been successfully synthesized utilizing both tetrapropylammonium hydroxide (TPAOH) and tetramethylammonium hydroxide (TMAOH) as co-templates. With the aid of molecular dynamic simulations and a series of experimental evidences, the formation mechanism of the one-dimensional feature is determined to arise from the synergic effects between TPA+ and TMA+. Two TPA+ and three TMA+ would co-exist in a unit MFI cell at a certain crystallization period depending on the composition of zeolite and precursor, and this configuration ensures a minimum stabilization energy required for the growth along [010] direction. Investigations manifest these needle-like fins with diameters of ca. 60 nm could function as pseudo nano crystals and introduce additional pores ranging from 10 to 90 nm, which effectively promotes the diffusion capability and substantially improves the catalytic performance in propane aromatization.

Lead Iodide Redistribution Enables In Situ Passivation for Blading Inverted Perovskite Solar Cells with 24.5% Efficiency.

Blade-coating stands out as an alternative for fabricating scalable perovskite solar cells. However, it demands special control of the precursor composition regarding nucleation and crystallization and currently exhibits lower performance than the spin-coating process. It is mainly the resulting film morphology and excess lead iodide (PbI2) distribution that influences the optoelectronic properties. Here, the effectiveness of introducing N-Methyl-2-pyrrolidone (NMP) to regulate the structure of the perovskite layer and the redistribution of PbI2 is found. The introduction of NMP leads to the accumulation of excess PbI2, mainly on the top surface, reducing residual PbI2 at the perovskite buried interface. This not only facilitates the passivation of perovskite grain boundaries but also eliminates the potential degradation of the PbI2 triggered by light illumination in the perovskite buried interface. The optimized NMP-modified inverted perovskite solar cell achieves a champion efficiency of 24.5%, among the highest reported blade-coated perovskite solar cells. Furthermore, 13.68cm2 blading perovskite solar modules are fabricated and demonstrate an efficiency of up to 20.4%. These findings underscore that with proper modulation of precursor composition, blade-coating can be a feasible and superior alternative for manufacturing high-quality perovskite films, paving the way for their large-scale applications in photovoltaic technology.

The catalytic wet air oxidation of pharmaceutical wastewater with alkali-activated Mn and Cu composites: preparation of precursors by calcination of kaolin with Mn and Cu

In recent decades, the concentration of pharmaceutical residues and narcotics has increased in municipal wastewater. Decomposing these toxic organic chemicals is challenging and requires new techniques and advanced catalytic materials. Precursors of metal composites were prepared by calcining an aqueous suspension of natural clay–based kaolin with Mn and Cu, binding chemically the active metals to the aluminosilicate frame structure of the precursor. The specific surface area of Mn and Cu composite was 67 m2/g and 81 m2/g, respectively. The mechanical durability was determined in terms of compressive strength, and 3.3 MPa and 3.6 MPa were obtained, respectively. In the CWAO of pharmaceutical wastewater, Mn composite gave the highest conversions of 54% and 46% of the chemical oxygen demand (COD) and total organic carbon (TOC), respectively. Metal composites were mechanically and chemically highly durable, inducing only 1.2 wt.% and 1.4 wt.% mass loss. In CWAO, Mn and Cu composite increased the biodegradation of organic species in the wastewater by 65% and 75%, respectively.

The Cahn–Hilliard model of coherent lamellar microstructure: application to alkali feldspar

The temporal evolution of coherent lamellar microstructures is significantly influenced by their elastic properties, particularly when the exsolved phases are coherent. This research utilizes the Cahn–Hilliard model to examine the morphological and energetic evolution of binary alkali feldspar, integrating anisotropic elastic energy into the Gibbs energy equation. The Cahn–Hilliard model successfully simulated the orientation of lamellae observed in natural samples and the elastic strain was consistent with previous research. We also computed the coherent solvus from the annealing simulation of various precursor compositions and temperatures. The temperature difference (ΔT\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta T$$\\end{document}) between the strain-free solvus and the coherent solvus was ΔT=85∘C\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\Delta T = 85\\,{}^\\circ \ ext {C}$$\\end{document}, which is slightly lower than previously reported values obtained from similar parameters. This discrepancy is likely due to the presence of non-planar lamellae at the onset of phase separation, which are more stable than planar ones. We also simulated the binodal curves of the coherent solvi for different precursor phase compositions. The computed solvi were not unique but varied depending on the precursor composition. Our model is flexible because it does not assume any specific shapes for the lamellar interfaces and is applicable to various coherent binary systems.

