Tailoring and understanding the lithium storage performance of triple-doped cobalt phosphide composites.

Cobalt phosphide (CoP) with high theoretical capacity as well as ceramic-like and metal-like properties is considered as a promising anode for lithium-ion batteries (LIBs). However, the large volume change and sluggish kinetic response limit its practical application. The optimization of composition, structural control and performance regulation of CoP electrodes can be achieved by the bottom-up assembly technique of metal-organic frameworks (MOFs). Due to the effective electronic regulation and lithiophilicity brought by the multiple heteroatoms doping and the synergistic effect of the unique structure derived from MOFs, the N, O, P triple-doped carbon and CoP composites (ZCP@NOP) exhibited excellent rate capability (554.61 mAh g-1 at 2 A g-1) and cycling stability (806.7 mAh g-1 after 500 cycles at 0.5 A g-1). The essence and evolution of lithium storage mechanism in CoP electrodes are also confirmed by the ex-situ techniques. The synergistic benefits of heteroatom co-doping carbon and cobalt phosphide, such as the decrease of the diffusion energy barrier of Li-ions and the optimization of electronic structures, are highlighted in theoretical calculations. In conclusion, new thoughts and ideas for the creation of future battery anode are provided by the combination of the N, O, P co-doping and the adaptable structural adjustment technique.

PBA-Derived Heteroatom-Doped Mesoporous Graphitic Spheroids as Peroxidase Nanozyme for In Vitro Tumor Cells Detection.

Inspired by the two kinds of naturally occurring peroxidases (POD) with vanadium or heme (iron)-based active catalytic centers, we have developed a dual metal-based nanozyme with dual V and Fe-based active catalytic centers. Co-doping of graphene with heteroatoms has a synergistic effect on the catalytic properties of the nanomaterial as the distances of migration of the substrates drastically reduce. However, a few studies have reported the codoping of heterometallic elements in the graphene structure due to the complexity of the synthesis procedures. Herein, we report the synthesis of in situ doped bimetallic VNFe@C mesoporous graphitic spheroids nanozyme via pyrolysis without the assistance of any template assisted method. The Prussian-blue analog-based precursor material was synthesized by a facile one-step low-temperature synthesis procedure. The bimetallic spheroids showed an excellent affinity toward H2O2, with a Km value of 0.26 mM when compared to 0.436 for the natural POD, which is much better than the natural POD, which was utilized to detect tumor cells in vitro through the intracellular H2O2 produced by these cells under high oxidative stress. The VNFe@C mesoporous spheroids generate dual reactive oxygen species, including the •OH and •O2H- radicals, in the presence of H2O2, which are responsible for the POD-like activity of these nanozymes, while the bimetallic V/Fe doping plays a synergistic role in the enhancement of the activity of codoped graphitic spheroids.

Metal-organic-framework derived Zn-V-based oxide with charge storage mechanism as high-performance anode material to enhance lithium and sodium storage.

Transition metal oxides have been extensively studied due to their large theoretical capacities, but their practical application has been hampered by low electrical conductivity and dramatic volume fluctuation during cycling. In this work, we synthesized Zn3V2O8 material using Zn-V-MOF (metal-organic framework) as a sacrificial template to improve the electrochemical characteristics of lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). Unique dodecahedral structure, larger specific surface area and higher ability to mitigate volume changes, improve the electrochemical reaction active site while accelerating ion transport. Zn3V2O8 with 2-methylimidazole as a ligand demonstrated a discharge capacity of 1225.9 mAh/g in LIBs and 761.6 mAh/g in SIBs after 300 cycles at 0.2 C. Density functional theory (DFT) calculation illustrates the smaller diffusion barrier energy and higher specific capacity in LIBs that is ascribed to the fact that Li has a smaller size and hence its diffusion is easier. This study may lead to a path for the manufacturing of high-performance LIBs and SIBs.

Metal-organic frameworks-derived MCo2O4 (M = Zn, Ni, Cu) two-dimensional nanosheets as anodes materials to boost lithium storage.

