Latest ArticlesNitrogen reduction reactions (NRR) under room conditions remain the challenge for N2 activation on metal-based catalysis materials. Herein, the M-doped CeO2(111) (M = Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) with oxygen vacancies, are systematically investigated by spin-polarized DFT + U calculations. We discuss briefly the situation of OVs on pure and reduced cerium, and we found that (1) doping TMs can promote the formation of oxygen defects, apart from Ti and V-dopant, (2) the O atoms are easier to escape connecting to M atoms than the ones of adjacent atoms connecting to the Ce(III), the value of OVs formation energies decrease as the TMs radius decrease. Also, our computational results show that Cr-doped, Mn-doped, Fe-doped, and Co-doped CeO2(111) adsorbs N2 strongly than the stoichiometric surface and other M-doped CeO2 surfaces with adsorption energies of −0.82, −1.02, −0.83 and −1.05 eV. Through COHP analysis, it is found that the predicted active sites have good catalytic performance.
Bio-based epoxy thermoset prepared from renewable biomass raw materials can alleviate fossil energy crisis and reduce environmental pollution, which satisfies the needs of sustainable social development. In this study, a bio-based epoxy thermoset precursor (MGOL-EP) was synthesized from a naturally occurring magnolol through a facile and efficient one-step process. And the fully bio-based epoxy thermoset (MGOL-EP-SC) was obtained by self-curing without adding any other hardener. MGOL-EP-SC revealed an extremely high glass-transition temperature (Tg) of 265 ℃ and char yield of 53.2% (in N2), which were at the highest level among the fully bio-based epoxy thermosets reported so far. In addition, when the MGOL-EP was cured with 4, 4′-methylenedianiline (DDM), Tg of the MGOL-EP/DDM was decreased by 61 ℃ and the other comprehensive performance had also been decreased, which was due to a reduction in biphenyl structure content and cross-linking density by adding the external curing agents. Moreover, the MGOL-EP-SC presented certain killing rate (48.4%) to Staphylococcus aureus. These findings provide a new design strategy for engineering high-performance and functional epoxy thermoset with high biomass content.
Chloride ion batteries (CIB) are considered to be one of the most promising energy storage devices. As cathode materials for CIBs, metal chlorides have many advantages, such as high theoretical energy density, abundant elemental resources and ideal discharge voltage plateau. However, the dissolution and huge volume change of metal chlorides during cycling lead to considerable short lifespan, which limits their potential application for CIBs. Herein, the bismuth chloride nanocrystal is confined in mesocellular carbon foam matrix by a new vacuum impregnation approach. The mesocellular carbon foam with large interconnected pores (15.7 or 23.2 nm) may buffer the large volume variation of bismuth chloride during charge and discharge, giving rise to significantly enhanced electrochemical performance. The as-prepared bismuth chloride@mesocellular carbon foam cathode delivered an initial discharge capacity of 298 mAh/g and a reversible capacity of 91 mAh/g after 60 cycles. In contrast, the pure bismuth chloride cathode almost cannot discharge after 30 cycles. This is the first report that the metal chloride cathode can achieve a prolonged cycling in CIBs.
In this study, novel iron-doped biochar (Fe-BC) was produced using a simple method, and it was used as an H2O2 activator for tetracycline (TC) degradation. Generally, iron loading can improve the separation performance and reactivity of biochar (BC). In the Fe-BC/H2O2 system, 92% of the TC was removed within 30 min with the apparent rate constant (kobs) of 0.155 min−1, which was 23.85 times that in the case of the BC/H2O2 system (0.0065 min−1). The effects of the H2O2 and Fe-BC dosage, initial pH, and TC concentration on the TC removal were investigated. The radical quenching and electron paramagnetic resonance (EPR) measurements demonstrated that the removal of TC using the Fe-BC/H2O2 process involved both radical (•OH and O2−•) and non-radical pathways (1O2 and electron transfer). In addition, the performance of the catalyst was also affected by the persistent free radicals (PFRs) and defective sites on the catalyst. Moreover, the degradation pathways of TC were proposed according to the intermediate products detected by LC-MS and the ecotoxicity of intermediates was evaluated. Finally, the Fe-BC/H2O2 showed high resistance to inorganic anions and natural organic matter in aquatic environments. Overall, Fe-BC is expected to be an economic and highly efficient heterogeneous Fenton catalyst for removing the organic contaminants in wastewater.
Exosomal microRNA (miRNA) is an ideal candidate of noninvasive biomarker for the early diagnosis of cancer. Sensitive and accurate sensing of abnormal exosomal miRNA plays essential role for clinical promotion due to its close correlation with tumor proliferation and progression. Herein, a microfluidic surface-enhanced Raman scattering (SERS) sensor was proposed for an on-line detection of exosomal miRNA based on rolling circle amplification (RCA) and tyramine signal amplification (TSA) strategy. The microfluidic chip consists of a magnetic enrichment chamber, a serpentine fluidic mixer and a plasmonic SERS substrate functionalized with capture probes. The released miRNA activates the capture probe, triggers RCA reaction, and generates a large number of single-stranded DNA products to drive the catalysis of nanotags deposition via TSA, producing numerous phot spotsq to enhance the SERS signals. In merit of the microfluidics chip and nucleic acid-tyramine cascade amplification, the developed SERS sensor significantly improves the sensitivity for the exosomal miRNA assay, resulting in a limit of detection (LOD) as low as 1 pmol/L and can be successfully applied in the analysis of exosomes secreted from breast tumor cells, which demonstrates the potential utility in practical applications.
