Fast Li Storage in MoS2‐Graphene‐Carbon Nanotube Nanocomposites: Advantageous Functional Integration of 0D, 1D,and 2D Nanostructures

A 3D porous composite consisting of nano‐0D MoS₂, nano‐1D carbon nanotubes (CNTs), and nano‐2D graphene is successful prepared using an electrostatic spray deposition (ESD) technique. Depending on the preparation procedure either nanodots of amorphous MoS₂ (0.5–5 nm) or nanocrystalline few‐layered MoS₂ (5–10 nm) bonded to graphene‐carbon nanotubes backbone are obtained. These functionalized carbon nanotubes adhere to a porous graphene‐based network. Such composites can be directly ­deposited on the current collectors without any binder or conductive additives to assemble a battery that shows superior rate performance and cycling ­stability. For nanodots, nucleation and diffusion issues usually connected with ­conversion are largely mitigated if not totally nullified. The use of mechanically and diffusionally isolated but electrochemically well connected electroactive nanodots offer an effective solution to render conversion reaction reversible. The use of nano‐1D and nano‐2D carbon structures offer additional electrical and mechanical advantages that are discussed. Furthermore, this technique, which is easily extendable to other electrode materials, seems to be of a great potential, especially for thin‐film batteries, flexible batteries, and future ­paintable batteries.     

Carbon nanodots with a controlled N structure by a solvothermal method for generation of reactive oxygen species under visible light

Carbon nanodots can function as photosensitizers that have the ability to generate reactive oxygen species such as singlet oxygen, hydroxy (OH) radicals, and superoxide ions. However, most of these can only be generated upon ultraviolet light excitation. Additionally, the mechanism of reactive oxygen species generation by carbon nanodots remains unclear. The development of carbon nanodots that can photosensitize under visible light irradiation is desirable for applications such as photodynamic therapy and pollutant decomposition under visible light. Here, we report novel carbon nanodot-based photosensitizers that generate reactive oxygen species under visible light; they were synthesized using a solvothermal method with two solvents (formamide and water) and amidol as the carbon source. Carbon nanodots from the solvothermal synthesis in formamide showed blue fluorescence, while those obtained in water showed green fluorescence. The photo-excited blue-fluorescent carbon nanodots produced OH radicals, superoxide ions, and singlet oxygen, and therefore could function as both type I and type II photosensitizers. In addition, photo-excited green-fluorescent carbon nanodots generated only singlet oxygen, therefore functioning as type II photosensitizers. It is proposed that the two photosensitizers have different origins of reactive oxygen species generation: the enrichment of graphitic N for blue-fluorescent carbon nanodots and molecular fluorophores for green-fluorescent carbon nanodots.     

One‐Step Controllable Synthesis of Catalytic Ni4Mo/MoOx/Cu Nanointerfaces for Highly Efficient Water Reduction

Currently, in addition to the electroactive non‐noble metal water‐splitting electrocatalysts, a scalable synthetic route and simple activity enhancement strategy is also urgently needed. In particular, the well‐controlled synthesis of the well‐recognized metal–metal nanointer face in a single step remains a key challenge. Here, the synthesis of Cu‐supported Ni₄Mo nanodots on MoO_x nanosheets (Ni₄Mo/MoO_x) with controllable Ni₄Mo particle size and d‐band structure is reported via a facile one‐step electrodeposition process. Density functional theory (DFT) calculations reveal that the active open‐shell effect from Ni‐3d‐band optimizes the electronic configuration. The Cu‐substrate enables the surface Ni–Mo alloy dots to be more electron‐rich, forming a local connected electron‐rich network, which boosts the charge transfer for effective binding of O‐related species and proton–electron charge exchange in the hydrogen evolution reaction. The Cu‐supported Ni₄Mo/MoO_x shows an ultralow overpotential of 16 mV at a current density of 10 mA cm^?2 in 1 m KOH, demonstrating the smallest overpotential, at loadings as low as 0.27 mg cm^?2, among all non‐noble metal catalysts reported to date. Moreover, an overpotential of 105 mV allows it to achieve a current density of 250 mA cm^?2 in 70 °C 30% KOH, a remarkable performance for alkaline hydrogen evolution with competitive potential for applications.     