Transition metal oxides (TMOs) have received significant consideration. Because of their enormous theoretical capacity, cheap, and less toxicity. Notably, cobalt-based materials hold promises as negative electrode materials for batteries, but they suffer from less electrical conductivity and significant volume changes during operation. In order to address these challenges, sacrificial templating techniques at the nanoscale offer a potential solution for improving the electrochemical stability and rate performance of these materials. More specifically, these tactics have proven popular for designing Li-ion storages. To ascertain the impact of multiple metal ions on the electrochemical capacity, metal organic frameworks (MOFs) derived MCo2O4-MOF (M = Zn, Ni, Cu) were developed. Among these, ZnCo2O4 showed the best electrochemical performance (927.2 mAh g-1 at 0.1 A g-1 after 250 cycles). Furthermore, calculations based on density functional theory (DFT) revealed that ZnCo2O4 had the lowest Li+ adsorption energy, with a minimum value of -1.61 eV. Moreover, this research aims to design controllable nanostructures in order to enhance the design of transition bimetallic oxide composites for energy storage applications.

Nanostructured conversion-type anode materials of metal-organic framework-derived spinel XMn2O4 (X = Zn, Co, Cu, Ni) to boost lithium storage.

Bimetallic spinel transition metal oxides play a major part in actualizing eco-friendly electrochemical energy storage systems (ESSs). However, structural precariousness and low electrochemical capacitance restrict their actual implementation in lithium-ion batteries (LIBs). To address these demerits, the sacrificial template approach has been considered as a prospective way to strengthen electrochemical stability and rate performance. Herein, metal-organic frameworks (MOFs) derived XMn2O4-BDC (H2BDC = 1,4-dicarboxybenzene, X = Zn, Co, Cu, Ni) are prepared by a hydrothermal approach in order to discover the effects of various metal cations on the electrochemical performance. Among them, ZnMn2O4-BDC displays best electrochemical properties (1321.5 mAh g-1 at the current density of 0.1 A g-1 after 300 cycles) and high efficiency with accelerated Li+ diffusivity. Density functional theory (DFT) calculations confirm the ZnMn2O4 possesses the weakest adsorption energy on Li+ with a minimized value of -0.92 eV. In comparison with other XMn2O4 through traditional fabrication method, MOF-derived XMn2O4-BDC possesses a higher number of Li+ transport channels and better electric conductivity. This tactic provides a feasible and effective method for preparing bimetallic transition metal oxides and enhances energy storage applications.

Regulating the Electronic Configuration of Spinel Zinc Manganate Derived from Metal-Organic Frameworks: Controlled Synthesis and Application in Anode Materials for Lithium-Ion Batteries.

In recent years, transition metal oxides have been considered as the most promising anode materials due to their high theoretical capacity, low price, and abundant natural reserves. Among them, zinc manganate is used as an electrode material for anodes, whose application is mostly hindered due to its poor ionic/electronic conductivity. In this work, a series of ZnMn2O4 (ZMO) are synthesized by a hydrothermal technique coordinated with a metal-organic framework-based high-temperature calcination process for their application as an anode in lithium-ion batteries (LIBs). Meanwhile, this study systematically explores the influence of carbon doping and the types of organic ligands and oxygen vacancies on the electrochemical properties of the synthesized ZMO. Density functional theory (DFT) calculations and experimental investigations reveal that the introduction of carbon and oxygen vacancies can enhance electronic conductivity, more active sites and faster Li+ adsorption, resulting in better electrochemical performances. As expected, all ZMOs with carbon doping (PMA-ZMO, MI-ZMO, and BDC-ZMO) derived from 1,2,4,5-benzenetetracarboxylic acid, 2-methylimidazole, and 1,4-dicarboxybenzene achieve outstanding electrochemical performance. Meanwhile, the introduction of oxygen vacancies can enhance the electronic conductivity and can significantly reduce the activation energy of Li+ transport, thereby accelerating the Li+ diffusion kinetics in the lithiation/delithiation process. Furthermore, an optimal ZMO anode material synthesized by 2-methylimidazole delivers a high reversible capacity of 1174.7 mA h g-1 after 300 cycles at 0.1 A g-1 and 600 mA h g-1 at 0.5 A g-1 after 300 cycles. After high-rate charge and discharge cycles, the specific capacity rapidly recovers to a value greater than the initial value, which proves the unusual activation and thereby an excellent rate property of the electrode. Hence, we conclude that ZMO provides potential application prospects as an anode electrode material for LIBs.