Transition metal-based bimetallic oxides can effectively activate peroxymonosulfate (PMS) for the degradation of organic contaminants, which may be attributed to the enhanced electron transfer efficiency between transition metals. Here, we investigated the high-efficiency catalytic activation reaction of PMS on a well-defined bimetallic Fe-Mn nanocomposite (BFMN) catalyst. The surface topography and chemical information of BFMN were simultaneously mapped with nanoscale resolution. Rhodamine B (RhB, as a model pollutant) was used to evaluate the oxidation activity of PMS activation system. The maximum absorption peak of RhB obviously blue shifted from 554 nm to 501 nm, and decreased sharply to disappear completely within 60 min. The removal performance is better than most of the reported single transition metal oxide. X-ray photoelectron spectroscopy (XPS) imaging of the BFMN electronic structure after catalytic activation confirmed that the accelerated internal electron transfer is mainly caused by the synergy effect of Mn and Fe sites at the catalysis boundary. The outstanding ability of BFMN for PMS chemical adsorption and activation may attribute to the enhanced covalency and reactivity of Mn-O. These results of this study can advance understandings on the origins of bimetallic oxides activity for PMS activation and developing the efficient metal oxide catalysts in real practice.
The difficulty in Fe(Ⅲ)/Fe(Ⅱ) conversion in the Fe(Ⅲ)/peroxymonosulfate (PMS) process limits its efficiency and application. Herein, l-cysteine (Cys), a green natural organic ligand with reducing capability, was innovatively introduced into Fe(Ⅲ)/PMS to construct an excellent Cys/Fe(Ⅲ)/PMS process. The Cys/Fe(Ⅲ)/PMS process, at room temperature, can degrade a variety of organic contaminants, including dyes, phenolic compounds, and pharmaceuticals. In subsequent experiments with acid orange 7 (AO7), the AO7 degradation efficiency followed pseudo-first-order kinetic which exhibited an initial "fast stage" and a second "slow stage". The rate constant values ranged depending on the initial Cys, Fe(Ⅲ), PMS, and AO7 concentrations, reaction temperature, and pH values. In addition, the presence of Cl−, NO3−, and SO42− had negligible impact while HCO3− and humic acid inhibited the degradation of AO7. Furthermore, radical scavenger experiments and methyl phenyl sulfoxide (PMSO) transformation assay indicated that sulfate radical, hydroxyl radical, and ferryl ion (Fe(Ⅳ)) were the dominant reactive species involved in the Cys/Fe(Ⅲ)/PMS process. Finally, based on the results of gas chromatography-mass spectrometry, several AO7 degradation pathways, including N=N cleavage, hydroxylation, and ring opening were proposed. This study provided a new insight to improve the efficiency of Fe(Ⅲ)/PMS process by accelerating Fe(Ⅲ)/Fe(Ⅱ) cycle with Cys.
Azulene, one of representative nonbenzenoid aromatic hydrocarbons, exhibits unique molecular structure and distinctive physical and chemical properties. Herein, azulenoisoindigo (AzII), an azulene-based isoindigo analogue, is designed and synthesized, which has a twisted molecular backbone and R/S-isomers in single crystals. Interestingly, AzII shows the characteristics of both isoindigo and azulene, such as reversible redox behavior and reversible proton responsiveness. UV-vis-NIR, 1H NMR and electron paramagnetic resonance (EPR) measurements were carried out to get insights into the possible mechanism of the proton-responsive property of AzII. The results demonstrated that only one azulenyl moiety of molecule of AzII was protonated and deprotonated, and the protonated AzII can be further oxidized to form azulenium cation radicals.
Application of matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) to investigate the spatiotemporal alterations of lipids in biological tissues has brought many significant results. However, the presence of structural isomers varying in C=C double bond (DB) locations makes isomer-resolved MSI an urgent need. Herein, we introduce a new type of light-driven on-tissue [2 + 2] cycloaddition reaction coupled with MALDI-MS/MS imaging to identify lipid DB position isomers and their spatial signatures in biological tissues. 3-Benzoylpyridine was introduced as a novel derivatization reagent, and it exhibited great reactivity toward lipid C=C bond to form oxetanes under both ultraviolet light and visible light irradiation. With this approach, DB position isomers of lipids were imaged with highly differential levels in distinct regions of rat brain, providing an accurate and spatially resolved approach to study tissue lipidomics.
No. 86 Xueyuan South Road, Haidian District, Beijing
010-62199257
qkjq@cast.org.cn
Copyright © 2025 China Association for Science and Technology. All rights reserved. For all open access content, the relevant licensing terms apply.
Sponsored by the Office of the Leading Group for Cybersecurity and Informatization of CAST, and supported by Science and Technology Review Publishing House