An LCA study on sludge retreatment processes in Japan

The majority of night soil (human excrements) is source separated from other sewage water and treated at night soil treatment plants in Japan. Efforts have been made to achieve material recovery from this organic mass, together with other organic wastes such as kitchen wastes and manure, by expanding the functions at night soil treatment plants. These facilities with expanded function are called ‘sludge retreatment centers’, which are promoted by the Japanese Ministry of Health and Welfare. Potential environmental impacts of sludge retreatment using two presently available systems in Japan are analyzed for comparison. Systems compared are: 1) Mebius system, a high-speed fermentation process with methane gas recovery and compost production and 2) a comparable system with a basic composting process. The functional unit for this study is concurrent treatment of 40 t/d of kitchen waste, 40 m³/d of night soil, and 60 m³/d of private sewage treatment tank sludge. Impact assessment on Global Warming (IPCC 1996, 20 yrs.), Acidification Potential (De Leeuv — AP), Eutrophication Potential (De Leeuv- EP) and Resource Index (Fava/SETAC & Heijungs) all indicated that sludge retreatment with Mebius system provides a better environmental performance. The main reasons are: 1) production of power using recovered methane and 2) reduction of sludge volume by digestion, which leads to reduction of fuel required for sludge drying. The collection and treatment of night soil and kitchen wastes involves many economic and social factors. Therefore, more studies with different functional units on these systems should be made to obtain a more complete picture that can be used for decision-making processes. The results of this study can be used as a starting point.     

Chemiluminescence detection of trace iodide with flow injection analysis of KMnO4‐carbon dots system

Ultra‐weak chemiluminescence (CL) from the reaction of iodide and KMnO₄ was strongly enhanced by carbon nanodots (CNDs) in an acidic medium. The CL intensity was directly proportional to the concentration of iodide in the solution. Therefore, a flow‐injection CL system with high sensitivity, selectivity and reproducibility is proposed for the determination of iodide. The proposed method exhibited advantages over a linear range of 3.0 × 10^?6–1.0 × 10^?4 mol/L and had a detection limit of 3.5 × 10^?7 mol/L. The method was successfully applied to the evaluation of iodide in food samples with recoveries of between 96 and 103%. The relative standard deviations were 2.1 and 4.1% for intra‐ and inter‐assay precision, respectively.     

DNA‐based chemiluminescent nanoprobes for highly sensitive and selective detection of mercury(II) ion

A simple and sensitive DNA‐stablized gold nanoparticle (AuNP)‐based chemiluminescent (CL) probe for detecting mercury ion (Hg²⁺) in aqueous solution has been developed. The CL strategy relies upon the catalytic activity of unmodified AuNPs on the luminol–H₂O₂ CL reaction, and the interaction of unmodified AuNPs with DNA. The unmodified AuNPs can effectively differentiate unstructured and folded DNA. The DNA desorbs from AuNPs in the presence of Hg²⁺, leading to the increase in CL signal. By rationally varying the number of thymine in single‐strand oligonucleotides, the detection range could be tuned. Employing single‐strand oligonucleotides with 14 thymine in the detecting system, a sensitive linear range for Hg²⁺ ions from 5.0 × 10^–10 to 1.0 × 10^–7 mol/L and a detection limit of 2.1 × 10^–10 mol/L are obtained. Changing the number of thymine to 10 and 6, it leads to a narrow detection range but a high sensitivity. Besides, DNA‐based CL nanoprobes exhibit a remarkable selectivity for Hg²⁺ ions over a variety of competing metal ions. Copyright © 2012 John Wiley & Sons, Ltd.     

