Recent advances and perspectives for intercalation layered compounds. Part 2: applications in the field of catalysis, environment and health.

Intercalation compounds represent a unique class of materials that can be anisotropic (1D and 2D-based topology) or isotropic (3D) through their guest/host superlattice repetitive organisation. Intercalation refers to the reversible introduction of guest species with variable natures into a crystalline host lattice. Different host lattice structures have been used for the preparation of intercalation compounds, and many examples are produced by exploiting the flexibility and the ability of 2D-based hosts to accommodate different guest species, ranging from ions to complex molecules. This reaction is then carried out to allow systematic control and fine tuning of the final properties of the derived compounds, thus allowing them to be used for various applications. This review mainly focuses on the recent applications of intercalation layered compounds (ILCs) based on layered clays, zirconium phosphates, layered double hydroxides and graphene as heterogeneous catalysts, for environmental and health purposes, aiming at collecting and discussing how intercalation processes can be exploited for the selected applications.

Recent advances and perspectives on intercalation layered compounds part 1: design and applications in the field of energy.

Herein, initially, we present a general overview of the global financial support for chemistry devoted to materials science, specifically intercalation layered compounds (ILCs). Subsequently, the strategies to synthesise these host structures and the corresponding guest-host hybrid assemblies are exemplified on the basis of some families of materials, including pillared clays (PILCs), porous clay heterostructures (PCHs), zirconium phosphate (ZrP), layered double hydroxides (LDHs), graphite intercalation compounds (GICs), graphene-based materials, and MXenes. Additionally, a non-exhaustive survey on their possible application in the field of energy through electrochemical storage, mostly as electrode materials but also as electrolyte additives, is presented, including lithium technologies based on lithium ion batteries (LIBs), and beyond LiBs with a focus on possible alternatives such XIBs (X = Na (NIB), K (KIB), Al (AIB), Zn (ZIB), and Cl (CIB)), reversible Mg batteries (RMBs), dual-ion batteries (DIBs), Zn-air and Zn-sulphur batteries and supercapacitors as well as their relevance in other fields related to (opto)electronics. This selective panorama should help readers better understand the reason why ILCs are expected to meet the challenge of tomorrow as electrode materials.

Fenton-like Degradation of Methylene Blue on Attapulgite Clay Composite by Loading of Iron-Oxide: Eco-Friendly Preparation and Its Catalytic Activity.

The continuous discharge of organic dyes into freshwater resources poses a long-term hazard to aquatic life. The advanced oxidation Fenton process is a combo of adsorption and degradation of pollutants to detoxify toxic effluents, such as anti-bacterial drugs, antibiotics, and organic dyes. In this work, an activated attapulgite clay-loaded iron-oxide (A-ATP@Fe3O4) was produced using a two-step reaction, in which attapulgite serves as an enrichment matrix and Fe3O4 functions as the active degrading component. The maximum adsorption capacity (qt) was determined by assessing the effect of temperature, pH H2O2, and adsorbent. The results showed that the A-ATP@Fe3O4 achieves the highest removal rate of 99.6% under optimum conditions: 40 °C, pH = 3, H2O2 25 mM, and 0.1 g dosage of the composite. The dye removal procedure achieved adsorption and degradation equilibrium in 120 and 30 min, respectively, by following the same processes as the advanced oxidation approach. Catalytic activity, kinetics, and specified surface characteristics suggest that A-ATP@Fe3O4 is one of the most promising candidates for advanced oxidation-enrooted removal of organic dyes.

Enhanced dispersion of prussian blue via intercalation into layered double hydroxides for efficient solar seawater evaporation.

Prussian blue (PB) is favored for its photothermal absorption capability in solar vapor generation applications. However, the photothermal conversion efficiency of current PB-based devices is limited by the material's poor dispersion. Herein, we report a method of incorporating PB in the interlayers of layered double hydroxides (LDHs) to prevent its aggregation. The dispersion is further enhanced and stabilized by the addition of sodium dodecyl sulfate (SDS). The thermal and water stability of PB is improved due to the rigid structure of LDHs and interactions between layers and anions. Elemental analysis confirms that with the increase of molar ratio of Mg/Al and the introduction of SDS, concentrations of PB are decreased accordingly. As a result, the rate of solar vapor generation is increased by 35.9% for powders containing 50 mg of equivalent PB. Of note, converting this material into a three-dimensional structure of high rebound foam further enhances solar water evaporation rate, from 0.79 kg m-2 h-1 to 0.98 kg m-2 h-1, with only 20 mg of equivalent PB, increasing the corresponding photothermal conversion efficiency from 53.8% to 66.3%.