Efficiency study of nickel-containing glass-fiber catalysts for CO2 methanation

The work is dedicated to the synthesis and investigation of Ni-containing catalysts based on glass-fiber carriers (GFC) with an additionally deposited secondary layer of porous SiO2 for the process of carbon dioxide methanation. Ni-based GFCs were prepared using the surface thermosynthesis (STS) and pulse surface thermosynthesis (PSTS) methods, involves heat treatment of the catalyst with the supported Ni precursor at a high heating rate; such procedure was not applied earlier for production of CO2 methanation catalysts. The GFC sample prepared by the PSTS method with a fuel additive in the precursor composition is characterized by a more uniform distribution of Ni particles on the catalyst surface and better dispersion of Ni, smaller crystallite size: NiO crystallites in this freshly prepared GFCs are smaller than 10 nm and Ni crystallites in reduced catalysts are <30 nm. As a result, this sample demonstrated the highest apparent activity in the methanation reaction among all synthesized GFCs, it has also showed a significantly higher specific activity per unit mass of nickel compared to the commercial Ni-Al2O3 analogue. The synthesized catalysts are original, they can be effectively applied for development of novel highly efficient technologies for energy conversion/storage systems and greenhouse gas emission control.

Omniphobic Photoresist‐Assisted Patterning of Porous Polymethacrylate Films

AbstractPatterning of various surface properties, including roughness, wettability, adhesiveness, and mechanical properties, can markedly enhance the functionality of test systems. Thus, porous polymethacrylates prepared by polymerization‐induced phase separation (PIPS) represent a promising class of functional materials for the construction of miniaturized test systems. Different porosity, surface chemistry, and wettability are achieved in porous polymethacrylates with different precursor compositions. Nevertheless, only wettability microstructuring has been highlighted for these materials thus far. Here, the study presents a novel method for the direct and selective deposition of porous polymethacrylate films with different surface chemistry and porosity. The selective adhesion of omniphobic–omniphilic wettability patterns is used to facilitate the polymer pattern formation. The feasibility of patterning with different monomers and porogenic solvents is demonstrated. The topological study confirms the selective application of polymer structures with different thickness and roughness. The wettability characterization of the omniphobic material shows no significant changes caused by the operations performed. Thus, a new pattern with a greater difference in the wettability of the areas is produced in the process. Discontinuous dewetting of different liquids is performed. The use of poly(2‐hydroxyethyl methacrylate‐co‐ethylene dimethacrylate) (HEMA‐EDMA) modified patterns for precise living cell patterning is also demonstrated.

Chemically Tailored Growth of 2D Semiconductors via Hybrid Metal-Organic Chemical Vapor Deposition.

Two-dimensional (2D) semiconducting transition-metal dichalcogenides (TMDCs) are an exciting platform for excitonic physics and next-generation electronics, creating a strong demand to understand their growth, doping, and heterostructures. Despite significant progress in solid-source (SS-) and metal-organic chemical vapor deposition (MOCVD), further optimization is necessary to grow highly crystalline 2D TMDCs with controlled doping. Here, we report a hybrid MOCVD growth method that combines liquid-phase metal precursor deposition and vapor-phase organo-chalcogen delivery to leverage the advantages of both MOCVD and SS-CVD. Using our hybrid approach, we demonstrate WS2 growth with tunable morphologies─from separated single-crystal domains to continuous monolayer films─on a variety of substrates, including sapphire, SiO2, and Au. These WS2 films exhibit narrow neutral exciton photoluminescence line widths down to 27-28 meV and room-temperature mobility up to 34-36 cm2 V-1 s-1. Through simple modifications to the liquid precursor composition, we demonstrate the growth of V-doped WS2, MoxW1-xS2 alloys, and in-plane WS2-MoS2 heterostructures. This work presents an efficient approach for addressing a variety of TMDC synthesis needs on a laboratory scale.

