Domain-limited thermal transformation preparation of novel graphitized carbon-supported layered double oxides for efficient tetracycline degradation.

The resource utilization of industrial lignin to construct high-performance catalysts for wastewater treatment field is pioneering research. Herein, the novel graphitized carbon-supported CuCoAl-layered double oxides (LDOs-GC) were successfully designed by the domain-limited thermal transformation technology using sodium lignosulfonate (LS) self-assembled CuCoAl-layered double hydroxides as the precursor. The optimized LDOs-GC catalyst owned the excellent tetracycline (TC) degradation of 98.0% within 15 min by activated peroxymonosulfate (PMS) under optimal conditions (20 mg/L catalyst, 1.5 mM PMS, 30 mg/L TC). The density of metal ions in the catalyst and the synergistic interaction between graphitized carbon (GC) and metal ions played a major role in TC degradation. Based on a comprehensive analysis, the TC degradation in LDOs-GC/PMS system was proved to be accomplished by a combination of free radicals (SO4·- and HO·) and non-radicals (1O2). Meanwhile, the possible degradation pathways of TC were proposed by the analysis of TC degradation intermediates and a comprehensive analysis of the rational reaction mechanism for TC degradation by LDOs-GC/PMS system was also performed. This work provides a new strategy for developing novel high-performance catalysts from industrial waste, while offering a green, cheap and sustainable approach to antibiotic degradation.

Ultralow ruthenium modification of cobalt metal-organic frameworks for enhanced efficient bifunctional water splitting.

Hydrogen economy has emerged as a promising alternative to the current hydrocarbon economy. It involves harvesting renewable energy to split water into hydrogen and oxygen and then further utilising clean hydrogen fuel for various applications. The rational exploration of advanced non-precious metal bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is critical for efficient water splitting. Herein, an ultralow Ru-modified cobalt metal-organic framework (CoRu0.06-MOF/NF) two-dimensional nanosheet array bifunctional catalyst was fabricated through a strategy under mild experimental conditions. The obtained CoRu0.06-MOF/NF exhibited excellent bifunctional electrocatalytic activity and stability in alkaline media, with low overpotentials of 37 and 181 mV and significant durability for more than 95 and 110 h toward the HER and OER at 10 mA cm-2, respectively. The experimental results showed that the two-dimensional nanoarray structure had a large specific surface area and abundant exposed active sites. Additionally, ultralow Ru modification optimized the electronic structure and improved the conductivity of the cobalt metal-organic frameworks, thereby reducing the energy barrier of the rate-limiting step and accelerating the water splitting reaction.

Managing intermediate phase transition of perovskite film with gearbox-like molecule for efficient and stable solar cells.

The smooth and dense light-absorbing layer is an essential factor in polycrystalline solar cells to achieve high photovoltaic performance, while it remains challenging in perovskite solar cells because of the difficulty balancing the speed of crystal nucleation and growth in a solution way. Here, we explored a perovskite nucleation/growth compatible model via manipulating the intermediate complex induced by n-hexylamine (NHA) molecule, guiding us to adjustments perovskite nucleation and growth process. We found that the NHA can act as a gearbox-like molecule to sequentially reduce the perovskite nucleation barrier, promote the nucleation velocity, and retard the perovskite growth simultaneously to obtain uniform perovskite films; correspondingly, this modulation also yields the buried interface with fewer voids and low defects density. In addition, the hydrophobic NHA with long alkyl chain improves the moisture tolerance of the perovskite. The treated solar cell power conversion efficiency was 21.91 %. Importantly, in âˆ¼ 70 % humidity at 25 °C for 30 days, the efficiency of the device declined less than 5 %, exhibiting a good stability performance.

A co-precipitation route for the preparation of eco-friendly Cu-Al-layered double hydroxides with efficient tetracycline degradation.