Engineering at Subatomic Scale: Achieving Selective Catalytic Pathways via Tuning of the Oxidation States in Functionalized Single-Atom Quantum Catalysts.

Regulating the catalytic pathways of single-atom sites in single atom catalysts (SACs) is an exciting debate at the moment, which has redirected the research towards understanding and modifying the single-atom catalytic sites through various strategies including altering the coordination environment of single atom for desirable outcomes as well as increasing their number. One useful aspect concerning the tunability of the catalytic pathways of SACs, which has been overlooked, is the oxidation state dynamics of the single atoms. In this study, iron single-atoms (FeSA) with variable oxidation states, dependent on the precursors, are harnessed inside a nitrogen-rich functionalized carbon quantum dots (CQDs) matrix via a facile one-step and low-temperature synthesis process. Dynamic electronic properties are imparted to the FeSAs by the simpler carbon dots matrix of CQDs in order to achieve the desired catalytic pathways of reactive oxygen species (ROS) generation in different environments, which are explored experimentally and theoretically for an in-depth understanding of the redox chemistry that drives the alternative catalytic pathways in FeSA@CQDs. These alternative and oxidation state-dependent catalytic pathways are employed for specific as well as cascade-like activities simulating natural enzymes as well as biomarkers for the detection of cancerous cells.

Prussian blue analogue/KB-derived Ni/Co/KB composite as a superior adsorption-catalysis separator modification material for Li-S batteries.

Lithium­sulfur batteries (LSBs) are gradually replacing conventional lithium-ion batteries (LIBs), credited to their high theoretical capacity, low cost, and non-toxicity. Nevertheless, the substantial capacity degradation caused by the polysulfide shuttling during charging and discharging has seriously hindered the commercialization of LSBs. Separator modification with functionalized carbon materials has been found to catalyze the breakdown of polysulfides, thereby improving the efficiency of LSBs. Herein, we synthesized Ni/Co-PBAs with KB structures to subsequently derive Ni/Co/KB composites by a carbonization process, which were later used as a modifier layer on the barrier in LSBs in order to effectively alleviate the shuttle problem. The capacity of the Ni/Co/KB composite decorated separator is found to be 1032 mAh/g at 0.5 C with a coulombic efficiency closer to 100%. In the long-term cycling capability evaluation, the initial cycle is approximately 802.9 mAh/g at 1 C, while capacity retention after 400 cycles is also 678.8 mAh/g, with a high-capacity retention rate of 84.5%. The potential of these composites as modifying materials for superior LSBs separators is verified by experimental and theoretical methods.

Nanostructural synergism as MnNC channels in manganese (IV) oxide and fluffy g-C3N4 layered composite with exceptional catalytic capabilities.

The avenues of catalysis and material science are always accepted and it is hoped that a state-of-the-art catalyst with exceptional intrinsic redox characteristics would be produced. This study focused on developing a multi-featured catalyst of high economical and commercial standards to meet the multi-directional applications of environmental and energy demands. Manganese (IV) oxide nanosheets made of fluffy-sheet-like g-C3N4 material were successfully synthesized by pyrolysis method. The electron-rich g-C3N4 network and semiconducting metallic oxides of MnO2 nanosheets generated high electron density interfaces within the intra-composite structure. The input of active interfaces along with strong metal-to-support interactions achieved between two parallel nanosheets in MnO2/g-C3N4 catalyst intrinsically boosted up its electrochemical and optical characteristics for it to be used in multi-catalytic fields. Successful trails of catalysts' performance have been made in three major catalytic fields with enhanced activities such as heterogeneous catalysis (reduction of nitrobenzene with rate constant of "K = 0.734 min-1" and hydrogenation of styrene with "100% conversion" efficiency, including negligible change in five consecutive cycles), photocatalysis (degradation of methylene blue dye model within 20 min with negligible change in five consecutive cycles) and electrocatalysis (oxygen reduction reactions having comparable "diffusion-limited-current density" behaviour with that of the commercial Pt/C catalyst). The enhanced performance of catalysts in transforming chemicals, degrading organic pollutant species and producing sustainable energy resources from air oxygen can mitigate the challenges faced in environmental and energy crises, respectively.

A review on metal-organic framework-derived anode materials for potassium-ion batteries.

