Electronic Structure Regulated Nickel-Cobalt Bimetal Phosphide Nanoneedles for Efficient Overall Water Splitting.

Transition metal phosphides (TMPs) have been widely studied for water decomposition for their monocatalytic property for anodic or cathodic reactions. However, their bifunctional catalytic activity still remains a major challenge. Herein, hexagonal nickel-cobalt bimetallic phosphide nanoneedles with 1-3 µm length and 15-30 nm diameter supported on NF (NixCo2-xP NDs/NF) with adjusted electron structure have been successfully prepared. The overall alkaline water electrolyzer composed of the optimal anode (Ni0.67Co1.33P NDs/NF) and cathode (Ni1.01Co0.99P NDs/NF) provide 100 mA cm-2 at 1.62 V. Gibbs Free Energy for reaction paths proves that the active site in the hydrogen evolution reaction (HER) is Ni and the oxygen evolution reaction (OER) is Co in NixCo2-xP, respectively. In the HER process, Co-doping can result in an apparent accumulation of charge around Ni active sites in favor of promoting HER activity of Ni sites, and ΔGH* of 0.19 eV is achieved. In the OER process, the abundant electron transfer around Co-active sites results in the excellent ability to adsorb and desorb *O and *OOH intermediates and an effectively reduced ∆GRDS of 0.37 eV. This research explains the regulation of electronic structure change on the active sites of bimetallic materials and provides an effective way to design a stable and effective electrocatalytic decomposition of alkaline water.

Capture and separation of circulating tumor cells using functionalized magnetic nanocomposites with simultaneous in situ chemotherapy.

Circulating tumor cells (CTCs) are a type of rare cell that are firstly shed from solid tumors and then exist in the bloodstream. The effective capture and separation of CTCs has significant meaning in cancer diagnosis and prognosis. In this study, novel Fe3O4-FePt magnetic nanocomposites (Fe3O4-FePt MNCs) were constructed by integrating face centered cubic (fcc) FePt nanoparticles (NPs) onto the surface of the Fe3O4@SiO2 core. After further modification with NH2-PEG-COOH and the tumor-targeting molecule tLyP-1, the acquired Fe3O4-FePt MNCs possesses excellent biocompatibility and stability and could efficiently target and capture tLyP-1 receptor-positive CTCs. Based on the acidic microenvironment within cancer cells, the FePt layer could rapidly release active Fe2+ ions, which could catalyze H2O2 into reactive oxygen species (ROS) and further induce in situ apoptosis in cancer cells while having no distinct cytotoxicity to normal cells. Moreover, the Fe3O4@SiO2 core with its intrinsic magnetism has huge potential for the bioseparation of CTCs. The in vitro ROS fluorescence imaging experiments and cell capture and separation experiments indicated that the Fe3O4-FePt MNCs could specifically capture and separate cancer cells in the CTCs model and further induce in situ apoptosis. Therefore, the Fe3O4-FePt MNCs could serve as a promising multifunctional nanoseparator for efficiently capturing CTCs and simultaneously inducing in situ chemotherapy.

Amperometric sensing of catechol by using a nanocomposite prepared from Ag/Ag2O nanoparticles and N,S-doped carbon quantum dots.

This work describes the synthesis of a nanocomposite consisting of Ag2O, silver nanoparticles and N,S-doped carbon quantum dots (Ag2O/Ag@NS-CQD). The NS-CQD were prepared by hydrothermal treatment of p-aminobenzenesulfonic acid. They act as both the reducing and stabilizing agent for synthesis of Ag2O/Ag@NS-CQD. The composite was characterized by UV-vis spectroscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The glassy carbon electrode (GCE) was modified by coating it with Ag2O/Ag@NS-CQD. It exhibits excellent amperometric response to catechol, typically at a low working potential of around 0.25 V. Under the best experimental conditions, the sensor has a wide linear response (0.2 to 180 µM) and a low detection limit (13 nM; at S/N = 3). The method was applied to analysis of spiked water samples and gave satisfactory results. Graphical abstract Schematic representation of the preparation of the Ag/Ag2O@N,S-doped carbon quantum dots composite using p-aminobenzenesulfonic acid and silver nitrate as the starting materials. The corresponding modified glassy carbon electrode exhibits the excellent amperometric sensing performance toward catechol at pH 7.0 with low detection limit and good selectivity.