On the thermodynamics of Barium Oxyfluoride precursor in YBCO growth via the MOD process

Abstract Barium Oxyfluoride plays an important role, as a precursor species, in the nucleation and growth of YBa2Cu3O7−δ (YBCO) via the low fluorine metal organic decomposition (MOD low-fluorine) route. In this contribution, we present a study on the thermodynamics of oxyfluoride by processing experimental data on YBCO growth on LaAlO3 (LAO) substrates. The analysis allows one to determine the standard enthalpy and the standard entropy changes for oxyfluoride formation from barium oxide and barium fluoride. To identify the thermodynamically more favorable route to oxyfluoride formation in the MOD low-fluorine process, the free energy change for the formation of the precursor, through reactions involving gas water, has been determined. The free energy of formation via fluoride and water indicates higher stability of oxygen rich oxyfluoride for P HF 2 P H 2 O &lt; 10 − 6 . In the framework of nucleation theory, the present results are needed to study the effect of precursor composition on film orientation.

The room temperature signature of micro to nanocrystalline calcium copper titanate (CCTO) thin film by a modified sol-gel technique and tailoring its material property

This study aims to identify an alternative route for the low-temperature synthesis of calcium copper titanate (CCTO) thin films and to explore a new understanding of precursor composition strategy and its relationship to thin-film combustion synthesis using a modified sol-gel technique. Micro-sized to nano-sized CCTO thin films were effectively deposited onto various substrates using a rapid and modified sol-gel process at remarkably low temperatures (∼100 °C), with room temperature phase formation of CCTO observed via FTIR and Raman spectroscopy. Calcium nitrate, copper nitrate, and titanium (IV) butoxide served as precursor materials to create the sol for spin coating. The resulting CCTO thin films were polycrystalline, uniform, and compact. The surface morphology and optical properties of these films were analyzed using Atomic Force Microscopy (AFM), Field Emission Scanning Electron Microscopy with Energy Dispersive X-Ray Analysis (FESEM-EDAX), X-Ray Diffraction (XRD), and UV–VIS spectrophotometry. XRD confirmed various phases of CCTO on different substrates, with significant intensity variations in the peaks at different annealing temperatures. The XRD patterns on three different substrates-glass, SnO2 coated glass, and SiO2 coated Si—revealed different CCTO phases such as CCTO (301), CCTO (220), CCTO (400), and CCTO (422). EDAX analysis confirmed the presence of Ca, Cu, Ti, and O. The band gap varied from 2.5 to 3.8 eV depending on the annealing temperature. Capacitive vs. frequency response, dielectric loss, and I-V characteristics of the films were measured using MIM (Metal-Insulator-Metal) or SIM (Semiconductor-Insulator-Metal) structures.

Yeast extracts weakened warmed-over flavor in surimi gels made from silver carp due to the masking effect by high concentrations of pyrazines and esters.

Warmed-over flavor (WOF) is an off-flavor in surimi gels. Yeast extract (YE) could improve the aroma properties of food. However, the effect of YE on the WOF in surimi gels and its mechanism was still unclear. In this study, aroma profiles, the composition of aroma compounds and aroma precursors, concentrations of WOF compounds, and thiobarbituric acid reactive substances (TBARS) of surimi gels with different amounts of YE were investigated by molecular sensory science and chromatographic techniques. Moreover, the effect of pyrazines and esters introduced by YE on WOF was also tested by sensory analysis. The addition of no less than 1% YE to surimi gels significantly weakened WOF. However, YE did not decrease the concentrations of WOF compounds and did not change the fatty acid composition and TBARS in surimi gels. Conversely, the addition of YE significantly increased the contents of free amino acids, N-containing compounds, and esters in surimi gels. The contents of total free amino acids, 2,6-dimethylpyrazine, and ethyl acetate in surimi gels with 2.5% YE were 1.5, 21, and 2.1 times higher than those in the control, respectively. Additionally, the sensory results of the spiked aroma models containing WOF compounds, 2,6-dimethylpyrazine, and esters showed that more than 9.4µg/kg of 2,6-dimethylpyrazine with a baked-potato note and more than 6.1µg/kg of ethyl acetate and 11.2µg/kg of butyl acetate with a fruity note could significantly mask WOF. In conclusion, WOF in surimi gels could be masked by YE due to the high concentrations of pyrazines and esters. Practical Application: Yeast extracts could decrease the warmed-over flavor (WOF) due to the high concentrations of pyrazines (baked-potato note) and esters (fruity note). This finding extends the application of yeast extracts in the food industry. On the other hand, this study presents a reasonable solution for the reduction of WOF in surimi products.

