Precursor Species Research Articles

Co-assembly-driven nanocomposite formation techniques toward mesoporous nanosphere engineering: A review

Mesoporous nanospheres are of great importance in the cutting-edge fields of energy, catalysis and sensor technology, mainly because of their multilevel architectures, tunable meso-structures, specific compositions and soft-templated synthesis approaches. In this review, the control mechanisms of aqueous polymer self-assembly are first elaborated based on the correlated driving forces, methods, and initial conditions. Then, recent advances of co-assembly-driven nanocomposite formation techniques toward mesoporous nanosphere engineering using amphiphilic block copolymers and low-molecular-weight surfactants as soft templates are systematically reviewed. Here, soft templates and organic or inorganic precursor species as well as their co-assembly processes and formation mechanisms are elaborated to thoroughly understand co-assembly-driven nanocomposite formation techniques. After soft template removal through high-temperature pyrolysis or solvent extraction, mesoporous nanospheres can be obtained. Generally, this review presents insights and a guideline to co-assembly-driven engineering of mesoporous nanospheres and promotes the development of this emerging interdisciplinary research field at the frontier between organic polymer co-assembly and inorganic nanomaterial fabrication. Co-assembly-driven nanocomposite formation techniques show great potential in manufacturing mesoporous nanospheres with multilevel architectures, in which the controllable soft template self-assemblies, precursor species and their nanocomposite formation techniques enable mesoporous nanospheres with tunable meso-structures and compositions, soft-templated synthesis approaches and functional applications. • A systematic summary of soft template-directed co-assembly techniques. • In-depth analysis on mesoporous nanospheres with controllable meso-structures. • Perspectives on the opportunities and challenges of mesoporous nanospheres.

Observation of an Intermediate to H2 Binding in a Metal-Organic Framework.

Coordinatively unsaturated metal sites within certain zeolites and metal-organic frameworks can strongly adsorb a wide array of substrates. While many classical examples involve electron-poor metal cations that interact with adsorbates largely through physical interactions, unsaturated electron-rich metal centers housed within porous frameworks can often chemisorb guests amenable to redox activity or covalent bond formation. Despite the promise that materials bearing such sites hold in addressing myriad challenges in gas separations and storage, very few studies have directly interrogated mechanisms of chemisorption at open metal sites within porous frameworks. Here, we show that nondissociative chemisorption of H2 at the trigonal pyramidal Cu+ sites in the metal-organic framework CuI-MFU-4l occurs via the intermediacy of a metastable physisorbed precursor species. In situ powder neutron diffraction experiments enable crystallographic characterization of this intermediate, the first time that this has been accomplished for any material. Evidence for a precursor intermediate is also afforded from temperature-programmed desorption and density functional theory calculations. The activation barrier separating the precursor species from the chemisorbed state is shown to correlate with a change in the Cu+ coordination environment that enhances π-backbonding with H2. Ultimately, these findings demonstrate that adsorption at framework metal sites does not always follow a concerted pathway and underscore the importance of probing kinetics in the design of next-generation adsorbents.

Numerical Investigation on the Effect of the Oxymethylene Ether-3 (OME3) Blending Ratio in Premixed Sooting Ethylene Flames

