Selective oxidation behavior based on iron-doped MOF derived carbon-based catalysts: Active site regulation and degradation mechanism analysis.

Selective removal of target organic pollutants in complex water quality of municipal sewage is extremely important for the deep treatment of water quality. Here, energetic MOF and Fe-MOF are doped in electrostatic spinning process to adjust the structure and composition of the catalysts, active oxygen species (ROSs), realizing the selective removal of organic pollutants. Non-azo and azo pollutants are selected as target pollutants. Catalysts PCFe-8 with Fe nanoclusters, EPCFe-8 with Fe-Nx, and EPC-8 without Fe doping are used to activate peroxymonosulfate (PMS) for degrading pollutants. The results show that the PCFe-8/PMS system can produce the most SO4- and exhibit superior removal of azo pollutants, whereas the degradation behavior of non-azo pollutants is more inclined to occur in the EPCFe-8/PMS system and the EPC-8/PMS system. This work provides a reference for elucidating the relationship between catalyst structure and components, types of ROSs, and selective degradation of pollutants.

Regulating Intramolecular Electron Transfer of Nickel-Based Coordinations through Ligand Engineering for Aqueous Batteries.

The integration of electronic effects into complexes for the construction of novel materials has not yet attracted significant attention in the field of energy storage. In the current study, eight one-dimensional (1D) nickel-based salicylic acid  complexes (Ni-XSAs, X = pH, pMe, pMeO, mMe, pBr, pCl, pF, and pCF3 ), are prepared by ligand engineering. The coordination environments in the Ni-XSAs are explored using X-ray absorption fine structure spectroscopy. The charge transfer of the complexes is modulated according to the difference in the electron-donating ability of the substituents, in combination with frontier orbital theory. Furthermore, density functional theory is used to investigate the effect of the substituent position on the electronic properties of the complexes. Ni-mMeSA exhibits better electrical conductivity than Ni-pMeSA. The electrochemical performance of Ni-mMeSA as an aqueous battery cathode is remarkably improved with a maximum energy density of 0.30 mWh cm-2 (125 Wh kg-1 ) and a peak power density of 33.72 mW cm-2 (14.03 kW kg-1 ). This study provides ideas for the application of new coordination chemistry in the field of energy materials science.

Fabrication of a Novel Au Star@AgAu Yolk-Shell Nanostructure for Ovarian Cancer Early Diagnosis and Targeted Therapy.

Purpose: A novel CYPA-targeted, SiO2 encapsulated Au star@AgAu yolk-shell nanostructure (YSNS) was synthesized and used for ovarian cancer early diagnosis and therapy. Methods: Diverse spectroscopic and microscopic methods were utilized to investigate the pattern of the yolk-shell nanostructure. In addition, in vitro and in vivo experiments were carried out. Results: It can be found that the ratio of HAuCl4 and AgNO3 played a critical role in the constitution of the yolk-shell nanostructure. The as-prepared yolk-shell nanostructure showed excellent SERS performance, which could be utilized as SERS substrate for specific sensitivity analysis of ovarian cancer markers cyclophilin A (CYPA) with detectable limit of 7.76*10-10 µg/mL. In addition, the as-prepared yolk-shell nanostructure possessed outstanding photothermal performance, which could be used as photothermal agent for ovarian cancer therapy. Experiments in vitro and in vivo proved that the as-prepared yolk-shell nanostructures are ideal candidate for early diagnosis and therapy for ovarian cancer in one platform. Conclusion: This work holds promise to offer a new method for the detection and therapy of ovarian cancer in the early stage.

Fe and Mo Co-Modulated Coral-like Nickel Pyrophosphate in†situ Derived from Nickel-Foam for Oxygen Evolution.

