Engineering Electron-Rich Sites on CoSe2-x Nanosheets for the Enhanced Electroanalysis of As(III): A Study on the Electronic Structure via X-ray Absorption Fine Structure Spectroscopy and Density Functional Theory Calculation.

Vacancy and doping engineering are promising pathways to improve the electrocatalytic ability of nanomaterials for detecting heavy metal ions. However, the effects of the electronic structure and the local coordination on the catalytic performance are still ambiguous. Herein, cubic selenium vacancy-rich CoSe2 (c-CoSe2-x) and P-doped orthorhombic CoSe2-x (o-CoSe2-x|P) were designed via vacancy and doping engineering. An o-CoSe2-x|P-modified glass carbon electrode (o-CoSe2-x|P/GCE) acquired a high sensitivity of 1.11 µA ppb-1 toward As(III), which is about 40 times higher than that of c-CoSe2-x, outperforming most of the reported nanomaterial-modified glass carbon electrodes. Besides, o-CoSe2-x|P/GCE displayed good selectivity toward As(III) compared with other divalent heavy metal cations, which also exhibited excellent stability, repeatability, and practicality. X-ray absorption fine structure spectroscopy and density functional theory calculation demonstrate that electrons transferred from Co and Se to P sites through Co-P and Se-P bonds in o-CoSe2-x|P. P sites obtained plentiful electrons to form active centers, which also had a strong orbital coupling with As(III). In the detection process, As(III) was bonded with P and reduced by the electron-rich sites in o-CoSe2-x|P, thus acquiring a reinforced electrochemical sensitivity. This work provides an in-depth understanding of the influence of the intrinsic physicochemical properties of sensitive materials on the behavior of electroanalysis, thus offering a direct guideline for creating active sites on sensing interfaces.

General Strategies to Construct Highly Efficient Sensing Interfaces for Metal Ions Detection from the Perspective of Catalysis.

Constructing high-effective electrode sensing interfaces has been considered an effective method for electrochemical detection toward heavy metal ions (HMIs). However, most research has been devoted to enhancing the stripping currents of HMIs by simply improving the adsorptive capacity and conductivity of the electrode modified materials, while lacking theoretical guidelines in fabricating catalytic sensing interfaces. Besides, the understanding of detection mechanisms is quite unscientific from the perspective of catalysis. This perspective summarizes five general strategies in designing highly efficient sensing interfaces in the recent five years, including modulating crystal phases, orientations and planes, defect engineering, ionic valence state cycle engineering, adsorption in situ catalysis strategy, and construction of atomic level catalytic active sites. What's more, the catalytic mechanisms for improving the signals of HMIs, such as boosting the electron transfer rates and conversion rates, lowering the energy barriers, etc., are introduced and emphasized. This study has a great significance in directionally controlling functionalized electrochemical sensors to achieve excellent sensitivity and selectivity in detecting environmental pollutants from the view of catalysis, and it also brings enlightenments and guidance to develop new electroanalytical methods.

Pump bleaching of Tm-doped fiber with 793 nm pump source.

We demonstrate, for the first time to our knowledge, the strong recovery of the optical-optical slope efficiency of gamma-ray-irradiated Tm-doped fiber under 793 nm laser diode (LD) pumping. The fiber optical-optical slope efficiency, the fiber cladding absorption spectra, and the fluorescence spectra of the Tm-doped fiber before and after 500 Gy gamma-ray irradiation have been measured for comparison. It is found that the fiber optical-optical slope efficiency had significant degradation from 56.3% to 26.7% after irradiation and recovered to 40.8% after 15 h pump bleaching. Based on comparative analysis of fiber cladding absorption spectra among pristine fiber, irradiation, and bleaching, the reasons for the strong recovery have also been discussed.

Fluorescence and molecular weight dependence of disinfection by-products formation from extracellular organic matter after ultrasound irradiation.