Nitrogen‐doped carbon dots as a fluorescent probe for the highly sensitive detection of Ag+ and cell imaging

An easy hydrothermal synthesis strategy was applied to synthesize green‐yellow emitting nitrogen‐doped carbon dots (N‐CDs) using 1,2‐diaminobenzene as the carbon source, and dicyandiamide as the dopant. The nitrogen‐doped CDs resulted in improvement in the electronic characteristics and surface chemical activities. N‐CDs exhibited bright fluorescence emission and could response to Ag⁺ selectively and sensitively. Other ions produced nearly no interference. A N‐CDs based fluorescent probe was then applied to sensitively determine Ag⁺ with a detection limit of 5 × 10^?8 mol/L. The method was applied to the determination of Ag⁺ dissolved in water. Finally, negligibly cytotoxic, excellently biocompatibile, and highly fluorescent carbon dots were applied for HepG2 cell imaging and the quenched fluorescence by adding Ag⁺, which indicated its potential applications.     

Water‐soluble polymeric chemosensor for selective detection of Hg2+ in aqueous solution using rhodamine‐based modified poly(acrylamide–acrylic acid)

We report the fabrication of a novel easily available turn‐on fluorescent water‐soluble polymeric chemosensor for Hg²⁺ ions that was simply prepared by micellar free radical polymerization of a water‐insoluble organic rhodamine‐based Hg²⁺‐recognizing monomer (GR6GH), with hydrophilic monomers acrylamide (AM) and acrylic acid (AA). The chemical structure of the polymeric sensor was characterized by FT‐IR and ¹H NMR spectroscopy. The apparent viscosity average molecular weight M_η of poly(acrylamide–acrylic acid) [poly(AM–NaAA)] and the water‐soluble polymeric chemosensor poly(AM–NaAA–GR6GH) were 1.76 × 10⁶ and 6.84 × 10⁴ g/mol, respectively. Because of its amphiphilic property, the water‐soluble polymeric chemosensor can be used as a chemosensor in aqueous media. Upon addition of Hg²⁺ ions to an aqueous solution of poly(AM–NaAA–GR6GH), fluorescence enhancements were observed instantly. Moreover, other metal ions did not induce obvious changes to the fluorescence spectra. This approach may provide an easily measurable and inherently sensitive method for Hg²⁺ ion detection in environmental and biological applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Two‐channel near‐infrared fluorescence Ag+ ion sensing of a new star‐shaped dendrimer

A new near‐infrared fluorescence sensor PDI‐PD for Ag⁺ ions was successfully prepared and its structure characterized by ¹H nuclear magnetic resonance (NMR), ¹³C NMR and high‐resolution mass spectrometry; matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (HRMS MALDI‐TOF). The probe exhibited rapid, sensitive, and selective two‐channel fluorescence responses towards Ag⁺ ions and protons. The probe has a marked high binding affinity and high sensitivity for Ag⁺, with a detection limit of 1.4 × 10^?6 M. An approximately five‐fold enhanced core emission at 784 nm was attributed to fluorescence resonance energy transfer (FRET). The enhanced core emission of the probe with Ag⁺ ions based on photo‐induced electron transfer and FRET is discussed. In addition, the probe presented a visible colour change. All experimental results demonstrated that PDI‐PD is an efficient tool for the selective, sensitive and rapid detection of Ag⁺ ions and protons using two‐channel fluorescence responses.     

A chelate complex‐enhanced luminol system for selective determination of Co(II), Fe(II) and Cr(III)

A determination method for Co(II), Fe(II) and Cr(III) ions by luminol‐H₂O₂ system using chelating reagents is presented. A metal ion‐chelating ligand complex with a Co(II) ion and a chelating reagent like ethylenediaminetetraacetic acid (EDTA) produced highly enhanced chemiluminescence (CL) intensity as well as longer lifetime in the luminol‐H₂O₂ system compared to metals that exist as free ions. Whereas free Cu(II) and Pb(II) ions had a strong catalytic effect on the luminol‐H₂O₂ system, significantly, the complexes of Cu(II) and Pb(II) with chelating reagents lost their catalytic activity due to the chelating reagents acting as masking agents. Based on the observed phenomenon, it was possible to determine Co(II), Fe(II) and Cr(III) ions with enhanced sensitivity and selectivity using the chelating reagents of the luminol‐H₂O₂ system. The effects of ligand, H₂O₂ concentration, pH, buffer solution and concentrations of chelating reagents on CL intensity of the luminol‐H₂O₂ system were investigated and optimized for the determination of Co(II), Fe(II) and Cr(III) ions. Under optimized conditions, the calibration curve of metal ions was linear over the range of 2.0 × 10^‐8 to 2.0 × 10^‐5 M for Co(II), 1.0 × 10^‐7 to 2.0 × 10^‐5 M for Fe (II) and 2.0 × 10^‐7 to 1.0 × 10^‐4 M for Cr(III). Limits of detection (3σ/s) were 1.2 × 10^‐8, 4.0 × 10^‐8 and 1.2 × 10^‐7 M for Co(II), Fe(II) and Cr(III), respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

