Solvothermal Guided V2O5 Microspherical Nanoparticles Constructing High-Performance Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries have attracted a lot of attention owing to their cost effectiveness and plentiful resources, but less research has been conducted on the aspect of high volumetric energy density, which is crucial to the space available for the batteries in practical applications. In this work, highly crystalline V2O5 microspheres were self-assembled from one-dimensional V2O5 nanorod structures by a template-free solvothermal method, which were used as cathode materials for zinc-ion batteries with high performance, enabling fast ion transport, outstanding cycle stability and excellent rate capability, as well as a significant increase in tap density. Specifically, the V2O5 microspheres achieve a reversible specific capacity of 414.7 mAh g-1 at 0.1 A g-1, and show a long-term cycling stability retaining 76.5% after 3000 cycles at 2 A g-1. This work provides an efficient route for the synthesis of three-dimensional materials with stable structures, excellent electrochemical performance and high tap density.

Enhanced electrocatalytic performance for H2O2 generation by boron-doped porous carbon hollow spheres.

Electrocatalytic generation of H2O2 via the 2-electron pathway of oxygen reduction reaction (2e-ORR) is an attractive technology compared to the anthraquinone process due to convenience and environmental friendliness. However, catalysts with excellent selectivity and high activity for 2e-ORR are necessary for practical applications. Reported here is a catalyst comprising boron-doped porous carbon hollow spheres (B-PCHSs) prepared using the hard template method coupled with borate transesterification. In an alkali electrolyte, the selectivity of B-PCHS for 2e-ORR above 90% in range of 0.4-0.7 VRHE and an onset potential of 0.833 V was obtained. Meanwhile, the generation rate of H2O2 reached 902.48 mmol h-1 gcat-1 at 0.4 VRHE under 59.13 mA cm-2 in batch electrolysis. The excellent catalytic selectivity of B-PCHS for 2e-ORR originates from the boron element, and the catalytic activity of B-PCHS for H2O2 generation is contributed to the morphology of porous hollow spheres, which facilitates mass transfer processes.

Study on Influence Factors of H2O2 Generation Efficiency on Both Cathode and Anode in a Diaphragm-Free Bath.

Electrosynthesis of H2O2 via both pathways of anodic two-electron water oxidation reaction (2e-WOR) and cathodic two-electron oxygen reduction reaction (2e-ORR) in a diaphragm-free bath can not only improve the generation rate and Faraday efficiency (FE), but also simplify the structure of the electrolysis bath and reduce the energy consumption. The factors that may affect the efficiency of H2O2 generation in coupled electrolytic systems have been systematically investigated. A piece of fluorine-doped tin oxide (FTO) electrode was used as the anode, and in this study, its catalytic performance for 2e-WOR in Na2CO3/NaHCO3 and NaOH solutions was compared. Based on kinetic views, the generation rate of H2O2 via 2e-WOR, the self-decomposition, and the oxidative decomposition rate of the generated H2O2 during electrolysis in carbonate electrolytes were investigated. Furthermore, by choosing polyethylene oxide-modified carbon nanotubes (PEO-CNTs) as the catalyst for 2e-ORR and using its loaded electrode as the cathode, the coupled electrolytic systems for H2O2 generation were set up in a diaphragm bath and in a diaphragm-free bath. It was found that the generated H2O2 in the electrolyte diffuses and causes oxidative decomposition on the anode, which is the main influent factor on the accumulated concentration in H2O2 in a diaphragm-free bath.

Hydrogen production by traditional and novel alkaline water electrolysis on nickel or iron based electrocatalysts.