Adsorption of Co2+ and Cr3+ in Industrial Wastewater by Magnesium Silicate Nanomaterials.

In this paper, two flower-like magnesium silicate nanomaterials were prepared. These and another two commercial magnesium silicate materials were characterized using a scanning electron microscope, the N2 adsorption-desorption method, and other methods. The structure-activity relationship between the adsorption performance of these four magnesium silicate materials and their specific surface area, pore size distribution, and pore structure was compared. The results showed that the 3-FMS modified by sodium dodecyl sulfonate (SDS) had the largest specific surface area and pore size, the best adsorption performance, and the largest experimental equilibrium adsorption capacity (qe,exp) for Co2+, reaching 190.01 mg/g, and Cr3+, reaching 208.89 mg/g. The adsorption behavior of the four materials for Co2+ and Cr3+ both fitted the pseudo-second-order kinetic model and Langmuir adsorption model, indicating that chemical monolayer uniform adsorption was the dominant adsorption process. Among them, the theoretical adsorption capacity (qm) of 3-FMS was the highest, reaching 207.62 mg/g for Co2+ and 230.85 mg/g for Cr3+. Through further research, it was found that the four materials mainly removed Co2+ and Cr3+ through electrostatic adsorption, surface metal ions (Mg2+), and acidic groups (-OH and -SO3H) exchanging with ions in solution. The adsorption performance of two self-made flower-like magnesium silicate materials for Co2+ and Cr3+ was superior to that of two commercial magnesium silicates.

Colloid Mill-Assisted Ultrasonic-Fractional Centrifugal Purification of Low-Grade Attapulgite and Its Modification for Adsorption of Congo Red.

Attapulgite (APT) is widely used in wastewater treatment due to its exceptional adsorption and colloidal properties, as well as its cost-effectiveness and eco-friendliness. However, low-grade APT generally limits its performance. Here, a colloid mill-assisted ultrasonic-fractional centrifugal purification method was developed to refine low-grade APT. This process successfully separated and removed impurity minerals such as quartz and dolomite from the raw ore, resulting in a refined APT purity increase from 16.9% to 60% with a specific surface area of 135.5 m2∙g-1. Further modifying of the refined APT was carried out through the hydrothermal method using varying dosages of cetyltrimethylammonium chloride (CTAC), resulting in the production of four different APT adsorbents denoted as QAPT-n (n = CTAC mole number) ranging from 0.5 to 5 mmol. Using Congo red (CR) as the target pollutant, the QAPT-5 sample exhibited the best adsorption capacity with the maximum quantity of 1652.2 mg∙g-1 in a neutral solution at 30 °C due to the highest surface charge (zeta potential = 8.25 mV). Moreover, the QAPT-5 pellets (~2.0 g adsorbent) shaped by the alginate-assisted molding method removed more than 96% of 200 mL aqueous solution containing 200 mg∙L-1 CR and maintained this efficiency in 10 adsorption-elution cycles, which exhibited the promising practical application.

A α-L-rhamnosidase from Echinacea purpurea endophyte Simplicillium sinense EFF1 and its application in production of Calceorioside B.