The construction of novel efficient catalysts for the treatment of organic pollutants in the aqueous environment is essential. The lamellar-like Cu-Al layered double hydroxides (CuAl-LDHs) with various mole ratios were synthesized by a simple route of co-precipitation, and the corresponding degradation characteristic was tested for the removal of tetracycline (TC) using PMS activation. The degradation efficiency of TC over CuAl-LDHs increased up to 93% within 10 min for the Cu/Al mole ratio of 3:1 and almost not changed at a higher mole ratio. For further calcining the optimal catalyst at 300 ℃, the degradation efficiency of TC was found to be increased to 96%. Sulfuric radicals and singlet oxygen were analyzed to be the main reason for the change in degradation characteristics, which was proved by radical quenching experiments and electron paramagnetic resonance technique. The parameters including PMS concentration, catalyst dosage, and reaction temperature on the TC degradation as well as the degradation mechanism for PMS activation were elaborated. The best proportion of CuAl-LDHs owned splendid stability and catalytic activity after reusing, which showed enormous potential in practical application.

Novel Engineered Carbon Cloth-Based Self-Cleaning Membrane for High-Efficiency Oil-Water Separation.

A novel engineered carbon cloth (CC)-based self-cleaning membrane containing a Cu:TiO2 and Ag coating has been created via hydrothermal and light deposition methods. The engineered membrane with chrysanthemum morphology has superhydrophilic and underwater superoleophilic performance. The cooperativity strategy of Cu doping and Ag coating to the TiO2 is found to be critical for engineering the separation efficiency and self-cleaning skill of the CC-based membrane under visible light due to the modulated bandgap structure and surface plasmon resonance. The CC-based membrane has excellent oil-water separation performance when Cu is fixed at 2.5 wt% and the Ag coating reaches a certain amount of 0.003 mol/L AgNO3. The contact angle of underwater oil and the separation efficiency are 156° and 99.76%, respectively. Furthermore, the membrane has such an outstanding self-cleaning ability that the above performance can be nearly completely restored after 30 min of visible light irradiation, and the separation efficiency can still reach 99.65% after 100 cycles. Notably, the membrane with exceptional wear resistance and durability can work in various oil-water mixtures and harsh environments, indicating its potential as a new platform of the industrial-level available membrane in dealing with oily wastewater.

Functionalized MoS2: circular economy SERS substrate for label-free detection of bilirubin in clinical diagnosis.

A one-pot hydrothermal synthesis of Fe-doped MoS2 nanoflowers (Fe-MoS2 NFs) has been developed as a surface-enhanced Raman spectroscopy (SERS) substrate. The Fe-MoS2 NFs display high reproducibility, stability, and recyclability, which is beneficial for the development of the sustainable ecological environment. The SERS substrate provides a high enhancement factor of 105, which can be ascribed to the inducing defects by doping Fe that can improve the charge transfer between probe molecules and MoS2. The Fe-MoS2 NFs have been used to detect bilirubin in serum. The Fe-MoS2 NF SERS substrate exhibits a linear detection range from 10-3 to 10-9 M with a low limit of detection (LOD) of 10-8 M. The substrate displays an excellent selectivity to bilirubin in the presence of other potentially interfering molecules (dextrose and phosphate). These results provide a novel concept to synthesize ultra-sensitive SERS substrates and open up a wide range of possibilities for new applications of MoS2 in clinical diagnosis.

Toward low-cost and sustainable SERS substrate: novel ultrasensitive AMS5 nanoflowers.

Surface-enhanced Raman scattering (SERS) is an analytical technique for the rapid detection of low-concentration analytes. However, the lack of uniform, stable, and recyclable substrate limits its wide applications. Here, Ag-doped MoS2 (AMSx) was prepared by the hydrothermal method. Band structures, LSV, and EIS characteristics confirmed that Ag doping can reduce the indirect band gap and increase the charge transfer between substrates and molecules. As a SERS substrate, AMSx displays excellent reproducibility, stability, and recyclability, which is beneficial for the application of the SERS substrate. Meanwhile, AMSx has excellent sensitivity with an enhancement factor of 4.07 × 106, comparable to that of precious metals. In addition, AMSx exhibits ultrahigh sensitivity in sensing bilirubin and Bisphenol A (BPA); the corresponding detection limit of both is 10-9 M, also better than that of previously reported semiconductors. This work provided a novel idea to synthesize low-cost ultrasensitive SERS substrates and the strategy of improving metal-chalcogenide semiconductor sensing.