Synthetic fuels, especially oxygenated fuels, which can be used as blending components, make it possible to modify the emission properties of conventional fossil fuels. Among oxygenated fuels, one promising candidate is oxymethylene ether-3 (OME3). In this work, the sooting propensity of ethylene (C2H4) blended with OME3 is numerically investigated on a series of laminar burner-stabilized premixed flames with increasing amounts of OME3, from pure ethylene to pure OME3. The numerical analysis is performed using the Conditional Quadrature Method of Moments combined with a detailed physico-chemical soot model. Two different equivalence ratios corresponding to a lightly and a highly sooting flame condition have been investigated. The study examines how different blending ratios of the two fuels affect soot particle formation and a correlation between OME3 blending ratio and corresponding soot reduction is established. The soot precursor species in the gas-phase are analyzed along with the soot volume fraction of small nanoparticles and large aggregates. Furthermore, the influence of the OME3 blending on the particle size distribution is studied applying the entropy maximization concept. The effect of increasing amounts of OME3 is found to be different for soot nanoparticles and larger aggregates. While OME3 blending significantly reduces the amount of larger aggregates, only large amounts of OME3, close to pure OME3, lead to a considerable suppression of nanoparticles formed throughout the flame. A linear correlation is identified between the OME3 content in the fuel and the reduction in the soot volume fraction of larger aggregates, while smaller blending ratios may lead to an increased number of nanoparticles for some positions in the flame for the richer flame condition.

Thiolation behaviors of methanol catalyzed by bifunctional ZSM-5@t-ZrO2 catalyst

The catalytic properties of bifunctional ZSM-5@t-ZrO2 catalyst for methanol thiolation were revealed by using methanol and H2S as probe molecules. Taking the ZSM-5/t-ZrO2 physically-blended catalyst, pure ZSM-5 and t-ZrO2 as control catalysts, we investigated the characteristics of adsorption and transformation of different reaction molecules on or over different catalysts by combination of in-situ diffuse reflectance Fourier transform infrared spectroscopy (Drifts) and a variety of techniques including XRD, XPS, XRF, FT-IR, N2 adsorption-desorption, CO2/NH3-TPD, and DSC. The results showed that the synergistic effect of acid sites between ZSM-5 phase and t-ZrO2 phase in the bifunctional catalyst enhanced the adsorption and dissociation of methanol molecules, while the base sites in t-ZrO2 phase were mainly responsible for the adsorption and dissociation of H2S molecules. Due to the small specific surface area of pure t-ZrO2 catalyst, precursor species for sulfur deposition and carbon deposition were easily formed. Presulfurization could improve the initial activity of methanol thiolation and shorten the induction period. The dissociation of H2S at the base sites was the rate-determining step of the bimolecular reaction, and the appropriate increase of base sites in the bifunctional components could construct the matching formation rate of sulfhydryl and methoxy groups. At the same time, the special composite structure and meso-microporous system of ZSM-5@t-ZrO2 could effectively reduce the formation rate of carbon and sulfur deposits.

Direct-simulation Monte Carlo modeling of reactor-scale gas-dynamic phenomena in a multiwafer atomic-layer deposition batch reactor

Atomic layer deposition (ALD) using multiwafer batch reactors has now emerged as the manufacturing process of choice for modern microelectronics at a massive scale. Stringent process requirements of thin film deposition uniformity within wafer (WiW) and wafer–wafer (WTW) in the batch, film conformity along submicrometer wafer features, thin film quality, and the utilization of expensive precursors in the reactor dictate ALD reactor design and process parameter optimization. This paper discusses a particle-based direct-simulation Monte Carlo (DSMC) of the full reactor scale simulation that overcomes the low Knudsen number limitation of typical continuum computational fluid dynamics approaches used for modeling low-pressure ALD reactors. A representative industrial multiwafer batch reactor used for the deposition of Si-based thin films with N2 and Si2Cl6 (hexachlorodisilane) as process feed gases with pressures in the range 43–130 Pa and a uniform reactor temperature of 600 °C is simulated. The model provides detailed insights into the flow physics associated with the transport of the precursor species from the inlets, through wafer feed nozzles, into the interwafer regions, and finally through the outlet. The reactor operating conditions are shown to be in the slip/transitional flow regime for much of the reactor volume and especially the feed gas nozzle and interwafer regions (where the Knudsen number approaches ∼0.2), justifying the need for a high-Knudsen number DSMC approach as in this work. For the simulated conditions, the nonuniformity of precursor species immediately above the wafer surface is predicted to be within <1% for a given wafer and <2% across the entire multiwafer stack. Results indicate that higher pressure degrades WiW and WTW uniformity. A reactor flow efficiency is defined and found to be ∼99%, irrespective of the chamber pressure.