Calceorioside B, a multifunctional phenylethanol glycosides (PhGs) derivative, exhibits a variety of notable properties, such as antithrombotic, anti-tumorigenic, anti-neocoronavirus, anti-inflammatory, and neuroprotective effects. However, the large-scale production of calceorioside B is routinely restricted by its existence as an intermediary compound derived from plants, and still unachieved through excellent and activity chemical synthesis. Here, a total of 51 fungal endophytes were isolated from four PhGs-producing plants, and endophyte Simplicillium sinense EFF1 from Echinacea purpurea was identified with the ability to de-rhamnosing isoacteoside to generate calceorioside B. According to the RNA-transcription of EFF1 under the various substrates, a key gene CL1206.Contig2 that undertakes the hydrolysis function was screened out and charactered by heterologous expression. The sequence alignment, phylogenetic tree construction and substrate specificity analysis revealed that CL1206 was a novel α-L-rhamnosidase that belongs to the glycosyl hydrolase family 78 (GH78). The optimum catalytic conditions for CL1206 were at pH 6.5 and 55 °C. Finally, the enzyme-catalyzed approach to produce calceorioside B from 50 % crude isoacteoside extract was explored and optimized, with the maximum conversion rate reaching 69.42 % and the average producing rate reaching 0.37 g-1.L-1.h-1, which offered a great biocatalyst for potential industrial calceorioside B production. This is the first case for microorganism and rhamnosidase to show the hydrolysis ability to caffeic acid-modified PhGs.

Characterization of three novel stem rot pathogens and their antagonistic endophytic bacteria associated with Cistanche deserticola.

Cistanche deserticola is a precious Chinese medicinal material with extremely high health care and medicinal value. In recent years, the frequent occurrence of stem rot has led to reduced or even no harvests of C. deserticola. The unstandardized use of farm chemicals in the prevention and control processes has resulted in excessive chemical residues, threatening the fragile desert ecological environment. Therefore, it is urgent to explore safe and efficient prevention and control technologies. Biocontrol agents, with the advantages of safety and environment-friendliness, would be an important idea. The isolation, screening and identification of pathogens and antagonistic endophytic bacteria are always the primary basis. In this study, three novel pathogens causing C. deserticola stem rot were isolated, identified and pathogenicity tested, namely Fusarium solani CPF1, F. proliferatum CPF2, and F. oxysporum CPF3. For the first time, the endophytic bacteria in C. deserticola were isolated and identified, of which 37 strains were obtained. Through dual culture assay, evaluation experiment and tissue culture verification, a biocontrol candidate strain Bacillus atrophaeus CE6 with outstanding control effect on the stem rot was screened out. In the tissue culture system, CE6 showed excellent control effect against F. solani and F. oxysporum, with the control efficacies reaching 97.2% and 95.8%, respectively, indicating its great potential for application in the production. This study is of great significance for the biocontrol of plant stem rot and improvement of the yield and quality of C. deserticola.

Fe(OH)x modified ultra-small Ru nanoparticles for highly efficient hydrogen evolution reaction and its application in water splitting.

Developing highly active electrocatalysts for overall water splitting is of remarkable significance for industrial production of H2. Herein, exceptionally active Fe(OH)x modified ultra-small Ru nanoparticles on Ni(OH)2 nanosheets array (Fe(OH)x-Ru/Ni(OH)2) for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are reported. The Fe(OH)x-Ru/Ni(OH)2 nanosheets array prepared with Fe/Ru molar ratio of 5 only requires extremely low overpotentials of 61, 127 and 170 mV to reach current densities of 100, 500 and 800 mA cm-2 in 1 M KOH, respectively, exceeding Pt/C catalyst (75, 160 and 177 mV). Meanwhile, the Fe(OH)x/Ni(OH)2 nanosheets array derived from Fe(OH)x-Ru/Ni(OH)2 exhibits excellent OER activity. It gains current densities of 100, 500 and 800 mA cm-2 at considerably low overpotentials of 265, 285 and 296 mV, respectively, much lower than those of RuO2 and most reported electrocatalysts. The introduction of Fe(OH)x significantly improves the HER activity of Ru nanoparticles by tunning the electronic structure and forming interfaces between Ru and Fe(OH)x. Dramatically, the integrated alkaline electrolyzer based on Fe(OH)x-Ru/Ni(OH)2 and Fe(OH)x/Ni(OH)2 nanosheets array pair just needs 1.649 V to yield a current density up to 500 mA cm-2, exceeding most reported water-splitting electrocatalysts. The strategy reported in this work can be facilely extended to prepare other similar Ru based materials and their derivatives with outstanding catalytic performance for water splitting.