In situ Observation of Evolving H2 and Solid Electrolyte Interphase Development at Potassium Insertion Materials within Highly Concentrated Aqueous Electrolytes

The solid-electrolyte interphase (SEI) is key to stable, high voltage lithium-ion batteries (LIBs) as a protective barrier that prevents electrolyte decomposition. The SEI is thought to play a similar role in highly concentrated water-in-salt electrolytes (WISEs) for emerging aqueous batteries, but its properties remain unknown. In this work, we utilized advanced scanning electrochemical microscopy (SECM) and operando electrochemical mass spectrometry (OEMS) techniques to gain deeper insight into the SEI that occurs within highly concentrated WISEs. As a model, we focus on a 55 mol/kg K(FSA)_0.6(OTf)_0.4 electrolyte and a 3,4,9,10-perylenetetracarboxylic diimide negative electrode. For the first time, our work showed distinctly passivating structures with slow apparent electron transfer rates alike to the SEI found in LIBs. In situ analyses indicated stable passivating structures when PTCDI was stepped to low potentials (≈−1.3 V vs. Ag/AgCl). However, the observed SEI was discontinuous at the surface and H₂ evolution occurred as the electrode reached more extreme potentials. OEMS measurements further confirmed a shift in the evolution of detectable H₂ from −0.9 V to <−1.4 V vs. Ag/AgCl when changing from dilute to concentrated electrolytes. In all, our work shows a combined approach of traditional battery measurements with in situ analyses for improving characterization of other unknown SEI structures.     

Restructuring and Activation of Cu(111) under Electrocatalytic Reduction Conditions

The dynamic restructuring of Cu surfaces in electroreduction conditions is of fundamental interest in electrocatalysis. We decode the structural dynamics of a Cu(111) electrode under reduction conditions by joint first-principles calculations and operando electrochemical scanning tunneling microscopy (ECSTM) experiments. Combining global optimization and grand canonical density functional theory, we unravel the potential- and pH-dependent restructuring of Cu(111) in acidic electrolyte. At reductive potential, Cu(111) is covered by a high density of H atoms and, below a threshold potential, Cu adatoms are formed on the surface in a (4×4) superstructure, a restructuring unfavorable in vacuum. The strong H adsorption is the driving force for the restructuring, itself induced by the electrode potential. On the restructured surface, barriers for hydrogen evolution reaction steps are low. Restructuring in electroreduction conditions creates highly active Cu adatom sites not present on Cu(111).     

Dynamically Restructuring NixCryO Electrocatalyst for Stable Oxygen Evolution Reaction in Real Seawater

In the pursuit of long-term stability for oxygen evolution reaction (OER) in seawater, retaining the intrinsic catalytic activity is essential but has remained challenging. Herein, we developed a Ni_xCr_yO electrocatalyst that manifested exceptional OER stability in alkaline condition while improving the activity over time by dynamic self-restructuring. In 1 M KOH, Ni_xCr_yO required overpotentials of only 270 and 320 mV to achieve current densities of 100 and 500 mA cm⁻², respectively, with excellent long-term stability exceeding 475 h at 100 mA cm⁻² and 280 h at 500 mA cm⁻². The combination of electrochemical measurements and in situ studies revealed that leaching and redistribution of Cr during the prolonged electrolysis resulted in increased electrochemically active surface area. This eventually enhanced the catalyst porosity and improved OER activity. Ni_xCr_yO was further applied in real seawater from the Red Sea (without purification, 1 M KOH added), envisaging that the dynamically evolving porosity can offset the adverse active site-blocking effect posed by the seawater impurities. Remarkably, Ni_xCr_yO exhibited stable operation for 2000, 275 and 100 h in seawater at 10, 100 and 500 mA cm⁻², respectively. The proposed catalyst and the mechanistic insights represented a step towards realization of non-noble metal-based direct seawater splitting.     

Bulk-like Pt(100)-oriented Ultrathin Surface: Combining the Merits of Single Crystals and Nanoparticles to Boost Oxygen Reduction Reaction

Single crystal surfaces with highly coordinated sites very often hold high specific activities toward oxygen reduction reaction (ORR) and others. Transposing their high specific activity to practical high-surface-area electrocatalysts remains challenging. Here, ultrathin Pt(100) alloy surface is constructed via epitaxial growth. The surface shows 3.1–6.9 % compressive strain and bulk-like characteristics as demonstrated by site-probe reactions and different spectroscopies. Its ORR activity exceeds that of bulk Pt₃Ni(100) and Pt(111) and presents a 19-fold increase in specific activity and a 13-fold increase in mass activity relative to commercial Pt/C. Moreover, the electrochemically active surface area (ECSA) is increased by 4-fold compared to traditional thin films (e.g. NSTF), which makes the catalyst more tolerant to voltage loss at high current densities under fuel cell operation. This work broadens the family of extended surface catalysts and highlights the knowledge-driven approach in the development of advanced electrocatalysts.     

Sustained Hydrogen Spillover on Pt/Cu(111) Single-Atom Alloy: Dynamic Insights into Gas-Induced Chemical Processes

Hydrogen spillover, involving the surface migration of dissociated hydrogen atoms from active metal sites to the relatively inert catalyst support, plays a crucial role in hydrogen-involved catalytic processes. However, a comprehensive understanding of how H atoms are driven to spill over from active sites onto the catalyst support is still lacking. Here, we examine the atomic-scale perspective of the H spillover process on a Pt/Cu(111) single atom alloy surface using machine-learning accelerated molecular dynamics calculations based on density functional theory. Our results show that when an impinging H₂ dissociates at an active Pt site, the Pt atom undergoes deactivation due to the dissociated hydrogen atoms that attach to it. Interestingly, collisions between H₂ and sticking H atoms facilitate H spillover onto the host Cu, leading to the reactivation of the Pt atom and the realization of a continuous H spillover process. This work underscores the importance of the interaction between gas molecules and adsorbates as a driving force in elucidating chemical processes under a gaseous atmosphere, which has so far been underappreciated in thermodynamic studies.     