Recovery and removal of uranium by using plant wastes

The uranium-adsorbing abilities of seven plant wastes were investigated. High abilities to adsorb uranium from non-saline water containing 10 mg dm⁻³ of uranium were observed with a number of plant wastes tested. However, with seawater supplemented with 10 mg dm⁻³ of uranium, similar results were found only with chestnut residues. When the plant wastes were immobilized with formaldehyde, their ability to adsorb uranium was increased. Uranium and copper ions were more readily adsorbed by all plant wastes tested than other metal ions from a solution containing a mixture of seven different heavy metals. The selective adsorption of heavy metal ions differs with different species of plant wastes. The immobilization of peanut inner skin, orange peel and grapefruit peel increased the selectivity for uranium.     

A fluorescent chemosensor based on naphthol for detection of Zn2+

A simple naphthol‐based fluorescent receptor 1 was prepared and evaluated for its fluorescence response to heavy metal ions. Receptor 1 exhibits an ‘off‐on‐type’ mode with high selectivity in the presence of Zn²⁺ ion. The selectivity of 1 for Zn²⁺ is the consequence of combined effects of chelation‐enhanced fluorescence (CHEF), C = N isomerization and π–π stacking interaction between the two naphthalene rings. Copyright © 2015 John Wiley & Sons, Ltd.     

A highly selective and simple fluorescent sensor for mercury (II) ion detection based on cysteamine‐capped CdTe quantum dots synthesized by the reflux method

Cysteamine (CA)‐capped CdTe quantum dots (QDs) (CA–CdTe QDs) were prepared by the reflux method and utilized as an efficient nano‐sized fluorescent sensor to detect mercury (II) ions (Hg²⁺). Under optimum conditions, the fluorescence quenching effect of CA–CdTe QDs was linear at Hg²⁺ concentrations in the range of 6.0–450 nmol/L. The detection limit was calculated to be 4.0 nmol/L according to the 3σ IUPAC criteria. The influence of 10‐fold Pb²⁺, Cu²⁺ and Ag⁺ on the determination of Hg²⁺ was < 7% (superior to other reports based on crude QDs). Furthermore, the detection sensitivity and selectivity were much improved relative to a sensor based on the CA–CdTe QDs probe, which was prepared using a one‐pot synthetic method. This CA–CdTe QDs sensor system represents a new feasibility to improve the detection performance of a QDs sensor by changing the synthesis method. Copyright © 2014 John Wiley & Sons, Ltd.     

Types of interaction of meso‐tetraphenylporphyrin with alkali and alkaline‐earth metal ions

The cavity in a porphyrin can accommodate metal ions through electron donor–acceptor (EDA) interaction in acetonitrile media without any specially designed fabrication with the porphyrin subunit. Alkali metal ion forms a complex with meso‐tetraphenylporphyrin (TP) in 2:1 stoichiometry, while the bivalent Mg²⁺ ion follows a 1:1 stoichiometry. A fluorescence interaction study indicated that TP can behave like a chemosensor for these ions present in the blood electrolytes. Specifically, for the alkali metal ions intensity‐based sensing was observed, due to inhibition of photoinduced electron transfer (PET), entailing enhancement of fluorescence intensity, and for the alkaline‐earth Mg²⁺ a mixed quenching was observed. Na⁺ and K⁺ ions can be differentiated depending upon the extent of fluorescence enhancement. Copyright © 2011 John Wiley & Sons, Ltd.     

