Reduction of (100)-Faceted CeO2 for Effective Pt Loading.

Although the function and stability of catalysts are known to significantly depend on their dispersion state and support interactions, the mechanism of catalyst loading has not yet been elucidated. To address this gap in knowledge, this study elucidates the mechanism of Pt loading based on a detailed investigation of the interaction between Pt species and localized polarons (Ce3+) associated with oxygen vacancies on CeO2(100) facets. Furthermore, an effective Pt loading method was proposed for achieving high catalytic activity while maintaining the stability. Enhanced dispersibility and stability of Pt were achieved by controlling the ionic interactions between dissolved Pt species and CeO2 surface charges via pH adjustment and reduction pretreatment of the CeO2 support surface. This process resulted in strong interactions between Pt and the CeO2 support. Consequently, the oxygen-carrier performance was improved for CH4 chemical looping reforming reactions. This simple interaction-based loading process enhanced the catalytic performance, allowing the efficient use of noble metals with high performance and small loading amounts.

Fusion Growth and Extraordinary Distortion of Ultrasmall Metal Oxide Nanoparticles.

Ultrasmall metal oxide nanoparticles (<5 nm) potentially have new properties, different from conventional nanoparticles. The precise size control of ultrasmall nanoparticles remains difficult for metal oxide. In this study, the size of CeO2 nanoparticles was precisely controlled (1.3-9.4 nm) using a continuous-flow hydrothermal reactor, and the atomic distortion that occurs in ultrasmall metal oxides was explored for CeO2. The crystalline nanoparticles grow rapidly like droplets via coalescence, although they reach a critical particle size (∼3 to 4 nm), beyond which they grow slowly and change shape through ripening. In the initial growth stage, the ultrasmall nanoparticles exhibit disordered atomic configurations, including stacking faults. In ultrasmall CeO2 nanoparticles (<3 to 4 nm), unusual electron localization occurs on Ce 4f orbitals (Ce3+) as a result of O disordering, regardless of O vacancy concentration. This behavior differs from ordinary electron localization caused by the presence of O vacancies. The ultrasmall metal oxides have extraordinary distortion states, making them promising for use in nanotechnology applications. Furthermore, the proposed synthesis method can be applied to various other metal oxides and allows exploration of their properties.

Enhanced photocatalytic performance of SnS2 under visible light irradiation: strategies and future perspectives.

Tin(II) sulfide (SnS2) has emerged as a promising candidate for visible light photocatalytic materials. As a member of the transition metal dichalcogenides (TMDs) family, SnS2 features a band gap of approximately 2.20 eV and a layered structure, rendering it suitable for visible light activation with a high specific surface area. However, the application of SnS2 as a visible light photocatalyst still requires improvement, particularly in addressing the high recombination of electrons and holes, as well as the poor selectivity inherent in its perfect crystal structure. Therefore, ongoing research focuses on strategies to enhance the photocatalytic performance of SnS2. In this comprehensive review, we analyze recent advances and promising strategies for improving the photocatalytic performance of SnS2. Various successful approaches have been reported, including controlling the reactive facets of SnS2, inducing defects in the crystal structure, manipulating morphologies, depositing noble metals, and forming heterostructures. We provide a detailed understanding of these phenomena and the preparation techniques involved, as well as future considerations for exploring new science in SnS2 photocatalysis and optimizing performance.

Editorial for the Special Issue: "Hydrothermal Synthesis of Nanoparticles".

Research and development in materials science has improved tremendously over the past few decades, resulting in benefits to the quality of life of people worldwide [...].

Forced Convective Heat Transfer Coefficient Measurement of Low Concentration Nanorods ZnO-Ethylene Glycol Nanofluids in Laminar Flow.

This paper presents the experimental forced convective heat transfer coefficient (HTC) of nanorods (NRs) zinc oxide-ethylene glycol nanofluids (ZnO-EG NFs) in laminar flow. First, ZnO NRs were synthesized using a hydrothermal method that uses zinc acetate dihydrate [Zn(CH3COO)2·2H2O] as a precursor, sodium hydroxide as a reducing agent, and polyvinylpyrrolidone (PVP) as a surfactant. The hydrothermal reaction was performed at 170 °C for 6 h in a Teflon-lined stainless-steel tube autoclave. The sample's X-ray diffraction (XRD) pattern confirmed the formation of the hexagonal wurtzite phase of ZnO, and transmission electron microscopy (TEM) analysis revealed the NRs of the products with an average aspect ratio (length/diameter) of 2.25. Then, 0.1, 0.2, and 0.3 vol% of ZnO-EG NFs were prepared by adding the required ZnO NRs to 100 mL of EG. After that, time-lapse sedimentation observation, zeta potential (ζ), and ultraviolet-visible (UV-vis) spectroscopy was used to assess the stability of the NFs. Furthermore, the viscosity (µ) and density (ρ) of NFs were measured experimentally as a function of vol% from ambient temperature to 60 °C. Finally, the HTC of NFs was evaluated utilizing a vertical shell and tube heat transfer apparatus and a computer-based data recorder to quantify the forced convective HTC of NFs in laminar flow at Reynolds numbers (Re) of 400, 500, and 600. The obtained results indicate that adding only small amounts of ZnO NRs to EG can significantly increase the HTC, encouraging industrial and other heat management applications.