Hydrogen production through alkaline water electrolysis holds great promise as a scalable solution for renewable energy storage and conversion. The development of non-precious metal-based electrocatalysts with low-overpotential for alkaline water electrolysis is essential to decrease the cost of electrolysis devices. Although the Ni-based and Fe-based electrocatalysts have been commercially employed in the cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER), it is imperative to persistently pursue the advancement of highly efficient electrocatalysts with enhanced current density and fast kinetics. This feature article overviews the progress of NiMo HER cathodes and NiFe OER anodes in the traditional alkaline water electrolysis process for hydrogen production, including the detailed mechanisms, preparation strategies, and structure-function relationship. Moreover, recent advances of Ni-based and Fe-based electrodes in the process of novel alkaline water electrolysis, involving small energetic molecule electro-oxidation and redox mediator decoupled water electrolysis, are also discussed for hydrogen production with low cell voltage. Finally, the perspective of these Ni-based and Fe-based electrodes in the mentioned electrolysis processes is proposed.

Green Environmentally Friendly "Zn(CH3SO3)2" Electrolyte for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries are considered as an ideal substitute for lithium-ion batteries due to their abundant resource storage, high safety, and low price. However, zinc anodes exhibit poor reversibility and cyclic stability in most conventional aqueous electrolytes. Herein, an environmentally friendly Zn(CH3SO3)2 electrolyte is proposed to solve the problems of common aqueous electrolytes. The bulky CH3SO3- anions can regulate the solvation structure of Zn2+ by replacing some water molecules in the primary solvation sheath of Zn2+, thus slowing the hydrogen evolution side reactions and formation of zinc dendrite. Additionally, the changing solvation structure weakens the bonding between Zn2+ and the surrounding water molecules, which is conducive to the transport and charge transfer of Zn2+, thus improving the battery capacity. In the Zn(CH3SO3)2 electrolyte, Zn plating/stripping exhibits a high Coulombic efficiency of >98% and long-term cyclic stability over 800 h. The specific capacity of the assembled Zn//V2O5 cell in 3 mol L-1 Zn(CH3SO3)2 reaches 350 mA h g-1 at 0.1 A g-1, much higher than that in the ZnSO4 electrolyte (213 mA h g-1). In conclusion, this work offers insights into the exploration of advanced green electrolyte systems for zinc-ion batteries.

Nano-Polycrystalline Cu Layer Interlaced with Ti3+-Self-Doped TiO2 Nanotube Arrays as an Electrocatalyst for Reduction of Nitrate to Ammonia.

The electrochemical nitrate reduction reaction (NO3RR) is considered as a promising strategy to degrade nitrate-containing wastewater and synthesize recyclable ammonia at atmospheric pressure and room temperature. In this work, the copper oxides-derived nano-polycrystalline Cu (NPC Cu) was integrated with Ti3+-self-doped TiO2 nanotube arrays (NTA) to fabricate the NPC Cu/H-TiO2 NTA. Ti3+-self-doped TiO2 NTAs and the NPC Cu facilitate electron transfer and mass transportation and create abundant active sites. The unique nanostructure in which Cu nano-polycrystals interlace with the TiO2 nanotube accelerates the electron transfer from the substrate to surface NPC Cu. The density functional theory calculations confirm that the built-in electric field between Cu and TiO2 improves the adsorption characteristic of the NPC Cu/H-TiO2 NTA, thereby converting the endothermic NO3- adsorption step into an exothermic process. Therefore, the high NO3- conversion of 98.97%, the Faradic efficiency of 95.59%, and the ammonia production yield of 0.81 mg cm-2 h-1 are achieved at -0.45 V vs reversible hydrogen electrode in 10 mM NaNO3 (140 mg L-1)-0.1 M Na2SO4. This well-designed NPC Cu/H-TiO2 NTA as an effective electrocatalyst for the 8e- NO3RR possesses promising potential in the applications of ammonia production.

Zn and N co-doped three-dimensional honeycomb-like carbon featured with interconnected nano-pools for dendrite-free zinc anode.