Sub-1.5 nm Ultrathin CoP Nanosheet Aerogel: Efficient Electrocatalyst for Hydrogen Evolution Reaction at All pH Values.

Transition metal phosphides (TMPs) are certified high performance electrocatalysts for the hydrogen evolution reaction (HER). The ultrathin 2D structure of TMPs can offer abundant adsorption sites to boost HER performance. Herein, an ice-templating strategy is developed to prepare CoP aerogels composed of 2D ultrathin CoP nanosheets (<1.5 nm) using sustainable alginate biomass (seaweed extract) as the precursor. The highly porous aerogel structure can not only deliver facile mass transfer, but also prevent aggregation of the nanosheets into layered structures. As expected, the obtained CoP nanosheet aerogels exhibit remarkable stability and excellent electrocatalytic HER performance at all pH values. For instance, the sample CoP-400 presents a low overpotential of 113, 154, and 161 mV versus RHE at a current density of 10 mA cm-2 in 0.5 m H2SO4, 1 m KOH, and 1 m phosphate buffer solution, respectively. In addition, CoP-400 displays low Tafel slopes at all pH values due to the interconnected highly porous structure of the aerogel, indicating that the sample can provide low-resistance channels for mass transport. Density functional theory calculations reveal that P-top and Co bridge on (011) facet of CoP are more favorable sites during the process of HER in acid and alkaline solutions, respectively.

Thread-like supercapacitors based on one-step spun nanocomposite yarns.

Thread-like electronic devices have attracted great interest because of their potential applications in wearable electronics. To produce high-performance, thread-like supercapacitors, a mixture of stable dispersions of single-walled carbon nanotubes and conducting polyaniline nanowires are prepared. Then, the mixture is spun into flexible yarns with a polyvinyl alcohol outer sheath by a one-step spinning process. The composite yarns show excellent mechanical properties and high electrical conductivities after sufficient washing to remove surfactants. After applying a further coating layer of gel electrolyte, two flexible yarns are twisted together to form a thread-like supercapacitor. The supercapacitor based on these two yarns (SWCNTs and PAniNWs) possesses a much higher specific capacitance than that based only on pure SWCNTs yarns, making it an ideal energy-storage device for wearable electronics.

Co-exposure of microplastics and polychlorinated biphenyls strongly influenced the cycling processes of typical biogenic elements in anoxic soil.

The co-exposure of microplastics (MPs) and polychlorinated biphenyls (PCBs) in soil is inevitable, but their combined effect on cycles of typical biogenic elements (e.g. C, N, Fe, S) is still unclear. And the co-exposure of MPs and PCBs caused more severe effects than single exposure to pollution. Therefore, in this study, a 255-day anaerobic incubation experiment was conducted by adding polyethylene microplastics (PE MPs, including 30 ± 10 µm and 500 µm) and PCB138. The presence of PE MPs inhibited the PCB138 degradation. Also, PE MPs addition (1%, w/w) enhanced the methanogenesis, Fe(Ⅲ) reduction, and sulfate reduction while inhibited nitrate reduction and the biodegradation of PCB138. And PCB138 addition (10 mg·kg-1) promoted the methanogenesis and Fe(Ⅲ) reduction, but inhibited sulfate reduction and nitrate reduction. Strikingly, the presence of PE MPs significantly reduced the impact of PCB138 on the soil redox processes. The abundance changes of special microbial communities, including Anaeromyxobate, Geobacter, Bacillus, Desulfitobacterium, Thermodesulfovibrio, Metanobacterium, etc., were consistent with the changes in soil redox processes, revealing that the effect of PE MPs and/or PCB138 on the cycle of typical biogenic elements was mainly achieved by altering the functional microorganisms. This study improves the knowledge of studies on the impact of MPs and combined organic pollutants to soil redox processes, which is greatly important to the stabilization and balance of biogeochemical cycling in ecology.

Photodegradation of bisphenol A (BPA) in coastal aquaculture waters: Influencing factors, products, and pathways.