Recent advances in hydrothermal synthesis of facet-controlled CeO2-based nanomaterials.

CeO2-based nanomaterials have received tremendous attention due to their variety of applications. This paper is focused on the recent advances in facet-controlled CeO2-based nanomaterials by the hydrothermal method. CeO2-based nanomaterials with controllable size and exposed facets can be prepared by adjusting the reaction parameters. Moreover, doping and loading metals can improve the oxygen storage capacity (OSC) of CeO2 and its catalytic activity. Various research studies on catalytic applications such as CO oxidation, water-gas shift reaction (WGSR), decomposition of hydrocarbons, and photocatalytic reaction have been carried out to exhibit the high potential of facet-controlled CeO2 nanomaterials. This review will provide readers with various ideas for facet-controlled CeO2-based nanomaterials.

Fabrication of Liquid Scintillators Loaded with 6-Phenylhexanoic Acid-Modified ZrO2 Nanoparticles for Observation of Neutrinoless Double Beta Decay.

The observation of neutrinoless double beta decay is an important issue in nuclear and particle physics. The development of organic liquid scintillators with high transparency and a high concentration of the target isotope would be very useful for neutrinoless double beta decay experiments. Therefore, we propose a liquid scintillator loaded with metal oxide nanoparticles containing the target isotope. In this work, 6-phenylhexanoic acid-modified ZrO2 nanoparticles, which contain 96Zr as the target isotope, were synthesized under sub/supercritical hydrothermal conditions. The effects of the synthesis temperature on the formation and surface modification of the nanoparticles were investigated. Performing the synthesis at 250 and 300 °C resulted in the formation of nanoparticles with smaller particle sizes and higher surface modification densities than those prepared at 350 and 400 °C. The highest modification density (3.1 ± 0.2 molecules/nm2) and Zr concentration of (0.33 ± 0.04 wt.%) were obtained at 300 °C. The surface-modified ZrO2 nanoparticles were dispersed in a toluene-based liquid scintillator. The liquid scintillator was transparent to the scintillation wavelength, and a clear scintillation peak was confirmed by X-ray-induced radioluminescence spectroscopy. In conclusion, 6-phenylhexanoic acid-modified ZrO2 nanoparticles synthesized at 300 °C are suitable for loading in liquid scintillators.

One-Pot Hydrothermal Synthesis of Victoria Green (Ca3Cr2Si3O12) Nanoparticles in Alkaline Fluids and Its Colour Hue Characterisation.

One-pot hydrothermal preparation of Ca3Cr2Si3O12 uvarovite nanoparticles under alkaline conditions was investigated for the first time. The experimental parameters selected for the study considered the concentration of the KOH solvent solution (0.01 to 5.0 M), the agitation of the autoclave (50 rpm), and the nominal content of Si4+ (2.2-3.0 mole). Fine uvarovite particles were synthesised at 200 °C after a 3 h interval in a highly concentrated 5.0 M KOH solution. The crystallisation of single-phase Ca3Cr2Si3O12 particles proceeded free of by-products via a one-pot process involving a single-step reaction. KOH solutions below 2.5 M and water hindered the crystallisation of the Ca3Cr2Si3O12 particles. The hydrothermal treatments carried out with stirring (50 rpm) and non-stirring triggered the crystallisation of irregular anhedral particles with average sizes of 8.05 and 12.25 nm, respectively. These particles spontaneously assembled into popcorn-shaped agglomerates with sizes varying from 66 to 156 nm. All the powders prepared by the present method exhibited CIE-L*a*b* values that correspond to the Victoria green colour spectral space and have a high near infrared reflectance property. The particle size and structural crystallinity are factors affecting the Victoria pigment optical properties, such as CIE-L*a*b* values, green tonality, and near-infrared reflectance.