The zinc-ion battery (ZIB) has been extensively researched as one of the promising electrochemical power sources. However, the problem of Zn-dendrite formation during repeated plating and stripping process seriously hinders the development of ZIBs. Herein, three-dimensional (3D) honeycomb-like porous carbon (HPC) with co-doping of zinc and nitrogen is prepared through confining growth of nanoscale zeolite imidazole framework-8 (ZIF-8) on the well-designed nano-pools walls of HPC followed by pyrolysis at 600 ℃ to obtain the final product ZnN/HPC-600, which exhibits large surface area and abundant zincophilic interfaces, ensuring homogeneous distribution of electronic field and low polarization during cycling process. Importantly, ZnN/HPC-600 facilitates the uniform distribution and migration of Zn2+ in this nano-pools structure, avoiding the growth of dendritic Zn crystal during charging stage. The symmetric and asymmetric cells with Zn/ZnN/HPC-600 anodes are assembled, demonstrating excellent cycling reversibility, good rate performance and long-term stability. Besides, a Zn||MnO2 full cell with Zn/ZnN/HPC-600 anode also exhibits robust cycling stability, fast reaction kinetics and almost 100 % coulombic efficiency. This work offers a novel and efficient carbonaceous nano-pools strategy to realize dendrite-free zinc anode in ZIBs.

A facile morphology tunable strategy of Zn-MOF derived hierarchically carbon materials with enhanced supercapacitive performance through the solvent effect.

Metal-organic framework (MOF) derived porous carbon materials have been widely applied as active materials for supercapacitors due to their large specific surface area and ordered pore structure. This paper presents a facile and effective strategy to regulate the morphology of a zinc-based metal-organic framework (Zn-trimesic acid, Zn-BTC) by adjusting the ethanol content in a solvent, which can effectively change the pore structure of Zn-BTC derived porous carbon (PC). The optimal PC prepared in 50% ethanol displays a rodlike structure with a large specific surface area (SSA) of 1930 m2 g-1 and an average pore size of 2.9 nm. This material shows an excellent rate performance with 78.8% capacitance retention when the current density increases from 1 A g-1 to 100 A g-1 and outstanding electrochemical stability with only 2.2% decline of capacitance after 200 000 cycles at 50 A g-1. Moreover, the assembled symmetrical capacitor shows a high energy density of 16.09 W h kg-1 at 698 W kg-1 and 11.89 W h kg-1 at a high power density of 41.56 kW kg-1. This method would provide a new pathway for the preparation of carbon materials with an adjustable pore size for high-performance supercapacitors.

Carbon Coated and Nitrogen Doped Hierarchical NiMo-Based Electrocatalysts with High Activity and Durability for Efficient Borohydride Oxidation.

Sodium borohydride is a promising candidate as hydrogen storage material. The direct borohydride fuel cell (DBFC) as an energy conversation device has attracted intensive attention owing to the low theoretical potential of borohydride oxidation reaction (BOR, -1.24 V vs SHE) on the anode. In this paper, the hierarchical sea urchin-like NiMoN@NC coated by thin carbon layer with optimal BH4- adsorption characteristic was synthesized as a superior electrocatalyst toward BOR. In 1 M NaOH-0.05 M NaBH4, the BOR working potentials are only -55 and 44 mV at the current densities of 10 and 200 mA cm-2 on NiMoN@NC, respectively. Furthermore, the membrane-free DBFC using NiMoN@NC as anodic electrocatalyst shows a maximum power density of 67 mW cm-2 at room temperature with appreciative stability. This well-designed carbon coated and nitrogen doped transition-metal material with hierarchical nano/microstructure as a highly efficient electrocatalyst shows promising potential and bright prospects in electrocatalysis research and practical application for energy conversion systems of DBFC.

Electrochemically controlled ON/OFF switching of NaBH4 hydrolysis based on NiMoN@NC for on-demand hydrogen production.

A facile and novel electrochemically controlled ON/OFF switching of NaBH4 hydrolysis is proposed for on-demand hydrogen production. A low potential can activate the catalyst to the ON state by promoting the adsorption and hydrolysis of BH4-, while a high potential can deactivate the catalyst to the OFF state by inhibiting the chemical hydrolysis.

Al-MOF-derived spindle-like hierarchical porous activated carbon for advanced supercapacitors.