Computational Simulation of a Hot Filament Chemical Vapor Deposition Process for Depositing SRO Films

In the present report, a two dimensional (2D) model was developed to describe the fluid dynamics, heat and mass transfer of a Chemical Vapor Deposition activated by a Hot Filament (HFCVD) reactor, as well as the chemical generation of the precursor species which are present in the growth of non-stoichiometric silicon rich oxide (SRO) films. The SRO is known for have excellent photo luminescent properties which are useful in optoelectronic applications. This material can be obtained by the HFCVD technique which offers important advantages such as the easily to obtain thin films with diverse structural, compositional and optical characteristics. During deposition is a priority to control key parameters as inlet flow, substrate temperature and pressure so it compels to know previous theoretical information about these parameters which can be obtained by computational simulation. Therefore, by means of commercial Computational Fluid Dynamics (CFD) were solved the continuity, momentum and energy equations in steady state. Also, a thermodynamic equilibrium study of the SiO2(s) + H2 (g) reaction was carried out with the Factsage software. The thermodynamic equilibrium results provide the main chemical species which are present during the deposit process of the SRO films. The 2D model was used to simulate the temperature and velocity distribution of the hydrogen in the deposit process. The theoretical calculated temperatures were compared with those obtained experimentally by thermocouple measurements. From the simulation results, the temperature and gas velocity profiles were obtained at different hydrogen flow levels (50, 75, 100 sccm) and temperature source-substrate distances (5, 6 and 7mm) for a 50 sccm level. SEM micrographs and profilometry measurements disclose that the outlet configuration affects substantially both the thickness and surface uniformity of the SRO films. This parameter was modified to obtain a better quality (thickness and uniformity) and a large deposit area.

Effect of Na on the condensation reaction of naphthalene molecules during coal pyrolysis

The soot produced in the process of coal pyrolysis seriously affect the atmosphere environment and health of human beings. This study used naphthalene-the most abundant precursor species in coal tar-was used as a raw material to conduct pyrolysis experiments in a self-designed drop tube furnace, combined with density functional theory, to explore the influence mechanism of Na in the formation of coal-derived soot. The microstructure and functional group information of soot derived from the pyrolysis of naphthalene are obtained through transmission electron microscopy, infrared spectroscopy, Raman spectroscopy and XPS analysis. The experimental result shows that Na can inhibit the aggregation of polycyclic aromatic hydrocarbons, resulting in a shorter average length of graphite-like crystallites in the soot particles, and promoting the oxidation of the soot surface. The simulation result shows that Na inhibits the polymerization of aromatic rings. These experiments and simulation results show that the ions formed by gaseous Na form a Na+-π structure with naphthalene, which increases the energy barrier of the reaction between naphthalene molecules and naphthalene radicals and inhibits the polymerization of aromatic rings.

Correlation of early-stage growth process conditions with dislocation evolution in MOCVD-based GaP/Si heteroepitaxy

To identify the complex relationships between early-stage growth processes and the resultant defect microstructure in GaP/Si heteroepitaxy, a holistic study of several key metal–organic chemical vapor deposition (MOCVD) parameters was conducted, focusing on Si surface preparation and GaP atomic layer epitaxy (ALE) based nucleation processes. Crystalline defects related to the lattice mismatch and/or interfacial heterovalency, namely misfit dislocations (MD), threading dislocations (TD), and stacking fault pyramids (SFP), were quantitatively characterized via electron channeling contrast imaging (ECCI) and correlated against the different process variations. Choice of Si surface preparation method between the two examined (dilute SiH4 annealing versus Si2H6 based homoepitaxy) had little impact on resultant GaP film morphology and defect content, whereas differing GaP ALE nucleation conditions produced much more substantial changes. In particular, the initial precursor species (tert-butylphosphine versus triethygallium) and ALE cycle purge times both yielded significant influence over threading dislocation densities (TDD) in thin (100 nm), post-critical thickness GaP/Si films, with TDD spanning two orders of magnitude, from 6.7 × 107 cm−2 to 7.1 × 105 cm−2, depending on the specific process conditions employed. SFP densities were also found to follow a similar trend, ranging from 2.0 × 107 cm−2 to 1.8 × 105 cm−2, but with no apparent causal relationship between SFP density and TDD. To help explain the dramatic differences observed, detailed, large-area MD network characterization was used to provide statistically-relevant quantitative analyses of the critical dislocation dynamics (introduction rates and glide velocities) associated with the different process variants. These extracted values are then correlated against the ALE process variants to provide insight into the potential mechanistic roles of the different growth processes.

