Electrochemical coverage of reduced graphene oxide layers on sulfur supported by biochar for enhancing performance of Li-S battery.

To improve the electrochemical performance of Li-S batteries, a cathodic material (rGO150/S/CF-75) was fabricated for Li-S batteries by adopting a melt-flow method to load sulfur on biomass-derived carbon fibers, then the reduced graphene oxide was electrochemically covered on the outside surface of the sulfur. The coverage of reduced graphite oxide layers endows the performance of S/CF-75 multiple improvements. The specific capacity of rGO150/S/CF-75 cathode delivers a specific capacity of 1451.4 mAh g-1 at 0.1 A g-1. The specific capacity of rGO150/S/CF-75 cathode can still maintain 537.3 mAh g-1 after 1000 cycles at 5 A g-1 (109 % capacity retention). The excellent performance of rGO150/S/CF-75 cathode is benefit from not only the conductive paths of reduced graphene oxide layers and protective function of reduced graphene oxide layers inhibiting that the soluble sulfur diffuse into bulk electrolyte, but also the redistribution of sulfur on conductive carbon components during the cycling process.

Enhanced electrochemical performance of MnO2 nanoparticles: graphene aerogels as conductive substrates and capacitance contributors.

An N-doped graphene aerogel (NGA) is used as a reactive container for growing MnO2 nanoparticles via a soaking-hydrothermal strategy. MnO2 nanoparticles pile up on the surface of reduced graphene oxide sheets with crosslinked structures serving as electrical conductors. Importantly, the NGA generates extra capacitance during the electrochemical process, which accomplishes a satisfactory compensation in the physical-chemical properties of MnO2. As a cathodic electrode for Zn-ion batteries, the MnO2/NGA exhibits a specific capacity of 275.8 mA h g-1 and pre-eminent cycling stability with a retention of 93.6% at 3 A g-1 after 1000 cycles. Meanwhile, the proposed electrode also shows a relatively high specific capacitance of 341 F g-1 for a supercapacitor in 1 M Na2SO4. Meanwhile, the long-term cycling stability shows only a slight decrease by 5.1% of the initial capacitance after 5000 continuous cycles at 3 A g-1, which indicates its superior electrochemical stability. Additionally, the assembled asymmetric supercapacitor also shows good electrochemical performance. This work highlights the extensive function of an N-doped graphene aerogel as a promising substrate for enhancing the electrochemical performance of MnO2, which opens the gate for wide potential applications of graphene aerogel composites emphasizing their complementary effects.

Ion-imprinted silica adsorbent modified diffusive gradients in thin films technique: Tool for speciation analysis of free lead species.

A new diffusive gradients in thin films (DGT) device, using Pb(II) ion-imprinted silica (IIS) as the binding agents and commercial cellulose acetate dialysis (CAD) membrane as the diffusion layer (CAD/IIS-DGT), has been developed and evaluated for sampling and measurement of free Pb(II) species. The CAD/IIS-DGT devices were successfully applied to the measurement of free Pb(II) species in synthetic solutions, in natural freshwaters and in industrial wastewaters. The CAD/IIS-DGT provides reliable results over pH range of 4.5-6.5 and a wide range of ionic strength from 1.0×10(-3) to 0.7 mol L(-1). The concentrations of the free Pb(II) species in synthetic solution containing different concentrations of ligands measured by CAD/IIS-DGT showed a good agreement with the value measured by Pb-ion selective electrode. Field deployments of the CAD/IIS-DGT devices allowed accurate measurements of the concentrations of free Pb(II) species.

Sampling 4-chlorophenol in water by DGT technique with molecularly imprinted polymer as binding agent and nylon membrane as diffusive layer.

