Nucleation of Hematite: A Nonclassical Mechanism

Hematite (α-Fe₂O₃) is thermodynamically stable under ambient conditions, of vast geological importance, and widely used in applications, for example, as corrosion protection and as a pigment. It forms at elevated temperatures, whereas room-temperature reactions typically yield metastable akaganéite or ferrihydrite. The mechanistic key changes underlying this observation were explored in the present study. The entropic contribution to the prenucleation hydrolysis reaction categorically implies the presence of prenucleation clusters (PNCs) as fundamental precursors. The formation of hematite is then due to a change in the reaction mechanism above approximately 50 °C, whereby the reaction limitation towards oxolation in phase-separated clusters is overcome. A model that rationalizes the occurrence of hematite, akaganéite, and ferrihydrite based on the chemistry of olation PNCs is proposed. Supersaturation and the temperature dependence of olation and oxolation rates from monomeric precursors are irrelevant in this nonclassical mechanism.     

Engineering Multifunctional Gold Decorated Dendritic Mesoporous Silica/Tantalum Oxide Nanoparticles for Intraperitoneal Tumor‐Specific Delivery

Nonspecific high‐energy radiation for treatment of metastatic ovarian cancer is limited by damage to healthy organs, which can be mitigated by the use of radiosensitizers and image‐guided radiotherapy. Gold (Au) and tantalum oxide (TaO_x) nanoparticles (NPs), by virtue of their high atomic numbers, find utility in the design of bimetallic NP systems capable of high‐contrast computed tomography (CT) imaging as well as a potential radiosensitizing effect. These two radio‐dense metals are integrated into dendritic mesoporous silica NPs (dMSNs) with radial porous channels for high surface‐area loading of therapeutic agents. This approach results in stable, monodispersed dMSNs with a uniform distribution of Au on the surface and TaO_x in the core that exhibits CT attenuation up to seven times greater than iodine or monometallic dMSNs without either TaO_x or Au. Tumor targeting is assessed in a metastatic ovarian cancer mouse model. Ex vivo micro‐CT imaging of collected tumors shows that these NPs not only accumulate at tumor sites but also penetrate inside tumor tissues. This study demonstrates that after intraperitoneal administration, rationally designed bimetallic NPs can simultaneously serve as targeted contrast agents for imaging tumors and to enhance radiation therapy in metastatic ovarian cancer.     

Reduced magnetic disorder at low temperature in Ca3Co2O6 via zinc substitution

ABSTRACT

The compound Ca₃Co₂O₆ undergoes a transition into a spin-density wave (SDW) state near 24?K. Below ～10?K, this unstable SDW state coexists with a nearly- degenerate commensurate antiferromagnetic state as well as short-range magnetic order. Clear signatures of this strong magnetic disorder have been observed in the response of entropy to changing magnetic field and temperature. We performed a calorimetry study of Ca₃Co₂O₆ and Ca₃Co_1.9Zn_0.1O₆ in order to compare their entropic responses at low temperature. Our results for Ca₃Co₂O₆ reveal that ΔS(T, H)?≡?S(T, H)?S(T, H?=?0) increases as either temperature or magnetic field increase. In contrast, ΔS data for Ca₃Co_1.9Zn_0.1O₆ were relatively unresponsive to changes in temperature or field, suggesting that Zn substitution may reduce the low-temperature magnetic disorder observed in Ca₃Co₂O₆. These results are discussed within the context of two cases (Ca₃Co₂O₆ under applied pressure and Ca_2.75R_0.25Co₂O₆ (R?=?Dy, Lu)) in which a single magnetic ground state is stabilised.     

Thin film photocatalysis for environmental remediation: A status review

This review accounts, various metal oxide and metal sulfide thin films available for photodegradation of several organic compounds. Due to difficulties in recycling and to avoid rigorous recollection of powder catalysts, the thin film catalyst are gaining rapid attention for photocatalytic applications. The semiconducting thin films are growing as promising photocatalyst for water treatment. This review focuses mainly on the photocatalytic activity of metal oxide thin films in terms of its stability, charge transport and absorption properties. Thin film photocatalyst provides the increased efficiency and cost reduction of device. Furthermore, this review summarizes some key factors regarding the enhancement in photocatalytic performance of thin films.     