Algal blooms have a negative impact on the safety of drinking water. Ultrasonic radiation technology is an "environment-friendly" technology that is widely used in algae removal. However, this technology leads to the release of intracellular organic matter (IOM), which is an important precursor of disinfection by-products (DBPs). This study investigated the relationship between the release of IOM in Microcystis aeruginosa and the generation of DBPs after ultrasonic radiation as well as analyzed the generation mechanism of DBPs. Results showed that the content of extracellular organic matter (EOM) in M. aeruginosa increased in the order of 740 kHz >1120 kHz >20 kHz after 2 min of ultrasonic radiation. Organic matter with a molecular weight (MW) greater than 30 kDa increased the most, including protein-like, phycocyanin (PC) and chlorophyll a, followed by small-molecule organic matter less than 3 kDa, mainly humic-like substances and protein-like. DBPs with an organic MW range of less than 30 kDa were dominated by trichloroacetic acid (TCAA), while those with an MW greater than 30 kDa had the highest trichloromethane (TCM) content. Ultrasonic irradiation changed the organic structure of EOM, affected the amount and type of DBPs, and tended to generate TCM.

Separation of dye from aqueous solution by a new gravity compression and aeration system.

Filtration is one of the important technologies for separating suspended particles. Under the condition of gravity compression, the filtration density can be increased and the separation effect of suspended particles can be improved. Considering the complex composition and the difficulty in degrading dye in industrial wastewater, a gravity compression aeration system with a modified polyester fibre ball (denoted as MPFB) was evaluated for the separation of dye from water. Congo red azo dye solution (0-40 mg/L) was selected as the model treatment compound. The MPFB was prepared by adjusting the concentrations of alkali (Quality score 0-25%), ß-cyclodextrin (0∼80 g/L), reaction temperature (40-90°C), and silane coupler concentration (Concentration fractions 0-0.8%). We used Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) to characterise the MPFB. The separation was affected significantly by adsorption conditions such as MPFB dose and pH. The lower the MPFB dose, the higher the expected adsorption capacity. For the treatment of a dye solution at 500 mg/L, 100% removal was achieved with 48 g/L MPFB, at pH 8 during adsorption under non-circulation aeration. For 24 h of reaction, the system could reach the maximum adsorption capacity of 11.2 mg/g, which followed the pseudo-first order kinetics model and the intraparticle diffusion model. We discovered that circulation aeration provided the best adsorption and electrostatic and hydrogen bonding were the dominant components of adsorption. Overall, the system is a promising technology and has the potential to treat large volumes of dye wastewater.

Noble-metal-free Fe3O4/Co3S4 nanosheets with oxygen vacancies as an efficient electrocatalyst for highly sensitive electrochemical detection of As(III).

The electrochemical method for highly sensitive determination of arsenic(III) in real water samples with noble-metal-free nanomaterials is still a difficult but significant task. Here, an electrochemical sensor driven by noble-metal-free layered porous Fe3O4/Co3S4 nanosheets was successfully employed for As(III) analysis, which was prepared via a facile two-step method involves a hydrothermal treatment and a subsequent sulfurization process. As expected, the electrochemical detection of As(III) in 0.1 M HAc-NaAc (pH 6.0) by square wave anodic stripping voltammetry (SWASV) with a considerable sensitivity of 4.359 µA/µg·L-1 was obtained, which is better than the commonly used noble metals modified electrodes. Experimental and characterization results elucidate the enhancement of As(III) electrochemical performance could be attributed to its nano-porous structure, the presence of oxygen vacancies and strong synergetic coupling effects between Fe3O4 and Co3S4 species. Besides, the Fe3O4/Co3S4 modified screen printed carbon electrode (Fe3O4/Co3S4-SPCE) shows remarkable stability and repeatability, valuable anti-interference ability and could be used for detection in real water samples. Consequently, the results confirm that as-prepared porous Fe3O4/Co3S4 nanosheets is identified as a promising modifier to detect As(III) in real sample analysis.

Enhanced peroxymonosulfate activation by hierarchical porous Fe3O4/Co3S4 nanosheets for efficient elimination of rhodamine B: Mechanisms, degradation pathways and toxicological analysis.