Metal organic frameworks (MOFs) and their derivatives have been widely used in electrochemistry due to their adjustable pore size and high specific surface area (SSA). Herein, a spindle-like hierarchical porous activated carbon (SPC) was synthesized through carbonizing the Al-BTEC precursor and then alkaline washing with NaOH. The fabricated SPC has a uniform shuttle-shaped structure, showing a large BET surface area of 1895 m2 g-1 and an average pore size of 2.4 nm. The SPC product displays a high specific capacitance (SC) of 337 F g-1 at 1 mV s-1 and 334 F g-1 at 1 A g-1. The retention of SC is about 95% after 100 000 cycles when the current density is 50 A g-1, indicating its excellent stability. Furthermore, the assembled symmetrical capacitor with a two-electrode system exhibits a high SC of 173 F g-1 at 1 A g-1 and an energy density of 15.3 W h kg-1 at a power density of 336 W kg-1. This work would provide a new pathway to design and synthesize carbon materials for supercapacitors with excellent properties in the future.

Fe-ZIF8 Coating Cu Foil Derived Carbon as A pH-Universal Electrocatalyst for Efficient Oxygen Reduction Reaction.

It is a great challenge to fabricate highly efficient pH-universal electrocatalysts for oxygen reduction reaction (ORR). Herein, a facile strategy, which includes coating the Fe modified ZIF8 on Cu foil and in situ pyrolysis to evaporate and dope Cu into the MOF derived carbon, is developed to fabricate Fe/Cu-N co-doped carbon material (Cu/Fe-NC). Profiting from the modulated electron distribution and textual properties, well-designed Cu/Fe-NC exhibits superior half-wave potential (E1/2 ) of 0.923 V in alkaline, 0.757 V in neutral and comparable 0.801 V in acid electrolytes, respectively. Furthermore, the ultralow peroxides yield of ORR demonstrates the high selectivity of Cu/Fe-NC in full pH scale electrolytes. As expected, the self-made alkaline and neutral zinc-air batteries equipped with Cu/Fe-NC cathode display excellent discharge voltages, outstanding peak power densities and remarkable stability. This work opens a new way to fabricate highly efficient and pH-universal electrocatalysts for ORR through strategy of Fe/Cu-N co-doping, Cu foil evaporation and carbon defects capture.

Groundwater remediation using Magnesium-Aluminum alloys and in situ layered doubled hydroxides.

In situ remediation of groundwater by zerovalent iron (ZVI)-based technology faces the problems of rapid passivation, fast agglomeration, limited range of pollutants and secondary contamination. Here a new concept of Magnesium-Aluminum (Mg-Al) alloys and in situ layered double hydroxides on is proposed for the degradation and removal of a wide variety of inorganic and organic pollutants from groundwater. The Mg-Al alloy provides the electrons for the chemical reduction and/or the degradation of pollutants while released Mg2+, Al3+ and OH- ions react to generate in situ LDH precipitates, incorporating other divalent and trivalent metals and oxyanions pollutants and further adsorbing the micropollutants. The Mg-Al alloy outperforms ZVI for treating acidic, synthetic groundwater samples contaminated by complex chemical mixtures of heavy metals (Cd2+, Cr6+, Cu2+, Ni2+ and Zn2+), nitrate, AsO33-, methyl blue, trichloroacetic acid and glyphosate. Specifically, the Mg-Al alloy achieves removal efficiency ≥99.7% for these multiple pollutants at concentrations ranging between 10 and 50 mg L-1 without producing any secondary contaminants. In contrast, ZVI removal efficiency did not exceed 90% and secondary contamination up to 220 mg L-1 Fe was observed. Overall, this study provides a new alternative approach to develop efficient, cost-effective and green remediation for water and groundwater.

Quantification of Trace Mercury in Water: Solving the Problem of Adsorption, Sample Preservation, and Cross-Contamination.