In recent years, metal-organic frameworks (MOFs) have been widely used in the field of electrochemical energy storage and conversion because of their excellent properties, such as high specific surface area, adjustable pore size, high porosity, structural diversity, and functional controllability. This paper reviews the applications of metal-organic framework-derived composites such as nitrogen-doped carbon, transition metal sulfides, transition metal selenides, transition metal phosphides and metal selenium compound modifications in potassium ion batteries (PIBs) as anode electrode materials. A variety of MOF-derived composites with different structures and morphologies based on several types of ligands, including 2-methylimidazole, aromatic carboxylic acids, and ferricyanide, have been discussed. Moreover, the current challenges faced by MOF-derived materials and possible countermeasures are proposed.

Nanostructured Iron Fluoride Derived from Fe-Based Metal-Organic Framework for Lithium Ion Battery Cathodes.

A comprehensive strategy for the morphological control of octahedral and spindle Fe-based metal-organic frameworks (Fe-MOFs) via microwave-assisted adjustment is proposed in this research. Afterward, in situ copyrolysis under N2 atmosphere contributes to the fabrication of two shape-maintained FeF3·0.33H2O nanostructures (named O-FeF3·0.33H2O and S-FeF3·0.33H2O, respectively) with confined hierarchical porosity and graphitized carbon skeleton. The lithium storage performances for the MOF-derived octahedral O-FeF3·0.33H2O and spindle S-FeF3·0.33H2O composites are investigated, and the prospective lithium storage mechanism is discussed. As a result, the main product of the porous O-FeF3·0.33H2O structure is found to be a promising cathode material for lithium ion batteries owing to its advantageous electrochemical capability. Even after being cycled over 1000 times at 2 C (1 C = 237 mAh g-1), the capacity attenuation rate of the as-prepared O-FeF3·0.33H2O electrode is as low as 0.039% per cycle. The combination of proper octahedral morphology and highly graphitized carbon modification can not only enhance the conductivity of the cathode but also promote the diffusion of Li+ effectively. The remarkable performance of octahedral O-FeF3·0.33H2O can be confirmed by the Li-ion diffusion coefficient (DLi+) calculation analysis and kinetics analysis of lithium storage behavior.

A Hybrid VOx Incorporated Hexacyanoferrate Nanostructured Hydrogel as a Multienzyme Mimetic via Cascade Reactions.

Inspired by the cascade reactions occurring in micro-organelles of living systems, we have developed a hybrid hydrogel, a nanozyme that mimics three key enzymes including peroxidase, superoxide dismutase, and catalase. The organic/inorganic nanostructured hydrogel constituting VOx incorporated hexacyanoferrate Berlin green analogue complex (VOxBG) is prepared by a simple one-step hydrothermal process, and its composition, structure, and properties are thoroughly investigated. Polyvinylpyrrolidone, a low-cost and biocompatible polymer, was utilized as a scaffold to increase the surface area and dispersion of the highly active catalytic centers of the nanozyme. Compared to the widely used horseradish peroxidase in enzyme-linked immunosorbent assay, our VOxBG analogue hydrogel displays an excellent affinity toward the chromogenic substrate that is used in these peroxidase-based assays. This higher affinity makes it a competent nanozyme for detection and oxidation of biomolecules, including glucose, in a cascade-like system which can be further used for hydrogel photolithography. The VOxBG analogue hydrogel also holds a good ability for the rapid and efficient oxidative degradation of environmentally unfriendly recalcitrant substrates under light irradiation. Detailed mechanistic studies of this multifaceted material suggest that different complex catalytic processes and routes are involved in these photo-Fenton and Fenton reactions that are responsible for the generation as well as consumption of reactive oxygen species, which are effectively activated by a multienzyme mimetic of the VOxBG analogue hydrogel.

Plasmonic MoO3-x nanoparticles incorporated in Prussian blue frameworks exhibit highly efficient dual photothermal/photodynamic therapy.