Fenton-like catalysts have usually superior catalytic activities, however, some drawbacks of ion leaching and difficult-to-recovery limit their applications. In this work, a hierarchical porous Fe3O4/Co3S4 catalyst was fabricated via a simple phase change reaction to overcome these shortcomings. The introduced iron cooperates with cobalt achieving high-efficiency activation of peroxymonosulfate (PMS) to eliminate Rhodamine B (RhB). The results showed that 0.05 g/L Fe3O4/Co3S4 and 1 mM PMS could quickly remove 100% of 200 mg/L RhB within 20 min, and the removal rate of RhB remained above 82% after 5 cycles. Moreover, the as-prepared Fe3O4/Co3S4 possessed a great magnetic separation capacity and good stability of low metal leaching dose. Radical quenching experiments and electron paramagnetic resonance (EPR) techniques proved that sulfate radicals (SO4•-) were the dominant reactive oxygen species responding for RhB degradation. X-ray photoelectron spectroscopy (XPS) pointed out that the synergism of sulfur promoted the cycling of Co3+/Co2+ and Fe3+/Fe2+, boosting the electron transfer between Fe3O4/Co3S4 and PMS. Moreover, the degradation pathways of RhB were deduced by combining liquid chromatography-mass spectrometry (LC-MS) analysis and density functional theory (DFT) calculations. The toxicities of RhB and its intermediates were evaluated as well, which provided significant assistance in the exploration of their ecological risks.

In-situ electronic structure redistribution tuning of single-atom Mn/g-C3N4 catalyst to trap atomic-scale lead(II) for highly stable and accurate electroanalysis.

Constructing catalysts with simple structures, uniform effective sites, and excellent performance is crucial for understanding the reaction mechanism of target pollutants. Herein, the single-atom catalyst of Mn-intercalated graphitic carbon nitride (Mn/g-C3N4) was prepared. It was found that the intercalated Mn atoms acted as strong electron donors to effectively tune the electronic structure distribution of the in-situ N atoms, providing a large number of negative potential atomic-scale sites for catalytic reactions. In the detection, the in-situ N atom established an electron bridge for the transient electrostatic trapping of free Pb(II), which induced Pb-N-Mn coordination bonding. Even in g-C3N4-loaded Mn nanoparticles, the N atom was again confirmed to be the interaction site for coupling with Pb. And the MnII-N4-C/MnIV-N4-C cycle actively participated in the electrocatalysis of Pb(II) was confirmed. Moreover, Mn/g-C3N4 achieved highly stable and accurate detection for Pb(II) with a sensitivity of 2714.47 µA·µM-1·cm-2. And excellent reproducibility and specific detection of real water samples made the electrode practical. This study contributes to understanding the changes in the electronic structure of chemically inert substrates after single-atom intercalation and the interaction between contaminants and the microstructure of sensitive materials, providing a guiding strategy for designing highly active electrocatalytic interfaces for accurate electroanalysis.

Boosting sensitive and selective detection toward Pb(II) via activation effect of Co and orbital coupling between Pb and O over Co@Co3O4 nanocatalyst.

Fruitful achievements on electrochemical detection toward Pb(II) have been achieved, and their good performance is generally attributed to the adsorption property of nanomaterials. However, the design of sensing interfaces from the electronic structure and electron transfer process is limited. Here, Co@Co3O4 acquired an ultra-high detection sensitivity of 103.11 µA µM-1 toward Pb(II), outperforming the results previously reported. The interfacial oxygen atoms build an electron bridge for Co activating Co3O4. Particularly, new energy levels of oxygen atoms were generated and matched with that of Pb(II). The strong orbital coupling effect between O and Pb makes the Co@Co3O4 sensitive and selective toward Pb(II). Compared with Co metal and Co3O4, Pb(II) got more electrons from Co@Co3O4, and longer Pb-O bonds were formed, allowing more Pb(II) to be catalyzed and reduced. Also, the superior stability and reproducibility of electrochemical detection make electrodes practicably. This work reveals that metals can stimulate intrinsically catalytic activity of their metal oxides, with the generation of orbit energy levels that match to a specific analyte. It provides a promising strategy for constructing sensitive and selective sensing interfaces toward ultra-low concentration analyte in body fluid and other complex samples.