In-Situ Constructing A Heterogeneous Layer on Lithium Metal Anodes for Dendrite-Free Lithium Deposition and High Li-ion Flux

Constructing efficient artificial solid electrolyte interface (SEI) film is extremely vital for the practical application of lithium metal batteries. Herein, a dense artificial SEI film, in which lithiophilic Zn/Li_xZn_y are uniformly but nonconsecutively dispersed in the consecutive Li⁺-conductors of Li_xSiO_y, Li₂O and LiOH, is constructed via the in situ reaction of layered zinc silicate nanosheets and Li. The consecutive Li⁺-conductors can promote the desolvation process of solvated-Li⁺ and regulate the transfer of lithium ions. The nonconsecutive lithiophilic metals are polarized by the internal electric field to boost the transfer of lithium ions, and lower the nucleation barrier. Therefore, a low polarization of ≈50 mV for 750 h at 2.0 mA cm⁻² in symmetric cells, and a high capacity retention of 99.2 % in full cells with a high lithium iron phosphate areal loading of ≈13 mg cm⁻² are achieved. This work offers new sights to develop advanced alkali metal anodes for efficient energy storage.     

Photocatalytic Free Radical-Controlled Synthesis of High-Performance Single-Atom Catalysts

Single-atom catalysts (SACs) have emerged as crucial players in catalysis research, prompting extensive investigation and application. The precise control of metal atom nucleation and growth has garnered significant attention. In this study, we present a straightforward approach for preparing SACs utilizing a photocatalytic radical control strategy. Notably, we demonstrate for the first time that radicals generated during the photochemical process effectively hinder the aggregation of individual atoms. By leveraging the cooperative anchoring of nitrogen atoms and crystal lattice oxygen on the support, we successfully stabilize the single atom. Our Pd₁/TiO₂ catalysts exhibit remarkable catalytic activity and stability in the Suzuki–Miyaura cross-coupling reaction, which was 43 times higher than Pd/C. Furthermore, we successfully depose Pd atoms onto various substrates, including TiO₂, CeO₂, and WO₃. The photocatalytic radical control strategy can be extended to other single-atom catalysts, such as Ir, Pt, Rh, and Ru, underscoring its broad applicability.     

Reduction of Platinum(IV) Prodrug Hemoglobin Nanoparticles with Deeply Penetrating Ultrasound Radiation for Tumor-Targeted Therapeutically Enhanced Anticancer Therapy

The development of Pt^IV prodrugs that are reduced into the therapeutically active Pt^II species within the tumor microenvironment has received much research interest. In order to provide spatial and temporal control over the treatment, there is a high demand for the development of compounds that could be selectively activated upon irradiation. Despite recent progress, the majority of Pt^IV complexes are excited with ultraviolet or blue light, limiting the use of such compounds to superficial application. To overcome this limitation, herein, the first example of Pt^IV prodrug nanoparticles that could be reduced with deeply penetrating ultrasound radiation is reported, enabling the treatment of deep-seated or large tumors. The nanoparticles were found to selectively accumulate inside a mouse colon carcinoma tumor upon intravenous injection and were able to eradicate the tumor upon exposure to ultrasound radiation.     

Alkaline-Earth Metal Mediated Benzene-to-Biphenyl Coupling

Complex [(^DIPePBDI)Ca]₂(C₆H₆), with a C₆H₆²⁻ dianion bridging two Ca²⁺ ions, reacts with benzene to yield [(^DIPePBDI)Ca]₂(biphenyl) with a bridging biphenyl²⁻ dianion (^DIPePBDI=HC[C(Me)N-DIPeP]₂; DIPeP=2,6-CH(Et)₂-phenyl). The biphenyl complex was also prepared by reacting [(^DIPePBDI)Ca]₂(C₆H₆) with biphenyl or by reduction of [(^DIPePBDI)CaI]₂ with KC₈ in presence of biphenyl. Benzene-benzene coupling was also observed when the deep purple product of ball-milling [(^DIPPBDI)CaI(THF)]₂ with K/KI was extracted with benzene (DIPP=2,6-CH(Me)₂-phenyl) giving crystalline [(^DIPPBDI)Ca(THF)]₂(biphenyl) (52 % yield). Reduction of [(^DIPePBDI)SrI]₂ with KC₈ gave highly labile [(^DIPePBDI)Sr]₂(C₆H₆) as a black powder (61 % yield) which reacts rapidly and selectively with benzene to [(^DIPePBDI)Sr]₂(biphenyl). DFT calculations show that the most likely route for biphenyl formation is a pathway in which the C₆H₆²⁻ dianion attacks neutral benzene. This is facilitated by metal-benzene coordination.     

Effect of bias voltage and electrodes size on the Pd conductance histograms

Conductance histograms of palladium nanocontacts in ultra high vacuum (UHV) were experimentally studied at room temperature using scanning tunneling microscope (STM). Our results show that the resolution of the pure Pd peaks, at 1.8 and around 3G₀, in the histograms, depends on the bias voltage and the electrodes size. The size of the electrodes should be as small as possible to achieve the higher extraction of hydrogen from them and therefore preventing the diffusion of H from the bulk to the nanocontacts during the conductance measurements, particularly at low bias voltage. This could explain why peaks have not been observed previously in the Pd histograms, using STM techniques in UHV.     