Engineering nanostructures of CuO-based photocatalysts for water treatment: Current progress and future challenges

Nowadays, increasing extortions regarding environmental problems and energy scarcity have stuck the development and endurance of human society. The issue of inorganic and organic pollutants that exist in water from agricultural, domestic, and industrial activities has directed the development of advanced technologies to address the challenges of water scarcity efficiently. To solve this major issue, various scientists and researchers are looking for novel and effective technologies that can efficiently remove pollutants from wastewater. Nanoscale metal oxide materials have been proposed due to their distinctive size, physical and chemical properties along with promising applications. Cupric Oxide (CuO) is one of the most commonly used benchmark photocatalysts in photodegradation owing to the fact that they are cost-effective, non-toxic, and more efficient in absorption across a significant fraction of solar spectrum. In this review, we have summarized synthetic strategies of CuO fabrication, modification methods with applications for water treatment purposes. Moreover, an elaborative discussion on feasible strategies includes; binary and ternary heterojunction formation, Z-scheme based photocatalytic system, incorporation of rare earth/transition metal ions as dopants, and carbonaceous materials serving as a support system. The mechanistic insight inferring photo-induced charge separation and transfer, the functional reactive radical species involved in a photocatalytic reaction, have been successfully featured and examined. Finally, a conclusive remark regarding current studies and unresolved challenges related to CuO are put forth for future perspectives.     

SCR performance enhancement of NiMnTi mixed oxides catalysts by regulating assembling methods of LDHs-Based precursor

A series of NiMnTi mixed metal oxides (Ni/Mn-TiO₂, Mn/NiTi-LDO and TiO₂/NiMn-LDO, NiMnTi-LDO) were synthesized via different assembling methods and evaluated in the selective catalytic reduction of NO_x with NH₃(NH₃-SCR). As the results presented, catalysts via diverse assembling methods of LDHs templates afforded different catalytic denitrification (DeNO_x) performance, which might be related to the exposure degree of active constituents and the interaction intensity between metal components. Noticeably, compared with Ni/Mn-TiO₂, Mn/NiTi-LDO and TiO₂/NiMn-LDO catalysts, the NiMnTi-LDO catalyst deriving from one step in-situ method NiMnTi-LDH precursor template exhibited the most desirable performance at temperature window of 150–360 °C in NH₃-SCR (above 90% NO_x conversion with 95% N₂ selectivity). The specific structure and property of samples were correlated by means of a series of characterizations, where the results indicated that NiMnTi-LDO possessed the highest surface area, the strongest redox ability, the most abundant acid amount and the best dispersion.     

A facile route to germanium(IV) binaphthoxide complexes: crystal structure of a chiral resolved germanium(IV) binaphthoxide

A method for the facile synthesis of chiral germanium(IV) binaphthoxide complexes from the corresponding binaphthols and an organogermanium trichloride has been developed, which allows these unusual types of compounds to be synthesized in high yields. The crystal structure of one such complex, (S)-[Ge{O2C20H10(SiMe3)2-3,3'}{Cl}{Ph}], has been determined.     

Assembly of ϵ-Keggin Polyoxometalate from Molecular Crystal to Zeolitic Octahedral Metal Oxide

Zeolitic octahedral metal oxides are inorganic crystalline microporous materials with adsorption and redox properties. New ϵ-Keggin nickel molybdate–based zeolitic octahedral metal oxides have been synthesized. ³¹P NMR spectroscopy shows that reduction of Mo^VI-based molybdates forms an ϵ-Keggin polyoxometalate that immediately transfers to the solid phase. Investigation of the formation process indicates that a low Ni concentration, insoluble reducing agent, and long synthesis time are the critical factors for obtaining the zeolite octahedral metal oxides rather than the ϵ-Keggin polyoxometalate molecule. The synthesized zeolitic nickel molybdate with Na⁺ is used as the adsorbent, which effectively separates C₂ hydrocarbon mixtures.     

Conductivity‐Dependent Completion of Oxygen Reduction on Oxide Catalysts

The electric conductivity‐dependence of the number of electrons transferred during the oxygen reduction reaction is presented. Intensive properties, such as the number of electrons transferred, are difficult to be considered conductivity‐dependent. Four different perovskite oxide catalysts of different conductivities were investigated with varying carbon contents. More conductive environments surrounding active sites, achieved by more conductive catalysts (providing internal electric pathways) or higher carbon content (providing external electric pathways), resulted in higher number of electrons transferred toward more complete 4e reduction of oxygen, and also changed the rate‐determining steps from two‐step 2e process to a single‐step 1e process. Experimental evidence of the conductivity dependency was described by a microscopic ohmic polarization model based on effective potential localized nearby the active sites.     

Synthesis of Nanoporous Ni‐Co Mixed Oxides by Thermal Decomposition of Metal‐Cyanide Coordination Polymers

A straightforward strategy to prepare nanoporous metal oxides with well‐defined shapes is highly desirable. Through thermal treatment and a proper selection of metal‐cyanide coordination polymers, nanoporous nickel‐cobalt mixed oxides with different shapes (i.e., flakes and cubes) can be easily prepared. Our nanoporous materials demonstrate high electrocatalytic activity for oxygen evolution reaction.