Transition metal phosphides: A wonder catalyst for electrocatalytic hydrogen production

Hydrogen evolution from water electrolysis has become an important reaction for the green energy revolution. Traditional precious metals and their compounds are excellent catalysts for producing hydrogen; however, their high cost limits their large-scale practical application. Therefore, the development of affordable electrocatalysts to replace these precious metals is important. Transition metal phosphides(TMPs) have shown remarkable performance for hydrogen evolution and garnered considerable ...     

3D microgel with extensively adjustable stiffness and homogeneous microstructure for metastasis analysis of solid tumor

3D microgels with various mechanical properties have been important platforms tumor metastasis analysis, and widely adjustable stiffness is crucial for deeper researches. Herein, by mixing biodegradable polylactic acid (PLA) nanofibers in the modified alginate with different concentrations of Ca²⁺, we significantly enhance the stiffness range of microgels while retaining the pore size, which provides bionic microenvironment for tumor analysis. As a proof of concept, we simulated the mechanical characteristics of breast tumors by encapsulating cells in 3D microgels with diverse stiffness, and analyzed cellular behaviors of two typical breast cancer cell lines: MCF-7 and SUM-159. Results showed that with the addition of 2.0% (w/v) PLA short nanofibers, the Young's modulus of modified alginate increased more than three-fold. Besides preserving high survival and proliferation rates, both cells also displayed stronger migration ability in soft microgel spheres, where RT-qPCR analysis revealed the underlying changes at the genetic level. This systematic study demonstrated our method is powerful for creating widely adjustable 3D mechanical microenvironment, and the results of cellular behavior analysis shows its promising application prospects in tumorigenesis and progression.     

Cooperative coupling of photocatalytic production of H2O2 and oxidation of organic pollutants over gadolinium ion doped WO3 nanocomposite

This work reported the lanthanide ion (Gd³⁺) doped tungsten trioxide (Gd-WO₃) nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H₂O₂ production. With doped lanthanide ion (Gd³⁺), Gd-WO₃ showed a much broad and enhanced solar light absorption, which not only promoted the photocatalytic degradation efficiency of organic compounds, but also provided a suitable bandgap for direct reduction of oxygen to H₂O₂. Additionally, the isolated Gd³⁺ on WO₃ surface can efficiently weaken the *OOH binding energy, increasing the activity and selectivity of direct reduction of oxygen to H₂O₂, with a rate of 0.58 mmol L⁻¹ g⁻¹ h⁻¹. The in-situ generated H₂O₂ can be subsequently converted to ^•OH based on Fenton reaction, further contributed to the overall removal of organic pollutants. Our results demonstrate a cascade photocatalytic oxidation-Fenton reaction which can efficiently utilize photo-generated electrons and holes for organic pollutants treatment.     

Bio-Inspired Aerobic-Hydrophobic Janus Interface on Partially Carbonized Iron Heterostructure Promotes Bifunctional Nitrogen Fixation

Competition from hydrogen/oxygen evolution reactions and low solubility of N₂ in aqueous systems limited the selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe₃C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe₃C/Fe@PCNF-F away from water infiltration and endow a N₂ molecular-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust “quasi-solid–gas” state micro-domain around the catalyst surface. In this proof-of-concept system, the Fe₃C/Fe@PCNF-F exhibits excellent electrocatalytic performance for nitrogen fixation (NH₃ yield rate up to 29.2 μg h⁻¹ mg⁻¹_cat. and Faraday efficiency (FE) up to 27.8 % in nitrogen reduction reaction; NO₃⁻ yield rate up to 15.7 μg h⁻¹ mg⁻¹_cat. and FE up to 3.4 % in nitrogen oxidation reaction).     

Zn2+@Polyvinylpyrrolidone and Urushiol Preparation of Nanofibrous Membranes and Their Synergistic Effect

In this study, lacquer is gathered from a lacquer tree and rotary evaporation is used to remove impurities to obtain urushiol. Next, 10 mL of anhydrous ethanol serves as the solvent for blending polyvinylpyrrolidone (PVP) at a specified content (0.7 g and 0.2–0.7 g urushiol) to form an electrospinning solution. Electrospinning is carried out with a voltage of 18 kV to prepare PVP/urushiol nanofibrous membranes. At a ratio of 7/4, the PVP/urushiol nanofibrous membranes are not eroded in 98% sulfuric acid and these membranes also demonstrate a 50–60% antibacterial effect against Staphylococcus aureus and Escherichia coli. Moreover, the antibacterial effect can be boosted to 98% with the incorporation of zinc ions. The results indicate that anhydrous ethanol can remove the sensitization of urushiol from PVP/urushiol membranes. Furthermore, animal test results indicate that when rats are in contact with PVP/urushiol anhydrous ethanol for 48 h, their skins are free from dark brown skin allergy. The presence of PVP eliminates the sensitization of urushiol, and the nanofibrous membranes demonstrate low toxicity. Hence, urushiol is the only natural material that enables PVP to withstand 98% sulfuric acid as well as acquire hydrolyzability, thereby qualify PVP as a medical material.     