Solvent accommodation effect on dispersibility of metal oxide nanoparticle with chemisorbed organic shell.

The dispersibility of nanoparticles in solvents remains difficult to predict and control. In this paper, the dispersibility of organically-modified nanoparticles in various solvents with different solvent properties and molecular sizes are investigated. The study indicates that solvent molecular size, in addition to the affinity between organic modifier and solvent molecules, affects the dispersibility of the nanoparticles. The experimental results imply that solvents with molecular size small enough can disperse nanoparticles more efficiently. In addition, based on the concept that solvent accommodation induces the enhancement of dispersibility, two approaches to improve nanoparticle dispersibility in desired solvents are proposed. One is the addition of a small amount of solvent with the right size and properties to both penetrate the modifier shell and to act as intermediate between the desired solvent and the organic modifier molecules. The other is dual-molecule modification to create additional space at modifier-shell surface for the penetration of the desired solvent molecules. The results of these approaches based on the concept of the solvent accommodation can enhance the dispersibility trends.

Atomic-Scale Valence State Distribution inside Ultrafine CeO2 Nanocubes and Its Size Dependence.

Atomic-scale analysis of the cation valence state distribution will help to understand intrinsic features of oxygen vacancies (VO ) inside metal oxide nanocrystals, which, however, remains a great challenge. In this work, the distribution of cerium valence states across the ultrafine CeO2 nanocubes (NCs) perpendicular to the {100} exposed facet is investigated layer-by-layer using state-of-the-art scanning transmission electron microscopy-electron energy loss spectroscopy. The effect of size on the distribution of Ce valence states inside CeO2 NCs is demonstrated as the size changed from 11.8 to 5.4 nm, showing that a large number of Ce3+ cations exist not only in the surface layers, but also in the center layers of smaller CeO2 NCs, which is in contrast to those in larger NCs. Combining with the atomic-scale analysis of the local structure inside the CeO2 NCs and theoretical calculation on the VO forming energy, the mechanism of size effect on the Ce valence states distribution and lattice expansion are elaborated: nano-size effect induces the overall lattice expansion as the size decreased to ≈5 nm; the expanded lattice facilitates the formation of VO due to the lower formation energy required for the smaller size, which, in principle, provides a fundamental understanding of the formation and distribution of Ce3+ inside ultrafine CeO2 NCs.

Green solvent for green materials: a supercritical hydrothermal method and shape-controlled synthesis of Cr-doped CeO2 nanoparticles.

This paper describes a supercritical hydrothermal synthesis method as a green solvent process, along with products based on this method that can be used as green materials that contribute to solving environmental problems. The first part of this paper summarizes the basics of this method, including the mechanism of the reactions, specific features of the supercritical state for nanoparticle synthesis, the continuous flow-type reactor and applications; this provides a better understanding of the suitability of this method to synthesize green materials. The second part of the paper describes the method used to synthesize Cr-doped CeO(2) nanoparticles, which show an extremely high oxygen storage capacity, suggesting their high potential as an environmental catalyst. Transmission electron microscopy and scanning electron microscope images showed octahedral Cr-doped CeO(2) nanoparticles with sizes of 15-30 nm and cubic Cr-doped CeO(2) nanoparticles with sizes of 5-8 nm. Octahedral Cr-doped CeO(2) nanoparticles exposing (111) facets and cubic Cr-doped CeO(2) nanoparticles exposing (100) facets were determined by high-resolution transmission electron microscopy and selected area electron diffraction. The X-ray diffraction peaks shifted to a high angle because the radius of the Cr ion is smaller than that of the Ce ion.

The reductive supercritical hydrothermal process, a novel synthesis method for cobalt nanoparticles: synthesis and investigation on the reaction mechanism.

Highly crystalline cobalt nanoparticles with low surface oxidation were synthesized by the reductive supercritical hydrothermal process in the temperature range from 340 to 420 °C. Under these reaction conditions, hydrogen generated from formic acid decomposition is maximally soluble in water, enabling the effective reduction of cobalt ions and cobalt oxide. The reaction mechanism was investigated by kinetic analysis on the formation of cobalt nanoparticles. This analysis assumed the first order irreversible reaction and two different types of shrinking core models (chemical reaction and inter-diffusion dominated). According to the proposed reaction mechanism, cobalt monoxide is probably formed at the early reaction stage, where insufficient H2 is available, or under high temperature conditions. Moreover, cobalt monoxide influences the entire reaction rate. Thus, suppressing the formation and growth of cobalt monoxide is of primary importance in the optimal synthesis of cobalt nanoparticles by the reductive supercritical hydrothermal process.