Investigation on formation of thin Si-B-N films on stainless steel by plasma chemical vapor deposition

Amorphous Si-B-N alloy films on SS304 stainless steel substrates prepared by using radio frequency plasma chemical vapor deposition (RF-PCVD) from the mixture gases of N2, Ar, B2H6 and SiH4. It is found that both hardness and wear resistance of the samples with film coating were improved significantly. There are N, Si, and B existing in deposited films through the XPS and the FT-IR measurement. SEM images of the film surface presents the morphology of hilly clusters composed of small particles. Energy dispersive spectrometry (EDS) and glow discharge optical emission spectrometry (GD-OES) were used to investigate the early nucleation and growth. At the early growth stage of 5 min, the continuous film formed is composed of small particles with a diameter of tens of nanometers on the substrate, suggesting that the precursor species easily nucleate on the stainless steel surface. The examination of cross-section for film coating indicates that an interface layer with diffusion forms during the deposition process, which is attributed to highly reactive species containing silicon, boron and nitrogen generated in discharging plasma. Those have high enough energy to induce diffusion effect in interface layer.

Combustion kinetics of alternative jet fuels, Part-I: Experimental flow reactor study

A comprehensive collection of technical aviation fuels enabled an experimental and numerical study on detailed combustion chemistry and pollutant formation presented in a series of 3 interlinking parts. Part-I: Experimental Flow Reactor Study focuses on the characterization of 42 technical jet fuels and provides experimental speciation data for model development presented in Part-II: Model and Surrogate Strategy. Model validation based on the presented technical fuels here is presented in Part-III: Model Application on Technical Jet Fuels.The fuels investigated in this study cover a broad range of approved SAFs (Sustainable Aviation Fuels), candidates for approval, and technical products outside the present ASTM-D7566 specification and is completed by reference fuels (ASTM-D1655). This includes SAF components such as HEFA (Hydroprocessed Esters and Fatty Acids), ATJ (Alcohol-To-Jet), SIP (Synthesized Iso-Paraffins), and Fischer-Tropsch-products as well as their blends.A systematic investigation of the soot precursor chemistry by analyzing the influence of the complex chemical fuel composition on the intermediate species pool is presented. The experimental set-up consists of an atmospheric flow reactor with coupled molecular-beam mass spectrometer (MBMS). Quantitative evolution of combustion reaction intermediates is recorded for fuel-rich (Φ = 1.2) and fuel-lean (Φ = 0.8) conditions at intermediate temperatures up to 1200 K including small intermediate species (e.g. ethylene, butene) and soot precursor species (e.g. benzene, naphthalene, phenanthrene).A general systematic dependency of the soot precursor concentration on the degree of unsaturation (Index of Hydrogen Deficiency) or the hydrogen content, respectively, is demonstrated. Furthermore, larger soot precursor concentrations depend on the naphthalene content of the fuel.