Apparent activity and specific activity of lanthanides (La, Ce, Nd) decorated Co-MOF derivatives for electrocatalytic water splitting.

Lanthanide (Ln) rare Earth (RE) elements are often used to incorporate and regulate the local coordination environment and electronic configuration of transition metal based electrocatalysts for acquiring improved electrocatalytic performance. But for a given pristine electrode, is a Ln element concentrated more on promoting the apparent activity of original electrode or on enhancing its specific activity? To address this issue, Ln (La, Ce and Nd) decorated ZIF-67 derivative electrodes (Ln/Co/NC) were fabricated following with the detailed experimental testing of apparent activity and specific activity of assembled electrodes. X-ray photoelectron spectroscopy data confirmed that Ce, Nd and La have played their own role in regulating the coordination electronic structure of the surface atoms of the derived Co/NC by forming different types of chemical bonds. Electrochemical (EC) results confirmed that Ce is concentrated more on the apparent activity of derived Co/NC electrode with the smallest overpotential at 50 mA cm-2(η50), while Nd contributes more to its reaction kinetic property with the smallest value of Tafel slope in alkaline hydrogen evolution reaction process. But for oxygen evolution reaction, all of La, Ce and Nd deteriorate the apparent activity of the pristine Co/NC electrode. Comparatively, La shows a greater ability to modulate the specific activity of Co/NC with a larger electrochemical active surface area normalized current density, while Nd exhibits the best ability to re-establish the properties of reaction centers. This work illustrates the difference influence of La, Ce and Nd on the apparent activity and specific activity of the ZIF-67 derivative Co/NC electrode. It will do some favors in engineering RE elements modified composite electrodes for EC applications.

Electron and ion transport behavior of Vanadium based MXene induced by pressure for Lithium ion intercalated electrodes.

Pressure, analogous with temperature and composition, is other meaningful variant for tuning the structure-activity properties of layered materials. In-situ high-pressure electrical results discover that Vanadium based MXene (V2CTx MXene) conductivity is increased by one order of magnitude from ambient to 10.4 GPa, and then the conductivity is still fixated on meeting growth as pressure releasing. Increased carrier concentration due to denser compactness is the most important factor in improving sample conductivity. Furthermore, abundant of V2CTx samples after preloading different pressures are prepared by the mean of the double-anvil hydraulic press for the first time, and results of increased conductivity were reproduced at ambient conditions. The first-principles calculation of V2C (non-functional group), V2CF, V2CO, and V2COH explains for the lattice expansion by tracing emotion of different function groups upon decompression. Electrochemical results obtain that once forming V2CTx MXene anode rapidly quenched from 2.0 GPa in hydraulic press shows better performance, obviously weakening electric polarization and increasing Li-ion transport rate due to its proper interlaminar densification and improved conductivity. This work opens up a new, simple, and universal approach to develop MXene materials with superior electrical and electrochemical properties, as well as expanding the potential applications for energy storage.

Phase Transitions and Electric Properties of PbBr2 under High Pressure: A First-Principles Study.

PbBr2 has recently attracted considerable attention as a precursor for lead halide perovskite-based devices because of its attractive properties. It is known that pressure can modify the chemical and physical properties of materials by altering the distance between atoms in the lattice. Here, a global structure-searching scheme was used to explore the high-pressure structures of PbBr2, whose structures and properties at high pressure are still far from clear. Three new phases of PbBr2 were predicted in the pressure range of 0-200 GPa, and the pressure-driven phase transition sequence of orthorhombic Pnma (0-52 GPa) → tetragonal I4/mmm (52-80 GPa) → orthorhombic Cmca (80-153.5 GPa) → orthorhombic Immm (153.5-200 GPa) is proposed. Electronic calculations indicate a semiconductor-to-metallic transition of PbBr2 in the Cmca phase at ~120 GPa. Our present results could be helpful in improving the understanding of fundamental physical properties and provide insights to modulate the structural and related photoelectric properties of PbBr2.