A highly active catalyst for the oxygen evolution reaction (OER) is critical to achieve high efficiency in hydrogen generation from water splitting. Direct conversion of nickel foam (NF) into nickel-based catalysts has attracted intensive interest due to the tight interaction of the catalysts to the substrate surface. However, the catalytic performances are still far below expectation because of the problems of low catalyst amount, thin catalyst layer, and small active area caused by the limitations of the synthesis method. Herein, we develop a Fe3+ -induced synthesis strategy to transform the NF surface into a thicker catalyst layer. In addition to the excellent conductivity and high stability, the as-prepared FeMo-Ni2 P2 O7 /NF catalysts expose more active sites and facilitate mass transfer due to their thicker catalyst layer and highly dense coral-like micro-nano structure. Furthermore, the Mo, Fe co-modulation optimizes the adsorption free energies of the OER intermediates, boosting catalytic activities. Its catalytic activity is among the highest, and it exhibits a small Tafel slope of 34.71 mV dec-1 and a low overpotential of 161 mV for delivering a current density of 100 mA cm-2 compared to reported Ni-based catalysts. The present strategy can be further used in the design of other catalysts for energy storage and conversion.

Dynamic orbital hybridization triggered spin-disorder renormalization via super-exchange interaction for oxygen evolution reaction.

The oxygen evolution reaction (OER) underpins many aspects of energy storage and conversion in modern industry and technology, but which still be suffering from the dilemma of sluggish reaction kinetics and poor electrochemical performance. Different from the viewpoint of nanostructuring, this work focuses on an intriguing dynamic orbital hybridization approach to renormalize the disordering spin configuration in porous noble-metal-free metal-organic frameworks (MOFs) to accelerate the spin-dependent reaction kinetics in OER. Herein, we propose an extraordinary super-exchange interaction to reconfigure the domain direction of spin nets at porous MOFs through temporarily bonding with dynamic magnetic ions in electrolytes under alternating electromagnetic field stimulation, in which the spin renormalization from disordering low-spin state to high-spin state facilitates rapid water dissociation and optimal carrier migration, leading to a spin-dependent reaction pathway. Therefore, the spin-renormalized MOFs demonstrate a mass activity of 2,095.1 A gmetal-1 at an overpotential of 0.33 V, which is about 5.9 time of pristine ones. Our findings provide a insight into reconfiguring spin-related catalysts with ordering domain directions to accelerate the oxygen reaction kinetics.

Ag nanoparticle in situ decorated on Ti3C2Tx with excellent SERS and EIS immunoassay performance for beta-human chorionic gonadotropin.

Two-dimensional transition metal carbides, nitrides, and carbonitrides (MXene), with excellent optical and electrical properties, are promising substrates for surface-enhanced Raman scattering (SERS) and electrochemical sensors. Therefore, a unique 3D-decorated structure containing silver (Ag) nanoparticles and Ti3C2Tx was designed as the substrates of SERS and electrochemical impedance spectroscopy (EIS) immunosensors. The Ag/Ti3C2Tx composite significantly increases Raman intensity, which is attributed to the synergistic effect of Ti3C2Tx and Ag nanoparticles. Based on the SERS performance of the Ag/Ti3C2Tx composite, the magnetic properties of Fe3O4 and the specificity of antigen-antibody, a sandwich-structured SERS immunosensor is constructed, which can effectively detect trace amounts of beta-human chorionic gonadotropin (ß-hCG). The SERS immunosensor exhibits a wide linear range of 5.0 × 10-6-1.0 mIU mL-1, and a low detection limit of 9.0 × 10-7 mIU mL-1. Meanwhile, the Ag/Ti3C2Tx-based EIS immunosensor is constructed for the portable detection of ß-hCG, which exhibits a wide linear range of 5.0 × 10-2-1.0 × 102 mIU mL-1, a low detection limit of 9.5 × 10-3 mIU mL-1. Moreover, two immunosensors can be used to detect actual serum samples with satisfactory recovery (98.5-102.2%). This work could guide the design of low-cost, sensitive, flexible, and portable biosensors. The SERS and EIS substrates composited with Ti3C2Tx and Ag nanoparticles enable excellent performance for detecting ß-hCG.

Highly Dispersed Antimony-Bismuth Alloy Encapsulated in Carbon Nanofibers for Ultrastable K-Ion Batteries.