Alkali influence on ZnO and Ag-doped ZnO nanostructures formation using the microwave-assisted hydrothermal method for fungicidal inhibition

This study reports on the effect of the alkali source in pure ZnO and Ag-doped ZnO samples formation quickly synthesized using the microwave-assisted hydrothermal (MAH) method. The flower-like morphology of ZnO and Ag-doped ZnO samples was controlled by the presence of ammonia under reaction conditions, which provided slower ZnO nucleation. In the presence of sodium hydroxide, the precursor species were instantaneously formed, promoting a rapid ZnO formation and the obtainment of Ag0 in the Ag-doped ZnO sample. The presence of Ag+ ions into ZnO wurtzite structure created defects, contributing to a local structural disorder, as observed by Raman spectra. All the samples studied herein presented antifungal activity for Saccharomyces cerevisiae, which was influenced because of the presence of Ag+ ions into ZnO lattice and the morphologies of the samples.

Smog Chamber Study on the Ozone Formation Potential of Acetaldehyde

Acetaldehyde is one of the important VOC species of O3 precursors in the atmospheric environment. The influences of relative humidity (RH) and initial VOC/NOx ratio (RCN) on the formation of O3 are studied in smog chamber experiments, and the MCM v3.3.1 mechanism of acetaldehyde is modified based on the experimental results. In low-RH conditions (RH = 11.6%±1.1%), the O3 concentration at 6 h increases first and then decreases with the increase of RCN, and the RCN at the inflection point of O3 concentrations is 3.2. In high-RH experiments (RH = 78.8%±1.0%), variation of the O3 concentration at 6 h with RCN is similar to that in low-RH experiments, but the RCN at the inflection point is 2.8. RH has no significant effect on the O3 concentrations under low RCN ( 3). Compared with the experimental results, original MCM v3.3.1 greatly underestimates the O3 concentrations. Addition of both the photolysis process of peroxyacetyl nitrate and the photolysis process of HNO3 on the reactor surface into the original MCM can reduce the difference between the simulated O3 concentrations and the experimental results at 6 h from 24%−35% and 17%−49% to 6%−26% and 10%−42% under low- and high-RH conditions, respectively. The maximum incremental reactivity (MIR) of acetaldehyde simulated with the modified MCM is 4.0 ppb ppb−1 without considering the effect of other VOCs.

Synthesis of ordered mesoporous carbon by soft template method

Much attention has been given to mesoporous carbons incorporated through soft template method because of its simple blend and easy power over the determined porous framework. Related to delicate template methods for mesoporous oxides of metal, its combination depends upon succession of shaping molecular plan of action of precursor species with delicate layouts, adjustment of the precursor system by polymerization lastly the template expulsion. Utilizing micelles of amphiphilic square copolymers as templates, effortless command over the structure and size of mesopores can be accomplished and centralization of the polymer template or synthesis and level of precursor polymerization. We depict recent synthesis models and use of mesoporous carbon materials prepared by soft template method. In addition, we emphasize central standards of self-accumulation, feature proposed blend components and present methods for regulating pore size.

Ni-modified Fe3O4(001) surface as a simple model system for understanding the oxygen evolution reaction

Electrochemical water splitting is an environmentally friendly technology to store renewable energy in the form of chemical fuels. Among the earth-abundant first-row transition metal-based catalysts, mixed Ni-Fe oxides have shown promising performance for effective and low-cost catalysis of the oxygen evolution reaction (OER) in alkaline media, but the synergistic roles of Fe and Ni cations in the OER mechanism remain unclear. In this work, we report how addition of Ni changes the reactivity of a model iron oxide catalyst, based on Ni deposited on and incorporated in a magnetite Fe3O4(001) single crystal, using a combination of surface science techniques in ultra-high vacuum such as low energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS), and scanning tunneling microscopy (STM), as well as atomic force microscopy (AFM) in air, and electrochemical methods such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in alkaline media. A significant improvement in the OER activity is observed when the top surface presents an iron fraction among the cations in the range of 20-40%, which is in good agreement with what has been observed for powder catalysts. Furthermore, a decrease in the OER overpotential is observed following surface aging in electrolyte for three days. At higher Ni load, AFM shows the growth of a new phase attributed to an (oxy)-hydroxide phase which, according to CV measurements, does not seem to correlate with the surface activity towards OER. EIS suggests that the OER precursor species observed on the clean and Ni-modified surfaces are similar and Fe-centered, but form at lower overpotentials when the surface Fe:Ni ratio is optimized. We propose that the well-defined Fe3O4(001) surface can serve as a model system for understanding the OER mechanism and establishing the structure-reactivity relation on mixed Fe-Ni oxides.