Unconventional Stoichiometries of Na-O Compounds at High Pressures.

It has been realized that the stoichiometries of compounds may change under high pressure, which is crucial in the discovery of novel materials. This work uses systematic structure exploration and first-principles calculations to consider the stability of different stoichiometries of Na-O compounds with respect to pressure and, thus, construct a high-pressure stability field and convex hull diagram. Four previously unknown stoichiometries (NaO5, NaO4, Na4O, and Na3O) are predicted to be thermodynamically stable. Four new phases (P2/m and Cmc21 NaO2 and Immm and C2/m NaO3) of known stoichiometries are also found. The O-rich stoichiometries show the remarkable features of all the O atoms existing as quasimolecular O2 units and being metallic. Calculations of the O-O bond lengths and Bader charges are used to explore the electronic properties and chemical bonding of the O-rich compounds. The Na-rich compounds stabilized at extreme pressures (P > 200 GPa) are electrides with strong interstitial electron localization. The C2/c phase of Na3O is found to be a zero-dimensional electride with an insulating character. The Cmca phase of Na4O is a one-dimensional metallic electride. These findings of new compounds with unusual chemistry might stimulate future experimental and theoretical investigations.

Detect, remove and re-use: Sensing and degradation pesticides via 3D tilted ZMRs/Ag arrays.

The objective of this study was to design a versatile and reusable pesticide detection surface-enhanced Raman scattering (SERS) substrate in combination with SERS enhancement and self-cleaning properties. In this paper, we present an inexpensive way to synthesize three-dimensional tilted ZnO micron rods with an Ag hierarchical structure (ZMRs/Ag arrays). Although expensive materials and complex methods were not used, the detection limit of thiram residue was 10-11 M, with a quantitative relationship (R2 = 0.9929) between the thiram concentration and the intensity of the SERS peaks. Additionally, the substrates exhibited fast and efficient photocatalytic activity for the degradation of adsorbed thiram, and the degradation rate in 30 min was close 100 % under visible-light irradiation. The enhancement and photocatalytic mechanism of this substrate were meticulously analyzed in detail. Furthermore, the residues of several mixed pesticides (e.g., thiram and methamidophos compounds) in various juices (such as grape, pear, orange, apple, and cherry juices) were quickly detected using ZMRs/Ag substrates. The main advantages of this substrate are recyclability, stability, selectivity, handiness, and cost-eff ;ectiveness. The substrate can prevent single-use problems associated with conventional SERS substrates and can be applied in pesticide residue and food security.

A Flexible Potassium-Ion Hybrid Capacitor with Superior Rate Performance and Long Cycling Life.

Potassium-ion batteries are promising candidates for large-scale energy storage applications owing to their merits of abundant resources, low cost, and high working voltage. However, the unsatisfying rate performance and cycling stability caused by sluggish K+ diffusion kinetics and dramatic volume expansion hinder the development of potassium-ion batteries. In this study, we design a flexible potassium-ion hybrid capacitor (PIHC) by combining the K-Sn alloying mechanism on the Sn anode and the fast capacitive behavior on the AC cathode with high surface area and mesoporous structure. After optimization, the fabricated Sn||AC PIHC achieves both a high energy density of 120 W h kg-1 and high power density of 2850 W kg-1, much better than other similar hybrid devices. Moreover, a gel polymer electrolyte with a 3D porous structure and high ionic conductivity was employed to improve the structural stability of the Sn anode, which not only realizes good flexibility but also achieves long cycling stability with a capacity retention of nearly 100% for 2000 cycles at a high current density of 3.0 A g-1.