Antimony-based alloys have appealed to an ever-increasing interest for potassium ion storage due to their high theoretical capacity and safe voltage. However, sluggish kinetics and the large radius of K+ lead to limited rate performance and severe capacity fading. In this Letter, highly dispersed antimony-bismuth alloy nanoparticles confined in carbon fibers are fabricated through an electrospinning technology followed by heat treatment. The BiSb nanoparticles are uniformly confined into the carbon fibers, which facilitate rapid electron transport and inhibit the volume change during cycling owing to the synergistic effect of the BiSb alloy and carbon confinement engineering. Furthermore, the effect of a potassium bis(fluorosulfonyl)imide (KFSI) electrolyte with different concentrations has been investigated. Theoretical calculation demonstrates that the incorporation of Bi metal is favorable for potassium adsorption. The combination of delicate nanofiber morphology and electrolyte chemistry endows the fiber composite with an improved reversible capacity of 274.4 mAh g-1, promising rate capability, and cycling stability upon 500 cycles.

Dealloying Synthesis of Silicon Nanotubes for High-Performance Lithium Ion Batteries.

The front cover artwork is provided by Dr. Ping Nie and Prof. Limin Chang at Jilin Normal University. The image shows one-dimensional silicon-nitrogen-doped carbon nanotube composite fabricated through a dealloying process. The nanotube engineered silicon coupled with conductive carbon coating synergistically boosts the electrochemical performance. Read the full text of the Research Article at 10.1002/cphc.202100832.

Dealloying Synthesis of Silicon Nanotubes for High-Performance Lithium Ion Batteries.

Practical applications of silicon-based anodes in lithium ion batteries have attracted unprecedented attentions due to the merits of extraordinary energy density, high safety and low cost. Nevertheless, the inevitable huge volume change upon lithiation and delithiation brings about silicon electrode integrity damage and fast capacity fading, hampering the large-scale application. Herein, a novel one-dimensional tubular silicon-nitrogen doped carbon composite (Si@NC) with a core-shell structure has been fabricated using silicon magnesium alloy and polydopamine as a template and precursor. The as-obtained composite exhibits remarkable specific capacity and ultrafast redox kinetics, an outstanding cycling stability with fine capacity of 583.6 mAh g-1 at 0.5 A g-1 over 200 cycles is delivered. Moreover, a full cell matched with LiFePO4 cathode has demonstrated a reversible capacity of 148.8 mAh g-1 with high Coulombic efficiency as well as an excellent energy density of 396 Wh kg-1 . The nanotube structure engineering and silicon confined in nitrogen doped carbon effectively alleviate the volume expansion and endow the composite with superior stability. The robust strategy developed here gives a new insight into designing silicon anodes for enhanced lithium storage properties.

One-step fabrication of Au-Ag alloys and its application for catalysts and SERS sensors.

Au-Ag alloy nanoparticles (NPs) with controllable size and composition were synthesized by a facile, one-pot hydrothermal method. Various characterization techniques including TEM, UV-vis, EDX, HAADF-STEM and XPS were used to discuss the influencing factors for the size and composition of Au-Ag alloy NPs. It is obvious that the size and composition of Au-Ag alloy NPs could be adjusted by the experimental parameters. Catalytic and SERS performance of the Au-Ag alloy NPs were further investigated. Ideal catalytic and SERS performance could be also obtained via optimizing the size and composition of Au-Ag alloy. This work is of importance in theory research and practical application of the noble metal nanocomposites.

Encapsulating silicon particles by graphitic carbon enables High-performance Lithium-ion batteries.