EMI shielding performance of electroless coated iron nanoparticles on graphite in low-density polyethylene composite for X-band applications

In the proposed work, an investigation of shielding effectiveness (SE) for varying compositions of Graphene, Multiwall carbon nanotubes (MWCNT), and Iron nanoparticles coated on Graphite (Fe@Graphite) was conducted in X-band (8.2 GHz–12.4 GHz). All these are mixed in an LDPE matrix. The nanomaterial was subjected to chemical characterization, i.e., Scanning electron microscopy (SEM), X-ray diffraction (XRD), and vibrating sample magnetometry (VSM). The shielding observed is dominantly due to absorption. The lattice structure which facilitates the shielding due to absorption was the hexagonal graphite structure on whose surface iron nanoparticles were embedded and used as the magnetic filler. At the same time, Graphene and MWCNT act as electrically conducting fillers. The Total shielding effectiveness(SE_T) was maximum for LDPE, MWCNT, Graphene, and Fe@Graphite, in the ratio of 50: 5: 25: 20 by weight %, and is 49 dB at 9.65 GHz for a sample thickness of 3 mm.     

Ruthenium(II)-catalyzed para-selective CH difluoroalkylation of aromatic aldehydes and ketones using transient directing groups

A Ru(II)-catalyzed para-difluoroalkylation of aromatic aldehydes and ketones with a transient directing group has been developed. It utilizes less expensive ruthenium catalysts and allows facile access to challenging difluoroalkylated aldehydes. The mechanism studies suggest that the distinct coordination mode of ruthenium complex with imine moieties is responsible for para-selectivity.     

Sequential separation of Cu(II)/Ni(II)/Fe(II) from strong-acidic pickling wastewater with a two-stage process based on a bi-pyridine chelating resin

A self-synthesized bi-pyridine chelating resin (PAPY) could separate Cu(II)/Ni(II)/Fe(II) sequentially from strong-acidic pickling wastewater by a two-stage pH-adjusted process, in which Cu(II), Ni(II), and Fe(II) were successively preferred by PAPY. In the first stage (pH 1.0), the separation factor of Cu(II) over Ni(II) reached 61.43 in Cu(II)-Ni(II)-Fe(II) systems. In the second stage (pH 2.0), the separation factor of Ni(II) over Fe(II) reached 92.82 in Ni(II)-Fe(II) systems. Emphasis was placed on the selective separation of Cu(II) and Ni(II) in the first-stage. The adsorption amounts of Cu(II) onto PAPY were 1.2 mmol/g in the first stage, while those of Ni(II) and Fe(II) were lower than 0.3 mmol/g. Cu(II) adsorption was hardly affected by Ni(II) with the presence of dense Fe(II), but Cu(II) inhibited Ni(II) adsorption strongly. Part of preloaded Ni(II) could be replaced by Cu(II) based on the replacement effect. Compared with the absence of Fe(II), dense Fe(II) could obviously enhance the separation of Cu(II)-Ni(II). More than 95.0% of Cu(II) could be removed in the former 240 BV (BV for bed volume of the adsorbent) in the fixed-bed adsorption column process with the flow rate of 2.5 BV/h. As proved by X-ray photoelectron spectrometry (XPS) and density functional theory (DFT) analyses, Cu(II) exerted a much stronger deprotonation and chelation ability toward PAPY than Ni(II) and Fe(II). Thus, the work shows a great potential in the separation and purification of heavy metal resources from strong-acidic pickling wastewaters.     

Selective sensing of CrVI and FeIII ions in aqueous solution by an exceptionally stable TbIII-organic framework with an AIE-active ligand

We herein report a new lanthanide metal-organic framework (MOF) that exhibits excellent chemical stability, especially in the aqueous solution over a wide pH range from 1 to 14. In contrast to many reported lanthanide MOFs, this Tb-based MOF emits cyan fluorescence inherited from the integrated AIE-active ligand, rather than Ln³⁺ ions. More remarkably, its fluorescence signal features a highly selective and sensitive “turn-off” response toward CrO₄²⁻, Cr₂O₇²⁻ and Fe³⁺ ions, highlighted with the low detection limits down to 68.18, 69.85 and 138.8 ppm, respectively. Thus, the exceptional structural stability and sensing performance render this material able to be a superior luminescent sensor for heavy metal ions in wastewater.     

溯源辨析“活化分子”概念在化学教材中的角色定位*

“活化分子”作为国内化学教育领域广为人知的科学概念,在各类相关化学教材中都有介绍。然而在国外多种经典化学教材中却完全没有“活化分子”的概念,反映出国内外化学教育领域对化学反应速率理论相关知识点的处理上存在明显的差异与分歧。通过溯源关键历史文献,回顾了“活化分子”概念的形成及其在化学反应速率理论发展过程中的角色演变,指出“活化分子”概念已经退出反应速率理论的舞台,在教材中应更多地呈现其在科学史方面的价值,而不是科学价值。