Multifunctional peptide‐based fluorescent chemosensor for detection of Hg2+, Cu2+ and S2− ions

A novel multifunctional fluorescent peptide sensor based on pentapeptide dansyl‐Gly‐His‐Gly‐Gly‐Trp‐COOH (D‐P5) was designed and synthesized efficiently using Fmoc solid‐phase peptide synthesis (SPPS). This fluorescent peptide sensor shows selective and sensitive responses to Hg²⁺ and Cu²⁺ among 17 metal ions and six anions studied in N‐2‐hydroxyethylpiperazine‐N‐2‐ethane sulfonic acid (HEPES) buffer solution. The peptide probe differentiates Hg²⁺ and Cu²⁺ ions by a ‘turn‐on’ response to Hg²⁺ and a ‘turn‐off’ response to Cu²⁺. Upon addition of Hg²⁺ or Cu²⁺ ions, the sensor displayed an apparent color change that was visible under an ultraviolet lamp to the naked eye. The limits of detection (LOD) of DP‐5 were 25.0 nM for Hg²⁺ and 85.0 nM for Cu²⁺; the detection limits for Cu²⁺ were much lower than the drinking water maximum contaminant levels set out by the United States Environmental Protection Agency (USEPA). It is noteworthy that both D‐P5‐Hg and D‐P5‐Cu systems were also used to detect S^2? successfully based on the formation of ternary complexes. The LODs of D‐P5‐Hg and D‐P5‐Cu systems for S^2? were 217.0 nM and 380.0 nM, respectively. Furthermore, the binding stoichiometry, binding affinity and pH sensitivity of the probe for Hg²⁺ and Cu²⁺ were investigated. This study gives new possibilities for using a short fluorescent peptide sensor for multifunctional detection, especially for anions.     

Vermicomposting of different types of waste using Eisenia foetida: a comparative study

A study (100 days duration) was conducted to evaluate the efficiency of an exotic earthworm species (epigeic-Eisenia foetida) for decomposition of different types of organic substrates (kitchen waste, agro-residues, institutional and industrial wastes including textile industry sludge and fibres) into valuable vermicompost. The percentage of, nitrogen, phosphorous and potassium in vermicompost was found to increase while pH and total organic carbon declined as a function of the vermicomposting period. 4.4-5.8-fold increases in TKN was observed in different feed mixtures at the end of vermicomposting period. The increase in TKN for different feed substrates was found in the order: textile sludge>textile fibre=institutional waste>agro-residues>kitchen waste. Available Phosphorus increased 1.4 to 6.5-fold in different feed mixtures in comparison to control. Reduction in TOC was highest in agro-residues (3-fold) followed by kitchen waste (2.2-fold), institutional waste (1.7-fold) and textile industrial wastes (sludge, 1.5-fold and fibre, 1.68-fold) in earthworm-inoculated pots than control. The data reveals that vermicomposting (using E. foetida) is a suitable technology for the decomposition of different types of organic wastes (domestic as well as industrial) into value-added material.     

Carbon Nanodot Surface Modifications Initiate Highly Efficient,Stable Catalysts for Both Oxygen Evolution and Reduction Reactions

Efficient, stable, and low‐cost electrocatalysts for the oxygen evolution and reduction reactions (OER and ORR) are essential components of energy conversion. Although much progress has been achieved in the development of platinum‐based electrocatalysts for ORR and iridium‐based electrocatalysts for OER, they are still not yet viable for large‐scale commercialization because of the high cost and scanty supply of the noble metals. Here, it is demonstrated that carbon nanodots surface‐modified with either phosphorus or amidogen can respectively achieve electrocatalytic activity approaching that of the benchmark Pt/C and IrO₂ /C catalysts for ORR and OER. Furthermore, phosphorus (amidogen)‐modified carbon nanodots with attached Au nanoparticles exhibit superior ORR (OER) activity better than commercial Pt/C (IrO₂/C) catalysts as well as excellent electrochemical stability under visible light.     