Silicon combines the advantages of high theoretical specific capacity, low potential and natural abundance, which exhibits great promise as an anode for lithium-ion batteries. However, the main challenges associated with Si anode are continuous volume expansion upon cycling and intrinsic low electronic conductivity, leading to sluggish reaction kinetics and rapid capacity fading. Herein we propose a novel in-situ self-catalytic strategy for the growth of highly graphitic carbon to encapsulate Si nanoparticles by chemical vapor deposition, where the magnesiothermic reduction byproducts are used as templates and catalysts for the formation of three-dimensional (3D) conductive network architecture. Benefiting from the improved electronic conductivity and significant suppression of volume expansion, the as-synthesized Si carbon composites exhibit excellent lithium storage capabilities in terms of high specific capacity (2126 mAh g-1 at 0.1 A g-1), remarkable rate capability (750 mAh g-1 at 5 A g-1), and good cycling stability over 450 cycles. Furthermore, the as-fabricated full cell (Si//Ni-rich LiNi0.815Co0.185-xAlxO2) shows high energy density of 395.1 Wh kg-1 and long-term stable cyclability. Significantly, this work demonstrates the effectiveness of in-situ self-catalysis reaction by using magnesiothermic reduction byproducts catalytically derived carbon matrix to encapsulate alloy-type anode material in giving rise to the overall energy storage performance.

Cerium oxide modified iridium nanorods for highly efficient electrochemical water splitting.

An Ir/CeO2 composite catalyst with Ir nanorods (NRs) on amorphous CeO2 was synthesized through a facile one-pot hydrothermal method, which shows excellent activity towards hydrogen evolution and oxygen evolution in alkaline media, even superior to the performance of commercial Pt/C, IrO2 and RuO2 catalysts. The enhanced performance could be attributed to the interfacial electron synergistic effect between Ir and CeO2.

Sulfurization-induced partially amorphous palladium sulfide nanosheets for highly efficient electrochemical hydrogen evolution.

A partially amorphous palladium sulfide was synthesized by sulfurizing crystalline palladium nanosheets facilely, which shows excellent activity and stability towards hydrogen evolution in alkaline media, even superior to the performance of the commercial Pt/C catalyst. The enhanced performance could be attributed to the amorphization transformation and the nanosheet morphology.

Preparation of Ag/TiO2 nanocomposites with controlled crystallization and properties as a multifunctional material for SERS and photocatalytic applications.

Ag/TiO2 nanocomposites with controlled crystallization and properties were prepared by a simple solvothermal method. By using the same raw materials with different ratio and reaction conditions, the morphologies and crystallization of nanocomposites can be tuned. The components of the products were analyzed by TEM and XRD methods respectively. The as-prepared Ag/TiO2 nanocomposites were used as surface-enhanced Raman spectroscopy (SERS) substrate to be evolved for detection of environmental organic dyes pollutants (CV and RhB) with excellent recyclability. Furthermore, it also showed enhanced catalytic performance of nitrophenol compounds (4-NP). After that, the Ag/TiO2 nanocomposites were also used as an active substrate and a superior catalyst for reduction of 4-NTP monitored by Raman spectroscopy.

Yolk-shell hierarchical catalyst with tremella-like molybdenum sulfide on transition metal (Co, Ni and Fe) sulfide for electrochemical water splitting.

Tremella-like MoS2 nano-sheets were directly synthesized on transition metal sulfides (TMS) via a solvothermal method, displaying extreme activities towards hydrogen and oxygen evolution in alkaline condition. The enhanced performance is attributed to the synergistic effect between the MoS2 shell and TMS yolk, expanded interlayer distance and the hierarchical structure.

Synthesis of octahedral Pt-Ni-Ir yolk-shell nanoparticles and their catalysis in oxygen reduction and methanol oxidization under both acidic and alkaline conditions.

Fuel cells are expected to be one of the most promising alternatives to the increasingly scarce fossil fuels, and Pt is the most commonly used catalyst for anodic and cathodic electrochemical reactions. To realize large-scale commercialization, it is most urgent to improve the efficiency of Pt and reduce the cost. Here, we synthesized an octahedral Pt-Ni-Ir yolk-shell catalyst through stepwise co-deposition (SCD), surface-limited Pt deposition (SLPD) and Ni-coordinating etching (NCE) processes. Experimental studies showed that the catalytic activities of the as-prepared trimetal yolk-shell catalyst were several times higher than that of the commercial Pt/C towards oxygen reduction and methanol oxidization under both acidic and alkaline conditions. This work may be extended to designing other multimetallic functional materials with complex hierarchical nanostructures, which is conducive to greatly enhancing the performance.