Development of near infrared (NIR) light-responsive nanomaterials for high performance multimodal phototherapy within a single nanoplatform is still challenging in technology and biomedicine. Herein, a new phototherapeutic nanoagent based on FDA-approved Prussian blue (PB) functionalized oxygen-deficient molybdenum oxide nanoparticles (MoO3-x NPs) is strategically designed and synthesized by a facile one-pot size/morphology-controlled process. The as-prepared PB-MoO3-x nanocomposites (NCs) with a uniform particle size of ∼90 nm and high water dispersibility exhibited strong optical absorption in the first biological window, which is induced by plasmon resonance in an oxygen-deficient MoO3-x semiconductor. More importantly, PB-MoO3-x NCs not only exhibited a high photothermal conversion efficiency of ∼63.7% and photostability but also offered a further approach for the generation of reactive oxygen species (ROS) upon singular NIR light irradiation which significantly improved the therapeutic efficiency of the PB agent. Furthermore, PB-MoO3-x NCs showed a negligible cytotoxic effect in the dark, but an excellent therapeutic effect toward two triple-negative breast cancer (TNBC) cell lines at a low concentration (20 µg mL-1) of NCs and a moderate NIR laser power density. Additionally, efficient tumor ablation and metastasis inhibition in a 4T1 TNBC mouse tumor model can also be realized by synergistic photothermal/photodynamic therapy (PTT/PDT) under a single continuous NIR wave laser. Taken together, this study paved the way for the use of a single nanosystem for multifunctional therapy.

Intrinsic peroxidase-like activity and enhanced photo-Fenton reactivity of iron-substituted polyoxometallate nanostructures.

Heteropolyacids (HPAs) are a class of polyoxometallates (POMs) with oxygen-rich surfaces. Herein, we have developed an Fe-containing heteropolyacid by cation-exchange and employed KFePW12O40 nanostructures for Fenton, photo-Fenton and enzyme-mimetic reactions. The as-prepared KFePW12O40 catalyst exhibits efficient degradation of Rhodamine B (RhB) via the photo-Fenton reaction. As an enzyme-mimetic, this material can effectively oxidize TMB and dopamine. The obtained nanomaterials were characterized via SEM, TEM, XPS, BET surface area, TGA, UV-Vis spectroscopy, FT-IR, and XRD techniques. The photocatalyst has a relatively large surface area of 38 m2 g-1, and the Keggin structure of phosphotungstic ions is kept intact during the preparation. The RhB dye pollutants can be efficiently bleached and degraded up to about 80% within a one hour photo-Fenton reaction under visible light irradiation. Our results indicate that the KFePW12O40 nanomaterial can effectively mimic the enzyme cascade reaction of horseradish peroxidase (HRP). It also has a high affinity toward 3,3',5,5'-tetramethylbenzidine (TMB) for oxidation and henceforth, it has been used for the colorimetric assay of dopamine and H2O2. Overall, our study suggests that KFePW12O40 can be used for the efficient degradation of environmental pollutants. The KFePW12O40 catalyst is stable and can be easily separated from the reaction system for reuse without an obvious loss of activity.

Highly dispersed ultra-small Pd nanoparticles on gadolinium hydroxide nanorods for efficient hydrogenation reactions.

Heterogeneous catalytic hydrogenation reactions are of great importance to the petrochemical industry and fine chemical synthesis. Herein, we present the first example of gadolinium hydroxide (Gd(OH)3) nanorods as a support for loading ultra-small Pd nanoparticles for hydrogenation reactions. Gd(OH)3 possesses a large number of hydroxyl groups on the surface, which act as an ideal support for good dispersion of Pd nanoparticles. Gd(OH)3 nanorods are prepared by hydrothermal treatment, and Pd/Gd(OH)3 catalyst with a low loading of 0.95 wt% Pd is obtained by photochemical deposition. The catalytic hydrogenation of p-nitrophenol (4-NP) to p-aminophenol (4-AP) and styrene to ethylbenzene is performed as a model reaction. The obtained Pd/Gd(OH)3 catalyst displays excellent activity as compared to other reported heterogeneous catalysts. The rate constant of 4-NP reduction is measured to be 0.047 s-1 and the Pd/Gd(OH)3 nanocatalyst shows no marked loss of activity even after 10 consecutive cycles. Additionally, the hydrogenation of styrene to ethylbenzene over Pd/Gd(OH)3 nanorods exhibits a turnover frequency (TOF) as high as 6159 h-1 with 100% selectivity. Moreover, the catalyst can be recovered by centrifugation and recycled for up to 5 consecutive cycles without obvious loss of activity. Our results indicate that Gd(OH)3 nanorods act as a promoter to enhance the catalytic activity by providing a synergistic effect from the strong metal support interaction and the large surface area for high dispersion of small sized Pd nanoparticles enriched with hydroxyl groups on the surface. The high performance of Pd/Gd(OH)3 in heterogeneous catalysis offers a new, efficient and facile strategy to explore other metal hydroxides or oxides as supports for organic transformations.

