Investigative properties of CeO2 doped with niobium: A combined characterization and DFT studies

Catalytic capacity of ceria mainly stems from a facile switch in the Ce oxidation states from +4 to +4 − x. While various experimental and computational studies pinpoint the reduction chemistry of Ce atom through the creation of oxygen vacancies, the analogous process when ceria surface is decorated with cations remains poorly understood. Where such results are available, a synergy between experimental and first principle calculation is scarce. Niobium materials are evolving and their use in catalysis is being widely investigated due to their high surface acidity and thermal and chemical stability. This study aims to report structural and electronic properties of various configurations of mixed Ce–Nb oxides and elaborates on factors that underpin potential catalytic improvements. Evaluations of the samples through X-ray diffraction (XRD), Fourier transform infrared (FTIR), N2-adsorption–desorption, scanning electron microscope (SEM), energy dispersive spectroscope (EDS), and thermogravimetric (TGA) analyses are examined and discussed. First principles density functional theory (DFT) calculations provide structural features of the Ce–Nb solutions at low concentration of Nb via computing atomic charge distribution. Contraction in the lattice parameter after Nb doping was confirmed with both XRD and DFT results. SEM analysis reveals particle growth at the loading of 50 wt%. FTIR results established the Ce–Nb–O bond at 1,100 cm−1 and the TGA analysis confirms the thermal stability of Nb-doped ceria. Tetrahedral O atoms demonstrate an increase in electronegativity and this in turn facilitates catalytic propensity of the material because the O atoms will exhibit higher affinity for adsorbed reactants. Cerium oxide (CeO2) after Nb doping displays a noticeable band gap narrowing, confirming the possible improvement in the catalytic behavior. The 4d states of the Niobium pentoxide (Nb2O5) is found to fill up the 4f states of CeO2 around the Fermi energy level promoting electrons excitation in the CeO2. Reported electronic, structural, and thermal characteristics herein indicate promising catalytic applications of niobium-promoted ceria.

Arctic fog chemistry induces the unexpected growth of Aitken mode particles to CCN-active particles

<p>New particle formation (NPF) and early growth are efficient processes producing high concentrations of cloud condensation nuclei (CCNs) precursors in the Arctic marine boundary layer (AMBL). However, due to short lifetime and lack of condensable vapors, newly formed particles do often not grow beyond 50 nm and cause low CCN particle concentrations in the AMBL. Thus, even the smallest amount of Aitken mode particle growth is capable to significantly increase the CCN budget. However, the growth mechanism of Aitken-mode particles from NPF into CCN range in the Arctic is still rather unclear and was therefore investigated during the cruise campaign PASCAL in 2017.</p> <p>During PASCAL, aerosol particles measurements were performed and an unexpected rapid growth of Aitken mode particles was observed right after fog episodes. Combined field data analyses and detailed multiphase chemistry box model simulations with the CAPRAM mechanism were performed to study the underlying processes. Resulting, a new mechanism is proposed explaining how particles with d < 50 nm are able to grow into CCN size range in the Arctic without requiring high water vapor supersaturation (SS). The investigations demonstrated that the rapid post-fog particle growth of Aitken mode is related to chemical processes within the Arctic fog. The redistribution of semi-volatile acidic (e.g., methanesulfonic acid) and basic (e.g., ammonia) compounds from processed CCN-active particles to smaller CCN-inactive particles can cause a rapid particle growth of Aitken mode particles after fog evaporation enabling them to grow towards CCN size. Comparisons of the model results with Berner impactor measurements supports the proposed growth mechanism.</p> <p>Overall, this study provided new insights on how the increasing frequency of NPF and fog-related particle processing can increase in the number of CCNs and cloud droplets leading to an increased albedo of Arctic clouds and thus affect the radiative balance in the Arctic. Since fogs will occur more frequently in the Arctic as a result of climate change, this growth mechanism and a deeper knowledge on its feedbacks can be essential to understand Arctic warming.</p>

Synthesis of metallic aluminum particles by electrolysis in aqueous solution

The present work proposes a method for fabricating metallic Al particles in aqueous solution. An aqueous colloidal solution was prepared from an aqueous aluminum nitrate nonahydrate solution by electrolysis using metallic Al plates as the anode and cathode under ultrasonic irradiation in water at 25–45 °C. The sizes of the particles in the colloidal solutions prepared at 25, 35, and 45 °C were 76.3, 77.0, and 84.7 nm, respectively. The powder obtained from the colloidal solution prepared at 25 °C was not crystalline. By contrast, the powders obtained from the colloidal solutions prepared at 35 and 45 °C had a crystal structure of cubic Al and crystal sizes of 55.7 and 59.3 nm, respectively. Thus, elevated temperatures promoted both particle growth and crystal growth, which was explained by higher temperatures increasing the frequency and energy of particle collisions. The metallic Al particles were chemically stable in both an aqueous solution and the ambient atmosphere. The chemically stable metallic Al particles are expected to be used as sources for fabricating materials related to fuels, energy storage, and pigments.