Open-atmosphere flame synthesis of monolayer graphene

An open-atmosphere, unconfined setup comprising a novel multiple inverse-diffusion flame (m-IDF) burner modified with extended precursor tubes is employed to synthesize graphene on substrates. Growth conditions of mono-, bi-, and few-layer graphene (MLG, BLG, and FLG, respectively) are investigated, with systematic variation of parameters such as substrate temperature, methane-to-hydrogen volume flow rate ratio (JCH4:JH2), growth duration, post-flame flow profiles, substrate material, precursor species (e.g., CH4, C2H2, C2H4), and in-situ post-growth hydrogen annealing. Graphene growth on copper is observed for a wide range of temperatures from 850 °C to 1000 °C, with high-quality BLG created at a substrate temperature of 1000 °C with JCH4:JH2 of 1:100 for 5 min growth duration. A sequential in-situ post-growth hydrogen annealing treatment, where the hydrocarbon precursor flow is terminated but the hydrogen m-IDFs are maintained, is found to be effective for etching adlayers of graphene. As such, BLG is reduced to MLG by increasing the post-growth hydrogen annealing duration at 1000 °C to 10 min. In-situ gas-phase Raman measurements characterize the evolution of the gas-phase precursor species in the synthesis flow field. CH2 is determined to be the main gas-phase carbon species needed near the substrate to form graphene in our flame synthesis system.

Photolysis of acetonitrile in a water-rich ice as a source of complex organic molecules: CH3CN and H2O:CH3CN ices

Context. Many C-, O-, and H-containing complex organic molecules (COMs) have been observed in the interstellar medium (ISM) and their formation has been investigated in laboratory experiments. An increasing number of recent detections of large N-bearing COMs motivates our experimental investigation of their chemical origin. Aims. We investigate the potential role of acetonitrile (CH3CN) as a parent molecule to N-bearing COMs, motivated by its omnipresence in the ISM and structural similarity to another well-known precursor species, CH3OH. The aim of the present work is to characterize the chemical complexity that can result from vacuum UV photolysis of a pure CH3CN ice and a more realistic mixture of H2O:CH3CN. Methods. The CH3CN ice and H2O:CH3CN ice mixtures were UV irradiated at 20 K. Laser desorption post ionization time-of-flight mass spectrometry was used to detect the newly formed COMs in situ. We examined the role of water in the chemistry of interstellar ices through an analysis of two different ratios of H2O:CH3CN (1:1 and 20:1). Results. We find that CH3CN is an excellent precursor to the formation of larger nitrogen-containing COMs, including CH3CH2CN, NCCN/CNCN, and NCCH2CH2CN. During the UV photolysis of H2O:CH3CN ice, the water derivatives play a key role in the formation of molecules with functional groups of: imines, amines, amides, large nitriles, carboxylic acids, and alcohols. We discuss possible formation pathways for molecules recently detected in the ISM.