The Role of -OEt Substituents in Molybdenum-Assisted Pentathiepine Formation-Access to Diversely Functionalized Azines.

1,2,3,4,5-pentathiepines (PTEs) are naturally occurring polysulfides of increasing scientific interest based on their identified pharmacological activities. Artificial PTEs with N-heterocyclic backbones are efficiently synthesized via mediation by a molybdenum-oxo-bistetrasulfido complex. A common feature of all precursor alkynes successfully used to date in this reaction is the presence of a -CH(OEt)2 group since the previously postulated mechanism requires the presence of one OEt- as the leaving group, and the second must become a transient ethoxonium moiety. This raised the question of whether there really is a need for two, maybe only one, or possibly even zero ethoxy substituents. This research problem was systematically addressed by respective variations in the precursor-alkyne derivatives and by employing one related allene species. It was found that the total absence of ethoxy substituents prevents the formation of PTEs entirely, while the presence of a single ethoxy group results in the possibility to distinctly functionalize the position on the resulting N-heterocyclic pyrrole five ring in the target compound. This position was previously exclusively occupied by an -OEt for all products of the molybdenum-mediated reaction. The allene was applied with similar success as precursor as with the related alkyne. The now-employable significant change in precursor composition gives access to a whole new PTE subfamily, allowing further modulation of (physico)-chemical properties such as solubility, and provides additional insight into the mechanism of PTE formation; it comprises a merely partial validation of the previous hypothesis. The new alkyne precursors and pentathiepines were characterized by a variety of instrumental analyses (NMR, mass spec, UV-vis) and in six cases (one alkyne precursor, one unexpected side product, and four PTEs) by single-crystal X-ray diffraction. Syntheses, isolation procedures, analytical data, and the impact of the findings on the previously proposed mechanism are described in detail herein.

From Wide-Bandgap to Narrow-Bandgap Perovskite: Applications from Single-Junction to Tandem Optoelectronics.

As perovskite solar device is burgeoning photoelectronic device, numerous studies to optimize perovskite solar device have been demonstrated. Amongst various advantages from perovskite light absorbing layer, attractive property of tunable bandgap allowed perovskite to be adopted in many different fields. Easily tunable bandgap property of perovskite opened the wide application and to get the most out of its potential, many researchers contributed as well. By precursor composition engineering, narrow bandgap with bandgap of less than 1.4 eV and wide bandgap with bandgap of more than 1.7 eV were achieved. Optimization of both narrow and wide bandgap perovskite solar cell could pave the way to all-perovskite tandem solar cell which is combination of top cell with wide bandgap and bottom cell with narrow bandgap. This review highlights numerous efforts to advance device performance of both narrow and wide bandgap perovskite solar cell and how they challenged the issues. And finally, efforts to operate and utilize all-tandem perovskite device in real world will be discussed.

Spray-Flame Synthesis of NASICON-Type Rhombohedral (α) Li1+xYxZr2-x(PO4)3 [x = 0-0.2] Solid Electrolytes.

Since solid electrolytes have a broad electrochemical stability window, are exceptionally electrochemically stable against Li metal, and function as a physical separator to prevent dendrite growth, they are at the forefront of alternate possibilities, further increasing the stability and energy density of Li-ion batteries. NASICON-type electrolytes are a promising candidate due to their negligible moisture sensitivity, which results in outstanding stability and a lower probability of Li2CO3 passivity under the ambient atmosphere. However, one of the most promising representatives, Li1+xYxZr2-x(PO4)3 (LYZP), has multiple stable phases with significant variation in their corresponding Li-ion conductivity. In this paper, we have successfully synthesized the highly ionically conductive rhombohedral phase of LYZP via spray-flame synthesis. Two different solvent mixtures (e.g., 2-ethyl hexanoic acid/ethanol, propanol/propanoic acid) were chosen to explore the effect of precursor composition and combustion enthalpy on the phase composition of the nanoparticle. The as-synthesized nanoparticles from spray-flame synthesis consisted of the crystalline tetragonal zirconia (t-ZrO2) phase, while lithium, yttrium, and phosphate were present on the nanoparticles' surface as amorphous phases. However, a short annealing step (1 h) was sufficient to obtain the NASICON phase. Moreover, we have shown the gradual phase conversion from orthorhombic β phase to rhombohedral α phase as the annealing temperature increased from 700 °C to 1300 °C (complete removal of β phase). In this context, Y3+ doping was also crucial, along with the appropriate solvent mixture and annealing temperature, for obtaining the much-desired rhombohedral α phase. Further, 0.2 at% Y3+ doping was added to the solvent mixture of 2-ethyl hexanoic acid/ethanol, and annealing at 1300 °C for 1 h resulted in a high ionic conductivity of 1.14∙10-5 S cm-1.