Bisphenol A (BPA), an endocrine-disrupting contaminant, is ubiquitous in the environment due to its presence in plastics, wastewater, and agricultural runoff. This study investigated the photodegradation behavior of BPA in coastal aquaculture waters near Qingdao, China. Lower salinity promoted BPA photodegradation, while higher salinity has an inhibitory effect, suggesting slower degradation in seawater compared to ultrapure water. Triplet-excited dissolved organic matter (3DOM*) was identified as the primary mediator of BPA degradation, with additional contributions from hydroxyl radicals (•OH), singlet oxygen (1O2), and halogen radicals (HRS). Alepocephalidae aquaculture water exhibited the fastest degradation rate, likely due to its high DOM and nitrate/nitrite (NO3-/NO2-) content, which are sources of 3DOM* and •OH. A positive correlation existed between NO3-/NO2- concentration and the BPA degradation rate. Ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) analysis identified the primary BPA photodegradation products, formed mainly through oxidative degradation, hydroxyl substitution, nitration, and chlorination pathways. Elucidating these photodegradation mechanisms provides valuable insights into the environmental fate and potential ecological risks of BPA in aquaculture environments. This knowledge can inform strategies for marine environmental protection and the development of sustainable practices.

Seaweeds as a major source of dietary microplastics exposure in East Asia.

Microplastics (MPs) occurrence in marine ecosystems is well known, but their accumulation in seaweeds and subsequent human exposure remain understudied. This research quantifies MPs presence in two commonly consumed seaweeds, kelp (Saccharina japonica) and nori (Pyropia yezoensis), in East Asia, revealing widespread contamination dominated by microfibers (<500 µm). Based on dietary patterns, human uptake through seaweed consumption was estimated and quantified. Notably, Chinese people consume an estimated 17,034 MPs/person/year through seaweed consumption, representing 13.1% of their total annual MPs intake. This seaweeds-derived exposure surpasses all other dietary sources, contributing up to 45.5% of overall MPs intake. The highest intake was in South Korea, followed by North Korea, China, and Japan. This research identifies seaweeds as a major, previously overlooked route of dietary MPs exposure. These findings are crucial for comprehensive risk assessments of seaweed consumption and the development of mitigation strategies, particularly for populations in East Asian countries.

Template-free synthesis of mesoporous hollow CuO microspheres as anode materials for Li-ion batteries.

We report the preparation and characterization of mesoporous hollow CuO (MPH-CuO) microspheres by thermal decomposition of hollow copper oxalate microspheres synthesized via the reaction of ammonium oxalate and copper chloride without using any template. The sample was characterized by Nitrogen adsorption, X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. The electrochemical performance of MPH-CuO microspheres as anode materials in Li-ion batteries was evaluated. It was found that the MPH-CuO microspheres possessed an average diameter of 2.5 microm, a pore size of 17.5 nm, and a BET surface area of 15.2 m2/g. Their shells were composed of CuO nanocrystals with a size of 17.9 nm. Compared with the dense CuO microspheres, the obtained MPH-CuO shows an enhanced electrochemical performance with a higher capacity of 599.4 mAh/g and a better cyclability (484 mAh/g after 15 cycles) because of its mesoporous hollow structure that provides quick intercalation and large accommodation of lithium ions together with short diffusion distance for lithium ions, suggesting a potential application in Li-ion batteries.

Electrostatic Interaction in Amino Protonated Chitosan-Metal Complex Anion Hydrogels: A Simple Approach to Porous Metal Carbides/N-Doped Carbon Aerogels for Energy Conversion.

In the face of the increasingly serious rapid depletion of fossil fuels, exploring alternative energy conversion technologies may be a promising choice to alleviate this crisis. Transition metal carbides (TMCs)/carbon composites are considered as prospective electrocatalysts due to their high catalytic activities and structural stability. In this work, we report the simple synthesis of TMCs/N-doping carbon aerogels (TMCs/NCAs, including Fe3C/NCA, Mo3C2/NCA, and Fe3C-Mo2C/NCA) for the oxygen reduction reaction (ORR) using protonated chitosan/metal complex anion-chelated aerogels. Among them, the Fe3C/NCA composite possesses efficient ORR activity (similar to Pt/C), and the Fe3C/NCA-assembled Zn-air battery exhibits high power densities of about 250 mW cm-2. The density functional theory calculation reveals that the presence of graphite-N, pyridine-N, and carbon defects in the carbon framework effectively reduces the free energy of ORR occurring in Fe3C. This work provides a simple and extensible strategy for the preparation of TMCs from chitosan, which is expected to be extended to other metal carbides.