Causes of deactivation of an amorphous silica-alumina catalyst used for processing of thermally cracked naphtha in a bitumen partial upgrading process

Thermally cracked naphtha represents a challenging feed for many catalytic processes. Its contaminant content and reactivity cause the deactivation of catalysts. Nevertheless, the use of an amorphous silica-alumina acid catalyst to convert and reduce the alkene content in thermally cracked naphtha was possible. The purpose of this study was to determine the cause(s) of catalyst deactivation by analysis of spent catalysts after conversion of cracked naphtha at different conditions in the range 250–350 °C, 6 MPa and WHSV of 0.5–2 h−1. It was found that nitrogen bases, suspected to be important acid catalyst poisons, were not the main cause of catalyst deactivation. Nitrogen was more abundant in deposits on the catalyst at the inlet compared to the outlet of the reactor, but the accumulated nitrogen in deposits represented only a minor fraction of the total amount of basic nitrogen to which the catalyst was exposed. Carbonaceous deposits were the main cause of catalyst deactivation and the profile of the deposition on the catalyst changed with temperature. At 325 °C the amount of deposits at the reactor outlet was higher, with lower H/C ratio and higher persistent free radical content than at the reactor inlet. Although some of the precursor species that formed deposits were present in the feed, some of the precursor species that formed deposits were produced during the conversion process. Although the contribution of acid catalysis was not ruled out, many observations in the study indicated that carbonaceous deposits formed mainly due to free radical reactions.

Surface-Directed Mineralization of Fibrous Collagen Scaffolds in Simulated Body Fluid for Tissue Engineering Applications.

The use of polymer additives that stabilize fluidic amorphous calcium phosphate is key to obtaining intrafibrillar mineralization of collagen in vitro. On the other hand, this biomimetic approach inhibits the nucleation of mineral crystals in unconfined extrafibrillar spaces, that is, extrafibrillar mineralization. The extrafibrillar mineral content is a significant feature to replicate from hard connective tissues such as bone and dentin as it contributes to the final microarchitecture and mechanical stiffness of the biomineral composite. Herein, we report a straightforward route to produce densely mineralized collagenous composites via a surface-directed process devoid of the aid of polymer additives. Simulated body fluid (1×) is employed as a biomimetic crystallizing medium, following a preloading procedure on the collagen surface to quickly generate the amorphous precursor species required to initiate matrix mineralization. This approach consistently leads to the formation of extrafibrillar bioactive minerals in bulk collagen scaffolds, which may offer an advantage in the production of osteoconductive collagen-apatite materials for tissue engineering and repair purposes.

Heterogeneous solar photo-Fenton treatment of industrial wastewater via δ-FeOOH

The wastewater from the textile industry has been treated with heterogeneous solar photo-Fenton using iron oxyhydroxides (δ-FeOOH and FeOOH)nanoparticles. δ-FeOOH and FeOOH catalysts have been prepared, respectively, from ferrous and ferric ions as precursor species using an easy and low-cost method. The FeOOH catalyst exhibits slightly higher catalytic activity than δ-FeOOH in the heterogeneous solar photo-Fenton process but is less stable. The oxidation efficiency of basic blue 9 and acid green 50, analytical textile dyes, is compared to that of wastewater dye. The as-prepared catalysts are highly efficient for the wastewater treatment and the synthetic solutions prepared from the analytical textile dyes. High mineralization (over 90%) of the organic components of wastewater was achieved at 5 h of solar photo-Fenton treatment.

Simulated annealing fitting: a global optimization method for quantitatively analyzing growth kinetics of colloidal Ag nanoparticles.

The involvement of heterogeneous solid/liquid reactions in growing colloidal nanoparticles makes it challenging to quantitatively understand the fundamental steps that determine nanoparticles' growth kinetics. A global optimization protocol relying on simulated annealing fitting and the LSW growth model is developed to analyze the evolution data of colloidal silver nanoparticles synthesized from a microwave-assisted polyol reduction reaction. Fitting all data points of the entire growth process determines with high fidelity the diffusion coefficient of precursor species and the heterogeneous reduction reaction rate parameters on growing silver nanoparticles, which represent the principal functions to determine the growth kinetics of colloidal nanoparticles. The availability of quantitative results is critical to understanding the fundamentals of heterogeneous solid/liquid reactions, such as identifying reactive species and reaction activation energy barriers.