Adsorption, sample preservation, and cross-contamination are the major impediments to the accurate and sensitive analysis of low-level mercury samples. Common measures to deal with this issue are to use Teflon, quartz, or borosilicate glass bottles for sampling, standard solution and sample preservation with oxidative chemicals, to prepare standard solutions daily and to use dedicated glassware. This paper demonstrates that these measures are neither efficient nor effective. Two common laboratory sample containers (borosilicate volumetric glass flasks and polypropylene tubes) are investigated for the preparation and preservation of water samples and standard solutions of 0.2-1 µg L-1 with 2% HNO3. Mercury adsorption rates of 6-22% are observed within 30 min and after 48 days, the adsorption is greater than 98%. In stark contrast, no adsorption is found during a testing period of 560 days when the solutions are subject to potassium permanganate-persulfate digestion. New glass flasks and polypropylene bottles are free of mercury contamination but reused flasks are a major source of mercury cross-contamination. To minimize adsorption and cross-contamination, standard solutions are treated by potassium permanganate-persulfate or BrCl digestion, and each individual sample and standard solution should be stored and prepared in single-use polypropylene bottle, without transference.

Hydrogen-motivated electrolysis of sodium carbonate with extremely low cell voltage.

Hydrogen-motivated electrolysis of Na2CO3 for energy-saving production of NaOH and CO2/NaHCO3 is realized by the hydrogen oxidation reaction to insert proton into anolyte and the hydrogen evolution reaction to extract proton out of catholyte. Electrolytic voltage at 100 mA cm-2 is as low as 0.88 V; this voltage is only 35% of the voltage used in the traditional electrolysis.

Enhanced antimicrobial, anti-oxidant applications of green synthesized AgNPs- an acute chronic toxicity study of phenolic azo dyes & study of materials surface using X-ray photoelectron spectroscopy.

The drug resistant bacteria and textile contaminations of water cause different sever health problem throughout the world. To overcome this issue, new environmental benign materials and methods are needed. Plant metabolites directed synthesis of nanoparticles is considered eco-friendly and easy in synthesis. Therefore, it was explicit for the synthesis of AgNPs. The prepared AgNPs were evaluated for antibacterial, antioxidant, photo-catalytic and electrochemical degradation properties as well as toxicity of degradation products on aquatic life. X-Ray Photoelectron Spectroscopy (XPS) has been used for analyzing the surface chemistry of prepared AgNPs. The particle size determines the interaction of nanoparticles with pathogens. Both Gram positive and negative bacteria (Escherichia coli and Staphylococcus areous) are used to determine the anti-microbial potency of the green synthesized AgNPs. The synthesized silver nanoparticles showed significant anti-bacterial applications against B. subtilus and S. aureus. The anti-oxidant applications of AgNPs also studied on comparison with vitamin C. The toxicity of the phenolic Azo dyes (PDA) has been studied against Fish, Daphnia and Green Algae. The electrode potential was studied in the electrochemical redox reaction of hydroxy phenol in aqueous media. Simple electrolyte was used to determine the current efficiency. For the stability of electrode multi cyclic voltammetry was also studied during redox reaction, which showed stability under the potential 0.4 to 0.2 V.

A Self-Supported λ-MnO2 Film Electrode used for Electrochemical Lithium Recovery from Brines.

Lithium recovery from an aqueous resource was accelerated by electrochemically driving the transformation of MnIV /MnIII with a spinel λ-MnO2 film electrode. A λ-MnO2 electrode without binders or conductive additives is preferred for achieving a large capacity at high current density and long-term cycling capability. In this study, a film of Mn(OH)2 was first deposited on the surface of Pt or graphite substrates owing to alkalization near the cathode, then it was oxidized to a Mn3 O4 film by air, followed by being hydrothermally lithiated to LiMn2 O4 spinel and, finally, it was turned into the λ-MnO2 film electrode through potentiostatic delithiation. The results show that the charging/discharging electric capacity of the fabricated λ-MnO2 film electrode was up to ≈100 mAh g-1 at a current density of 50 mA g-1 in 30 mm Li+ aqueous solution, twice that of the λ-MnO2 powder electrode. Also, 82.3 % lithium capacity remained after 100 cycles of an electrochemically assisted lithium recovery process, indicating high availability and good stability of the λ-MnO2 spinel on the electrode. The energy consumption for each cycle is estimated to be approximately 1.55±0.09 J, implying that only 4.14 Wh is required for recovery of one mole of lithium ions by this method.