Synthesis of nitrogen-doped amorphous carbon nanotubes from novel cobalt-based MOF precursors for improving potassium-ion storage capability

Amorphous carbon materials with sophisticated morphologies, variable carbon layer structures, abundant defects, and tunable porosities are favorable as anodes for potassium-ion batteries (PIBs). Synthesizing amorphous carbon materials typically involves the pyrolysis of carbonaceous precursors. Nonetheless, there is still a lack of studies focused on achieving multifaceted structural optimizations of amorphous carbon through precursor formulation. Herein, nitrogen-doped amorphous carbon nanotubes (NACNTs) are derived from a novel composite precursor of cobalt-based metal–organic framework (CMOF) and graphitic carbon nitride (g-CN). The addition of g-CN in the precursor optimizes the structure of amorphous carbon such as morphology, interlayer spacing, nitrogen doping, and porosity. As a result, NACNTs demonstrate significantly improved electrochemical performance. The specific capacities of NACNTs after cycling at current densities of 100 mA/g and 1000 mA/g increased by 194 % and 230 %, reaching 346.6 mAh/g and 211.8 mAh/g, respectively. Furthermore, the NACNTs anode is matched with an organic cathode for full-cell evaluation. The full-cell attains a high specific capacity of 106 mAh/gcathode at a current density of 100 mA/g, retaining 90.5 % of the specific capacity of the cathode half-cell. This study provides a valuable reference for multifaceted structural optimization of amorphous carbon to improve potassium-ion storage capability.

Synthesis of Metallic and Metal Oxide Nanoparticles Using Homopolymers as Solid Templates: Luminescent Properties of the Eu+3 Nanoparticle Products

Starting from poly(4-vinylpyridine) ((P4VP)n), poly(2-vinylpyridine) ((P2VP)n), and [N=P(O2CH2CF3)]m-b-P2VP20 block copolymers, a series of metal-containing homopolymers, (P4VP)n⊕MXm, (P2VP)n⊕MXm, and [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm MXm = PtCl2, ZnCl2, and Eu(NO3)3, have been successfully prepared by using a direct and simple solution methodology. Solid-state pyrolysis of the prepared metal-containing polymeric precursors led to the formation of a variety of different metallic and metal oxide nanoparticles (Pt, ZnO, Eu2O3, and EuPO4) depending on the composition and nature of the polymeric template precursor. Thus, whereas Eu2O3 nanostructures were obtained from europium-containing homopolymers ((P4VP)n⊕MXm and (P2VP)n⊕MXm), EuPO4 nanostructures were achieved using phosphorus-containing block copolymer precursors, [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm with MXm = Eu(NO3)3. Importantly, and although both Eu2O3 and EuPO4 nanostructures exhibited a strong luminescence emission, these were strongly influenced by the nature and composition of the macromolecular metal-containing polymer template. Thus, for P2VP europium-containing homopolymers ((P4VP)n⊕MXm and (P2VP)n⊕MXm), the highest emission intensity corresponded to the lowest-molecular-weight homopolymer template, [P4VP(Eu(NO3)3]6000, whereas the opposite behavior was observed when block copolymer precursors, [N=P(O2CH2CF3)]m-b-P2VP20]⊕MXm MXm= Eu(NO3)3, were used (highest emission intensity corresponded to [N=P(O2CH2CF3)]100-b-[P2VP(Eu(NO3)3)x]20). The intensity ratio of the emission transitions: 5D0 → 7F2/5D0 → 7F1, suggested a different symmetry around the Eu3+ ions depending on the nature of the polymeric precursor, which also influenced the sizes of the prepared Pt°, ZnO, Eu2O3, and EuPO4 nanostructures.