Role of Divalent Metals in Polymer Degradation

The role of divalent metals in the degradation of the physico-mechanical properties of radiation-vulcanized natural rubber latex (RVNRL) films was investigated. RVNRL films were prepared by the addition of metals (Cu, Mg, etc.) of different concentrations (0–30ppm) to natural rubber latex and irradiated with various radiation doses (0–20kGy). The radiation doses were optimized (12kGy), and the adverse effect of metal ions was studied against a reference film prepared with no metal ions. Tensile strength, tear strength, and cross-linking density of the irradiated rubber films decreased with increasing metal ion concentrations and decreasing radiation doses. The mechanical properties of the films were reduced by 10–15% for 30ppm metal ions and at the optimum dose. In contrast, elongation at break, permanent set, and swelling ratio of the films increased at the same conditions. The relative effect of metal ions can be explained by the classical electron concept, reported in this article.     

Local structure of core/shell nanocrystalline particles produced by surfactant-assisted ball milling of Fe powder in paraffin

Surfactant-assisted ball milling of the Fe powder in paraffin has been used for fabrication of core–shell nanocrystalline particles. The local atomic structure of the bulk and surface layers of the mechanically milled particles has been studied using X-ray absorption spectroscopic techniques with synchrotron radiation from the DORIS storage ring at DESY, Hamburg. Regardless of milling environment composition, the as-prepared powders were shown to be characterized by a significant drop in the EXAFS signal intensity and coordination numbers of the Fe–Fe pairs due to the formation of nanocrystalline state in the particles. It has been shown that an addition of perfluorononanoic acid as a surfactant has a more prominent effect on the structure of the shell layers. The effect is revealed as an appearance of light element atoms (O, F, C) in the local atomic environment of the Fe atoms due to formation of oxide, carbide and adsorbed structures of different types in the particle shell.     

Polymer-Mercury Coated Screen-Printed Sensors for Electrochemical Stripping Analysis of Heavy Metals

In the perspective of in-field stripping analysis of heavy metals, the use and disposal of toxic mercury solutions (necessary to plate a mercury film on a carbon electrode surface) presents a problem. The aim of this work was the development of mercury coated screen-printed electrodes previously prepared in the lab and ready to use in-field. Thus some commercially available polymers like Nafion®, Eastman Kodak AQ29®, and Methocel® were investigated as mercury entrapping systems for electrochemical stripping analysis of heavy metals. Screen-printed disposable cells with a silver pseudo-reference electrode, a graphite counter electrode, and a graphite working electrode were used. To modify the sensor, the polymer solution was cast onto the carbon working electrode surface. Detection limits of 0.8 and 1 μg/L were obtained for lead and cadmium respectively. Since Methocel® based electrodes showed the best performance, they were used for the analysis of real samples. The results were compared with those obtained using a classical thin mercury film electrode and ICP spectroscopy.

All the experiments reported here were performed in un-deareated solutions as required for in-field analysis.     

Concave Pt-Cu-Fe ternary nanocubes:One-pot synthesis and their electrocatalytic activity of methanol and formic acid oxidation

Concave nanostructures may be developed to improve the specific mass activity of a catalyst for formic acid and methanol electro-oxidation. In this work, we report the elctrocatalytic oxidation of methanol and formic acid in acid medium over concave Pt-Cu-Fe ternary nanocubes (NCs), obtained by the galvanic exchange of Pt and Fe on Cu NCs. The concave Pt-Cu-Fe NCs exhibited improved electrooxidation performance contrasted to Pt-Cu NCs and purchased commercial Pt/C as demonstrated by their improved durability, lower onset potential, and more preferable anti-poisoning properties. These properties are believed to originate from the tailored concave structure of the catalyst and possible synergetic effects among the components of the Pt-Cu-Fe NCs.     

Rapid reduction of titanium dioxide nano-particles by reduction with a calcium reductant

Micro-, submicron-, and nano-scale titanium dioxide particles were reduced by reduction with a metallic calcium reductant in calcium chloride molten salt at 1173 K, and the reduction mechanism of the oxides by the calcium reductant was explored. These oxide particles, metallic calcium as a reducing agent, and calcium chloride as a molten salt were placed in a titanium crucible and heated under an argon atmosphere. Titanium dioxide was reduced to metallic titanium through a calcium titanate and lower titanium oxide, and the materials were sintered together to form a micro-porous titanium structure in molten salt at high temperature. The reduction rate of titanium dioxide was observed to increase with decreasing particle size; accordingly, the residual oxygen content in the reduced titanium decreases. The obtained micro-porous titanium appeared dark gray in color because of its low surface reflection. Micro-porous metallic titanium with a low oxygen content (0.42 wt%) and a large surface area (1.794 m² g⁻¹) can be successfully obtained by reduction under optimal conditions.