ZnO nanoparticles on MoS2 microflowers for ultrasensitive SERS detection of bisphenol A.

A heterojunction microcomposite was synthesized that consists of ZnO nanoparticles (ZnO NPs) anchored on MoS2 microflowers (MoS2 MFs). The material is shown to enable trace level detection of the pollutant bisphenol A (BPA). The microcomposite was characterized by XRD, XPS, SEM and TEM. In addition, coupling reaction between phenolic estrogens and Pauly's reagents was adopted to greatly enhance the SERS signal. BPA display a characteristic Raman band at 1592 cm-1 which can be used for its selective detection. The assay is highly sensitive and has a 1 nM detection limit which is the lowest among the reported semiconductor substrates. Graphical abstract MoS2/ZnO MCs SERS substrate broke through the application barrier of semiconductor composite materials in SERS substrates. It also sheds light on a deeper understanding of the charge-transfer based enhancement mechanism.

Improved Charge Transfer and Hot Spots by Doping and Modulating the Semiconductor Structure: A High Sensitivity and Renewability Surface-Enhanced Raman Spectroscopy Substrate.

Here, we develop a new method to improve the surface-enhanced Raman spectroscopy (SERS) activity of ZnO using Mg doping combined with noble metals. Highly aligned silver nanoparticles (AgNPs) decorated on an array of Mg-doped ZnO (MZO@Ag) were fabricated. Using rhodamine 6G as the probe molecule, SERS indicated that the MZO@Ag substrate possesses perfect sensitivity, homogeneity, and chemical stability. The enhancement mechanism of this substrate was analyzed in detail, and finite-difference time-domain (FDTD) simulations were used to examine "hot spot" distribution which generated gaps between the balls, the rods, and the stems. FDTD simulation calculated ( E/ E0)4 to be 2.5 × 106. Furthermore, the prepared substrates could degrade the target molecules in situ irradiated by visible light irradiation over the course of 40 min and then efficiently recover detectability through a recycling process. Our substrates were easy to fabricate, self-cleaning, and reusable. They are expected to provide new opportunities for the use of SERS in biological sensors, biomedical diagnostics, and food safety.

Development of composite membranes with irregular rod-like structure via atom transfer radical polymerization for efficient oil-water emulsion separation.

Development of superhydrophilic, stable and cost-effective composite membranes for efficient oil-water emulsion separation is highly desirable. Herein, an irregular rod-like composite membrane was prepared through 3-aminopropyltriethoxysilane (APTES) modification, followed by acrylamide polymerization with atomic transfer radical polymerization (ATRP). The as-prepared membrane exhibits superhydrophilicity/underwater superoleophobicity due to its irregular rod-like structure and pores-induced capillary actions. The composite membrane has demonstrated sufficient stability in acidic, alkaline and salty environments due to the polymerization of acrylamide. Moreover, the as-prepared composite membrane has effectively separated various oil-water emulsions and demonstrated high permeation and superior flux recovery. The present work demonstrates that the ATRP-assisted composite membrane is a promising material in a wide range of applications, such as industrial wastewater recovery and drinking water treatment.

A Multi-Ion Strategy towards Rechargeable Sodium-Ion Full Batteries with High Working Voltage and Rate Capability.

Sodium-ion batteries (SIBs) are a promising alternative for the large-scale energy storage owing to the natural abundance of sodium. However, the practical application of SIBs is still hindered by the low working voltage, poor rate performance, and insufficient cycling stability. A sodium-ion based full battery using a multi-ion design is now presented. The optimized full batteries delivered a high working voltage of about 4.0 V, which is the best result of reported sodium-ion full batteries. Moreover, this multi-ion battery exhibited good rate performance up to 30 C and a high capacity retention of 95 % over 500 cycles at 5 C. Although the electrochemical performance of this multi-ion battery may be further enhanced via optimizing electrolyte and electrode materials for example, the results presented clearly indicate the feasibility of this multi-ion strategy to improve the electrochemical performance of SIBs for possible energy storage applications.