Effect of glyphosate on X-ray diffraction of copper films prepared by electrochemical deposition.

In the process of electrochemical deposition of metals, the additives can directly affect the final morphology of the metal. Using glyphosate as the additive, copper thin films were prepared by the electrochemical deposition method from a CuSO4 aqueous solution under a specific voltage. The copper thin films were grown on the surface of the indium tin oxide (ITO) film, which was used as the working electrode in a classical three-electrode cell. Glyphosate combined with the copper ion to form a complex, and hindered further reduction and crystallization of the copper ions. The results indicated that the peak intensities of the X-ray diffraction peaks decreased with the increase in the glyphosate concentrations, which can be used as a basis for quantitative detection. The method is simple and highly sensitive.

Preparation of recyclable MoO3 nanosheets for visible-light driven photocatalytic reduction of Cr(vi).

The exploitation of stable and earth-abundant photocatalysts with high catalytic activity remains a significant challenge for removing heavy metals from wastewater. Different from complex nanostructuring, this work focuses on a simple and feasible way to design catalysts. Herein, MoO3 nanosheets were fabricated and grown vertically on the surface of a quartz tablet using a one-step chemical vapor deposition method. The morphology, construction and optical properties of the MoO3 were characterized by XRD, XPS, SEM, HRTEM and UV-Vis methods, and the possible growth mechanism was also discussed. It can be found that the MoO3 nanosheets exhibited significantly enhanced visible light photocatalytic reduction capacity with stable recyclability to Cr(vi). The results show that the MoO3 nanosheets can be used as a cost-effective and recyclable photocatalyst for the removal of Cr(vi) from water. Our findings provide new inspiration for the design of new types of catalysts.

Synthesis of uniform Ag nanosponges and its SERS application.

With the aid of amino acid, various Ag nanostructures were successfully synthesized via the reaction between silver nitrate and hydrazine hydrate at room temperature. The as-prepared products were characterized by X-ray diffraction and scanning electron microscopy. It was found that the morphology of the as-prepared Ag products depended on the sorts of amino acid and solvents. The uniform Ag nanosponges could be obtained in glycol with aid of glycine. Using rhodamine 6G (R6G) as probe, the surface-enhanced Raman scattering (SERS) performance was also investigated, which showed that the uniform Ag nanosponges exhibited an intensive and enhanced Raman scattering. Pazufloxacin mesilate (PM) were detected conveniently using these uniform nanosponges as SERS substrates. The present work might afford some guidance for the rationally controllable synthesis of other metal nanomaterials.

Pt-Pd Bimetal Popcorn Nanocrystals: Enhancing the Catalytic Performance by Combination Effect of Stable Multipetals Nanostructure and Highly Accessible Active Sites.

Exploration of highly efficient electrocatalysts is significantly urgent for the extensive adoption of the fuel cells. Because of their high activity and super stability, Pt-Pd bimetal nanocrystals have been widely recognized as one class of promising electrocatalysts for oxygen reduction. This article presents the synthesis of popcorn-shaped Pt-Pd bimetal nanoparticles with a wide composition range through a facile hydrothermal strategy. The hollow-centered nanoparticles are surrounded by several petals and concave surfaces. By exploring the oxygen reduction reaction on the carbon supported Pt-Pd popcorns in perchloric acid solution, it is found that compared with the commercial Pt/C catalyst the present catalysts display superior catalytic performances in aspects of catalytic activity and stability. More importantly, the Pt-Pd popcorns display minor performance degradations through prolonged potential cycling. The enhanced performances can be mainly attributed to the unique popcorn structure of the Pt-Pd components, which allows the appearance and long existence of the high active sites with more accessibility. The present work highlights the key roles of accessible high active sites in the oxygen reduction reaction, which will ultimately guide the design of highly durable Pt-Pd catalysts.