New natural product -an efficient antimicrobial applications of new newly synthesized pyrimidine derivatives by the electrochemical oxidation of hydroxyl phenol in the presence of 2-mercapto-6-(trifluoromethyl) pyrimidine-4-ol as nucleophile.

Some new pyrimidine derivatives have been synthesised by electrochemical oxidation of catechol (1a) in the existence of 2-mercapto-6-(trifluoromethyl) pyrimidine-4-ol (3) as a nucleophile in aqueous solution using Cyclic Voltammetric and Controlled Potential Coulometry. The catechol has been oxidised to o-quinone through electrochemical method and participative in Michael addition reaction, leading to the development of some new pyrimidine derivatives. The products were achieved in good yield with high pureness. The mechanism of the reaction has been conformed from the Cyclic Voltammetric data and Controlled Potential Coulometry. After purification, the compounds were characterised using modern techniques. The synthesised materials were screened for antimicrobial actions using Gram positive and Gram negative strain of bacteria. These new synthesised pyrimidine derivatives showed very good antimicrobial activity.

Rapid removal of chloroform, carbon tetrachloride and trichloroethylene in water by aluminum-iron alloy particles.

Water contamination with chlorinated hydrocarbons such as chloroform (CHCl3), carbon tetrachloride (CCl4) and trichloroethylene (TCE) is one of the major public health concerns. In this study, we explored the use of aluminum-iron alloys particles in millimeter scale for rapid removal of CHCl3, CCl4 and TCE from water. Three types of Al-Fe alloy particles containing 10, 20 and 58 wt% of Fe (termed as Al-Fe10, Al-Fe20 and Al-Fe58) were prepared and characterized by electrochemical polarization, X-ray diffraction and energy dispersive spectrometer. For concentrations of 30-180 µg/L CHCl3, CCl4 and TCE, a removal efficiency of 45-64% was achieved in a hydraulic contact time of less than 3 min through a column packed with 0.8-2 mm diameter of Al-Fe alloy particles. The concentration of Al and Fe ions released into water was less than 0.15 and 0.05 mg/L, respectively. Alloying Al with Fe enhances reactivity towards chlorinated hydrocarbons' degradation and the enhancement is likely the consequence of galvanic effects between different phases (Al, Fe and intermetallic Al-Fe compounds such as Al13Fe4, Fe3Al and FeAl2) and catalytic role of these intermetallic Al-Fe compounds. The results demonstrate that the use of Al-Fe alloy particles offers a viable and green option for chlorinated hydrocarbons' removal in water treatment.

Biomedical applications of green synthesized Nobel metal nanoparticles.

Synthesis of Nobel metal nanoparticles, play a key role in the field of medicine. Plants contain a substantial number of organic constituents, like phenolic compounds and various types of glycosides that help in synthesis of metal nanoparticles. Synthesis of metal nanoparticles by green method is one of the best and environment friendly methods. The major significance of the green synthesis is lack of toxic by-products produced during metal nanoparticle synthesis. The nanoparticles, synthesized by green method show various significant biological activities. Most of the research articles report the synthesized nanoparticles to be active against gram positive and gram negative bacteria. Some of these bacteria include Escherichia coli, Bacillus subtilis, Klebsiella pneumonia and Pseudomonas fluorescens. The synthesized nanoparticles also show significant antifungal activity against Trichophyton simii, Trichophyton mentagrophytes and Trichophyton rubrum as well as different types of cancer cells such as breast cancer cell line. They also exhibit significant antioxidant activity. The activities of these Nobel metal nano-particles mainly depend on the size and shape. The particles of small size with large surface area show good activity in the field of medicine. The synthesized nanoparticles are also active against leishmanial diseases. This research article explores in detail the green synthesis of the nanoparticles and their uses thereof.