Chemical composition of nanoparticles from <i>α</i>-pinene nucleation and the influence of isoprene and relative humidity at low temperature

Biogenic organic precursors play an important role in atmospheric new particle formation (NPF). One of the major precursor species is α-pinene, which upon oxidation can form a suite of products covering a wide range of volatilities. Highly oxygenated organic molecules (HOMs) comprise a fraction of the oxidation products formed. While it is known that HOMs contribute to secondary organic aerosol (SOA) formation, including NPF, they have not been well studied in newly formed particles due to their very low mass concentrations. Here we present gas- and particle-phase chemical composition data from experimental studies of α-pinene oxidation, including in the presence of isoprene, at temperatures (−50 and −30 ∘C) and relative humidities (20 % and 60 %) relevant in the upper free troposphere. The measurements took place at the CERN Cosmics Leaving Outdoor Droplets (CLOUD) chamber. The particle chemical composition was analyzed by a thermal desorption differential mobility analyzer (TD-DMA) coupled to a nitrate chemical ionization–atmospheric pressure interface–time-of-flight (CI-APi-TOF) mass spectrometer. CI-APi-TOF was used for particle- and gas-phase measurements, applying the same ionization and detection scheme. Our measurements revealed the presence of C8−10 monomers and C18−20 dimers as the major compounds in the particles (diameter up to ∼ 100 nm). Particularly, for the system with isoprene added, C5 (C5H10O5−7) and C15 compounds (C15H24O5−10) were detected. This observation is consistent with the previously observed formation of such compounds in the gas phase. However, although the C5 and C15 compounds do not easily nucleate, our measurements indicate that they can still contribute to the particle growth at free tropospheric conditions. For the experiments reported here, most likely isoprene oxidation products enhance the growth of particles larger than 15 nm. Additionally, we report on the nucleation rates measured at 1.7 nm (J1.7 nm) and compared with previous studies, we found lower J1.7 nm values, very likely due to the higher α-pinene and ozone mixing ratios used in the present study.

Chain length of bioinspired polyamines affects size and condensation of monodisperse silica particles

Polyamines play a major role in biosilicification reactions in diatoms and sponges. While the effects of polyamines on silicic acid oligomerization and precipitation are well known, the impact of polyamines chain length on silica particle growth is unclear. We studied the effects of polyamine chain length on silica particle growth and condensation in a known, simple, and salt-free biphasic reaction system; with tetraethyl orthosilicate as organic phase and polyamine dissolved in the aqueous phase. The particles at various growth stages were characterized by Cryo- Transmission Electron Microscopy, Scanning Electron Microscopy, Thermogravimetric Analysis, Zeta Potential, and solid-state NMR analysis. Polyamines were found co-localized within silica particles and the particle diameter increased with an increase in polyamine chain length, whereas silica condensation showed the opposite trend. Particle growth is proposed to progress via a coacervate intermediate while the final particles have a core shell structure with an amine-rich core and silica-rich shell. The results presented in this paper would of interest for researchers working in the field of bioinspired materials.

A Fast and Improved Tunable Aggregation Model for Stochastic Simulation of Spray Fluidized Bed Agglomeration

Agglomeration in spray fluidized bed (SFB) is a particle growth process that improves powder properties in the chemical, pharmaceutical, and food industries. In order to analyze the underlying mechanisms behind the generation of SFB agglomerates, modeling of the growth process is essential. Morphology plays an imperative role in understanding product behavior. In the present work, the sequential tunable algorithm developed in previous studies to generate monodisperse SFB agglomerates is improved and extended to polydisperse primary particles. The improved algorithm can completely retain the given input fractal properties (fractal dimension and prefactor) for polydisperse agglomerates (with normally distributed radii of primary particles having a standard deviation of 10% from the mean value). Other morphological properties strongly agreed with the experimental SFB agglomerates. Furthermore, this tunable aggregation model is integrated into the Monte Carlo (MC) simulation. The kinetics of the overall agglomeration at various operating conditions, like binder concentration and inlet fluidized gas temperature, are investigated. The present model accurately predicts the morphological descriptors of SFB agglomerates and the overall kinetics under various operating parameters.

Microwave Sintering Rapid Synthesis of Nano/Micron β-SiC from Waste Lithium Battery Graphite and Photovoltaic Silicon to Achieve Carbon Reduction

The paper describes one promising method and approach for the recycling, reuse, and co-resource treatment of waste photovoltaic silicon and lithium battery anode graphite. Specifically, this work considers the preparation of nano/micron silicon carbide (SiC) from waste resources. Using activated carbon as a microwave susceptor over a very short timeframe, this research paper shows that nano/micron β-SiC can be successfully synthesized using microwave sintering technology. The used sintering temperature is significantly faster and more energy-efficient than traditional processes. The research results show that the β-SiC particle growth morphology greatly affected by the microwave sintering time. In a short microwave sintering time, the morphology of the β-SiC product is in the form of nano/micron clusters. The clusters tended to be regenerated into β-SiC nanorods after appropriately extending the microwave sintering time. In the context of heat conversion and resource saving, the comprehensive CO2 emission reduction is significantly higher than that of the traditional SiC production method.

A microfluidic approach for synthesis and kinetic profiling of branched gold nanostructure

Automatized approaches for nanoparticle synthesis and characterization represent a great asset to their applicability in the biomedical field by improving reproducibility and standardization, which help to meet the selection criteria of regulatory authorities. The scaled-up production of nanoparticles with carefully defined characteristics, including intrinsic morphological features, minimal intra-batch, batch-to-batch, and operator variability, is an urgent requirement to elevate nanotechnology towards more trustable biological and technological applications. In this work, microfluidic approaches were employed to achieve fast mixing and good reproducibility in synthesizing a variety of gold nanostructures. The microfluidic setup allowed exploiting spatial resolution to investigate the growth evolution of the complex nanoarchitectures. By physically isolating intermediate reaction fractions, we performed an advanced characterization of the shape properties during their growth, not possible with routine characterization methods. Employing an in-house developed method to assign a specific identity to shapes, we followed the particle growth/deformation process and identified key reaction parameters for more precise control of the generated morphologies. Besides, this investigation led to the optimization of a one-pot multi-size and multi-shape synthesis of a variety of gold nanoparticles. In summary, we describe an optimized platform for highly controlled synthesis and a novel approach for the mechanistic study of shape-evolving nanomaterials.