Management of soybean oil refinery wastes through recycling them for producing biosurfactant using Pseudomonas aeruginosa MR01

Biosurfactant production through a fermentation process involving the biodegradation of soybean oil refining wastes was studied. Pseudomonas aeruginosa MR01 was able to produce extracellular biosurfactant when it was cultured in three soybean oil refinement wastes; acid oil, deodorizer distillate and soapstock, at different carbon to nitrogen ratios. Subsequent fermentation kinetics in the three types of waste culture were also investigated and compared with kinetic behavior in soybean oil medium. Biodegradation of wastes, biosurfactant production, biomass growth, nitrate consumption and the number of colony forming units were detected in four proposed media, at specified time intervals. Unexpectedly, wastes could stimulate the biodegradation activity of MR01 bacterial cells and thus biosurfactant synthesis beyond that of the refined soybean oil. This is evident from higher yields of biodegradation and production, as revealed in the waste cultures (Y_{deg|(Soybean oil)} = 53.9 % < Y_deg|(wastes) and Y_P/S|(wastes) > Y_{P/S|(Soybean oil)} = 0.31 g g^?1, respectively). Although production yields were approximately the same in the three waste cultures (Y_P/S|(wastes) ? 0.5 g g^?1), microbial activity resulted in higher yields of biodegradation (96.5 ± 1.13 %), maximum specific growth rate (μ _max  = 0.26 ± 0.02 h^?1), and biosurfactant purity (89.6 %) with a productivity of 14.55 ± 1.10 g l^?1, during the bioconversion of soapstock into biosurfactant. Consequently, applying soybean oil soapstock as a substrate for the production of biosurfactant with commercial value has the potential to provide a combination of economical production with environmental protection through the biosynthesis of an environmentally friendly (green) compound and reduction of waste load entering the environment. Moreover, this work inferred spectrophotometry as an easy method to detect rhamnolipids in the biosurfactant products.     

Highly selective ratiometric fluorescent Zn2+ chemosensor based on diarylethene derivative with bi‐8‐carboxamidoquinoline unit

An asymmetrical diarylethene (1O) with a bi‐8‐carboxamidoquinoline unit was synthesized. Its photochromic and fluorescence performances on stimulation with both light and metal ions showed that the diarylethene could serve as a highly selective ratiometric fluorescent chemosensor to detect Zn²⁺ ions based on internal charge transfer and chelation‐enhanced fluorescence processes. The diarylethene could selectively discriminate Zn²⁺ from Cd²⁺ in acetonitrile. Furthermore, Job's plots based on fluorescence titration and electrospray ionization mass spectrometry analysis showed 1 : 1 binding stoichiometry between 1O and Zn²⁺. The binding constant of 1O with Zn²⁺, estimated using the Benesi–Hildebrand method, and the limit of detection were 3.37 × 10⁵ M^–1 and 4.6 × 10^–8 mol/L, respectively. Additionally, the light and metal‐responsive fluorescence behavior of 1O was used successfully to construct a molecular logic circuit with four inputs and one output. Copyright © 2016 John Wiley & Sons, Ltd.     

Luminescence of lemon‐derived carbon quantum dot and its potential application in luminescent probe for detection of Mo6+ ions

This article reports on the first attempt of a systematic study on the synthesis of carbon dots (C‐dots) for the potential applications in labeling and detection of molybdenum ion (Mo⁶⁺). Carbon dots (C‐dots) were synthesized directly via a simple hydrothermal method using lemon juices as carbon precursor with different temperatures to control the luminescence of C‐dots. The obtained C‐dots had strong green light emission and the ability to use its luminescence properties as probes for Mo⁶⁺ detection application, which is based on Mo⁶⁺ induced luminescence quenching of C‐dots. This analysis system exhibits strong sensitivity and good selectivity for Mo⁶⁺ ion, and a detection limit as low as 20 ppm is achieved. These results suggest that the present C‐dots have potential application in optoelectronic, labeling and luminescent probing of Mo⁶⁺ ions.