Establishing TA-Pb/Cu and SA-Pb/Cu interface catalyst shells on HMX surfaces via in situ coprecipitation to ameliorate the performances of HMX

Lead/copper tannate (TA-Pb/Cu) and lead/copper salicylate (SA-Pb/Cu) interface catalyst shells are established on the surface of 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) via in situ coprecipitation to prepare HMX@TA-Pb/Cu and HMX@SA-Pb/Cu composites. The structures and properties of the obtained HMX@TA-Pb/Cu and HMX@SA-Pb/Cu composites are characterized in detail. Molecular dynamics simulations are performed to study the adsorption mechanism of TA-Pb/Cu and SA-Pb/Cu on HMX surface. The residues after HMX@TA-Pb/Cu and HMX@SA-Pb/Cu combusted in air are collected and characterized to study the catalytic effect of TA-Pb/Cu and SA-Pb/Cu on combustion. The study results show that TA-Pb/Cu shells are coated on HMX surface due to the excellent membrane-forming properties of TA, while SA-Pb/Cu shells are embedded in the gullies and holes of HMX surface. TA-Pb/Cu and SA-Pb/Cu shells can decrease the mechanical sensitivities and catalyze the decomposition and combustion of HMX, and the catalytic effects of in situ coprecipitation are better than that of physical mixing. In addition, the phase transition temperature of HMX in HMX@TA-Pb/Cu is increased while that of HMX@SA-Pb/Cu is decreased, illustrating that TA-Pb/Cu can enhance the thermal stability of HMX while SA-Pb/Cu can catalyze the phase transition of HMX.     

Rapid synthesis of bovine serum albumin-conjugated gold nanoparticles using pulsed laser ablation and their anticancer activity on hela cells

Nanoscience research aims to produce nanoparticles without adverse effects for medical applications. The pulsed laser ablation (PLA) technique was utilized in this study to synthesize gold nanoparticles (AuNPs) using bovine serum albumin (BSA) in simulated body fluid (SBF) at the fundamental wavelength of the Nd: YAG laser (1064 nm). BSA acted as a stabilizer, reducing and capping agent to produce spherically shaped AuNPs (diameter 3–10 nm). The successful synthesis of AuNPs was confirmed through color changes and UV–vis spectroscopy. The agglomeration and precipitation of AuNPs are attributed to the presence of BSA in the solution, and electrostatic repulsion interactions between BSA and Au nanoclusters. The effect of salt concentration of SBF on BSA stability as well as the interaction of BSA conjugated AuNPs to form complexes was studied using molecular dynamic simulations. Our results show that the stability of AuNPs-BSA conjugates increase with the salt concentration of BSA. Moreover, the synthesized AuNPs exhibit low toxicity and high biocompatibility, supporting their application in drug delivery. Investigation of the cytotoxic effect of the synthesized AuNPs show that normal fibroblast cells (L929) remain intact after treatment whereas a dose-dependent inhibition effect on the growth of cervix cancer cells (HeLa) is observed. In general, this study presents an effective, environmentally-friendly, and facile approach to the synthesis of multifunctional AuNPs using the PLA technique, as a promising efficacious therapeutic treatment of cervical cancer.     

Electrochemical performance of a nano SnO2-modified LiNi1/3Co1/3Mn1/3O2 cathode material

The nano SnO₂-modified LiNi_1/3Co_1/3Mn_1/3O₂ was successfully prepared by a carrier transfer method. The pristine and modified samples were characterized with various techniques such as XRD, SEM, XPS and EDS. The results showed that the SnO₂ particles did not enter the crystal structure of LiNi1/3Co1/ 3Mn1/3O₂, many nano SnO₂ particles were uniformly covered on the surface of LiNi_1/3Co_1/3Mn_1/3O₂ and the modified thin layer could inhibit the dissolution of transition metal oxides. The electrochemical tests indicated that the existence of nano SnO₂ could improve the discharge capacity and rate capability owing to the decreased interfacial polarization. The cycling stability was remarkably improved at room temperature and 55 ℃. The XRD patterns of the fresh NCM electrode and after 50 cycles proved that the structural change of NCM was not so effective on the capacity fade.     

超声波促进手性双酰基氧化膦的合成

以L-薄荷醇为原料,经3步反应制备得到中间体薄荷基二氯化膦.该中间体首先通过与超声波辐射制备的微米级钠粒反应形成薄荷基膦二钠盐,然后依次经过偶联及氧化反应合成了目标产物(-)-双(薄荷基甲酰基)薄荷基氧化膦(BMMPO),并经过1 H NMR、13 C NMR、31P NMR和元素分析进行了表征.     

Non‐Invasive Salivary Electrochemical Quantification of Paraquat Poisoning Using Boron Doped Diamond Electrode

The present work describes the first electrochemical method for quantifying paraquat herbicide poisoning in human saliva samples. Paraquat shows two couples of well‐defined peaks in aqueous solution using a boron doped diamond (BDD) electrode. By using square wave voltammetry (SWV) technique under optimum experimental conditions, a linear analytical curve was obtained for paraquat concentrations ranging from 0.800 to 167 µmol L^?1, with a detection limit of 70 nmol L^?1. This method was applied to quantify paraquat spikes in human saliva samples and in two different water samples (tap and river). The recovery values obtained ranged from 83.0 to 104 % and 99.1 to 105 %, respectively, which highlight the accuracy of the proposed method.