One-Step Growth of Iron-Nickel Bimetallic Nanoparticles on FeNi Alloy Foils: Highly Efficient Advanced Electrodes for the Oxygen Evolution Reaction.

Electrochemical water splitting is an important process to produce hydrogen and oxygen for energy storage and conversion devices. However, it is often restricted by the oxygen evolution reaction (OER) due to its sluggish kinetics. To overcome the problem, precious metal oxide-based electrocatalysts, such as RuO2 and IrO2, are widely used. The lack of availability and the high cost of precious metals compel researchers to find other resources for the development of cost-effective, environmentally friendly, earth-abundant, nonprecious electrocatalysts for OER. Such catalysts should have high OER performance and good stability in comparison to those of available commercial precious metal-based electrocatalysts. Herein, we report an inexpensive fabrication of bimetallic iron-nickel nanoparticles on FeNi-foil (FeNi4.34@FeNi-foil) as an integrated OER electrode using a one-step calcination process. FeNi4.34@FeNi-foil obtained at 900 °C shows superior OER activity in alkaline solution with an overpotential as low as 283 mV to achieve a current density of 10 mA cm-2 and a small Tafel slope of 53 mV dec-1. The high performance and durability of the as-prepared nonprecious metal electrode even exceeds those of the available commercial RuO2 and IrO2 catalysts, showing great potential in replacing the expensive noble metal-based electrocatalysts for OER.

Highly Efficient Fenton and Enzyme-Mimetic Activities of Mixed-Phase VOx Nanoflakes.

Artificial enzyme mimetics is a current research area with much interest from scientific community. Some nanomaterials have been found to possess intrinsic enzyme-mimetic activity. In this study, VOx nanoflakes with mixed-phases are synthesized via a quick and facile one-pot synthetic process and their Fenton reaction and enzyme-mimetic activities have been studied. The results show that obtained VOx is not only highly effective Fenton reagent, completely decomposing Rhodamine B (RhB) within less than 1 min, but also exhibits excellent intrinsic peroxidase-like activity as well as H2O2 catalase-like activity. Our results suggest that this VOx nanomaterial can effectively mimic the enzyme cascade reaction of horseradish peroxidase (HRP). VOx nanoflakes have excellent affinity toward 3,3',5,5'-tetramethylbenzidine (TMB) for oxidation and henceforth, it can be used for the colorimetric assay of glucose and H2O2. Moreover, this study indicates that VOx nanoflakes can also be used for the efficient degradation of environmental pollutants.

Multifunctional flexible free-standing titanate nanobelt membranes as efficient sorbents for the removal of radioactive (90)Sr(2+) and (137)Cs(+) ions and oils.

For the increasing attention focused on saving endangered environments, there is a growing need for developing membrane materials able to perform complex functions such as removing radioactive pollutants and oil spills from water. A major challenge is the scalable fabrication of membranes with good mechanical and thermal stability, superior resistance to radiation, and excellent recyclability. In this study, we constructed a multifunctional flexible free-standing sodium titanate nanobelt (Na-TNB) membrane that was assembled as advanced radiation-tainted water treatment and oil uptake. We compared the adsorption behavior of (137)Cs(+) and (90)Sr(2+) on Na-TNB membranes under various environmental conditions. The maximum adsorption coefficient value (Kd) for Sr(2+) reaches 10(7) mL g(-1). The structural collapse of the exchange materials were confirmed by XRD, FTIR and XPS spectroscopy as well as Raman analysis. The adsorption mechanism of Na-TNB membrane is clarified by forming a stable solid with the radioactive cations permanently trapped inside. Besides, the engineered multilayer membrane is exceptionally capable in selectively and rapidly adsorbing oils up to 23 times the adsorbent weight when coated with a thin layer of hydrophobic molecules. This multifunctional membrane has exceptional potential as a suitable material for next generation water treatment and separation technologies.