For the first time, a diffusive gradients in thin films (DGT) device using molecularly imprinted polymer (MIP) as the binding agent and nylon membrane (NM) as the diffusive layer (NM-MIP-DGT) has been developed for sampling 4-chlorophenol (4-CP) in water. The MIP was prepared by precipitation polymerization with methacrylic acid as monomer and ethyleneglycoldimethacrylate as cross-linker. The diffusion coefficient of 4-CP through NM was obtained to be 0.788±0.040 µ cm(2) s(-1) by diffusion cell method. The ratio was 1.01±0.05 (mean±standard deviation) for the concentration of 4-CP sampled by NM-MIP-DGT and analyzed by HPLC method to the total concentration of 4-CP in the synthetic solution where free 4-CP species dominated. The results showed that NM-MIP-DGT could sample 4-CP in synthetic solution accurately. The performance of NM-MIP-DGT for sampling 4-CP was independent of pH in the range of 3-7 and ionic strength in the range of 0.0001-0.1 mol L(-1) NaCl solution. The concentration of free form of 4-CP sampled by NM-MIP-DGT decreased with the increasing concentration of dissolved organic carbon in different water samples due to the electrostatic interaction of natural organic compounds with 4-CP. 1.8 mg L(-1) of the free form of 4-CP was determined by HPLC which was sampled by NM-MIP-DGT in an intermediate untreated industrial effluent. The NM-MIP-DGT can be a potential passive tool for sampling the free form of 4-CP in water.

Application of poly (ethyleneimine) solution as a binding agent in DGT technique for measurement of heavy metals in water.

A 0.050 mol L(-1) solution of poly (ethyleneimine) (PEI), had been used as a novel binding agent of diffusive gradients in thin-films (DGT) technique (PEI-DGT) for measuring the concentrations of labile Cu(2+), Cd(2+) and Pb(2+) in waters. The binding capacities of the PEI-DGT for Cu(2+), Cd(2+) and Pb(2+) were 11.8, 10.2 and 10.6 µmol L(-1), respectively. The performance of PEI-DGT was independence of pH in the range of 4-8 and ionic strength in the range from 1×10(-4) to 0.1 mol L(-1) (as NaNO3). PEI-DGT could measure 104.7±5.2% of the total concentration of Cd(2+) (0.500 mg L(-1)), 95.2±4.3% of the total Cu(2+) (0.500 mg L(-1)) and 99.2±3.4% of the total Pb(2+) (0.500 mg L(-1)) in synthetic solution. Effects of the ligands on the measurement of labile metals were also investigated in synthetic solutions containing the various concentrations of EDTA and humic acid. In EDTA solution, the concentrations of labile metals measured by PEI-DGT showed good agreement with the theoretical concentrations of free metal ions. In humic acid solution, the concentrations of labile metals measured by PEI-DGT decreased with the increase of the concentrations of humic acid. Several DGT devices with various binding agents, including PEI, sodium polyacrylate and poly(4-styrenesulfonate) solution, were used for the measurement of labile fractions of Cu(2+), Cd(2+) and Pb(2+) in the spiked waters and in mine wastewaters. The results showed that the concentrations of labile metal measured by DGT devices with different binding agents could be significantly different, indicating that the labile fractions of metals were dependent on the binding strength of the binding agents with metals. By choosing binding agents, the useful information on the speciation and bioavailability of the analytes can be provided.

Use of polymer-bound Schiff base as a new liquid binding agent of diffusive gradients in thin-films for the measurement of labile Cu²âº, Cd²âº and Pb²âº.

A new diffusive gradients in thin-films (DGT) device with solution of polymer-bound Schiff base (Py-PEI) derived from poly(ethyleneimine) and 2-pyridinecarboxaldehyde as the binding agent (Py-PEI DGT) was developed for measuring labile Cu(2+), Cd(2+) and Pb(2+) in waters. In synthetic solution, uptake percentages of Cu(2+), Cd(2+) and Pb(2+) by Py-PEI DGT were 99.2 ± 4.4%, 103.7 ± 4.8% and 98.7 ± 5.5% of the total metals, respectively. Performance of Py-PEI DGT was independent of pH 4-8.5 and ionic strength 1 × 10(-4)-0.1 mol L(-1). The uptake of labile metals showed agreement with the theoretical values of free ions in EDTA solution, and decreased with increase of humic acid (HA) and dissolved organic carbon (DOC) contents in water due to the complexation of HA and DOC with metals. DGT devices containing different liquid binding agents (Py-PEI, polyacrylate (PA) and poly(4-styrenesulfonate) (PSS)) were deployed in the same solution. The higher uptake percentages of Py-PEI DGT (13.2 ± 1.1, 26.5 ± 2.4 and 62.7 ± 3.2% of total Cu(2+), Cd(2+) and Pb(2+)) were obtained with respective to PSS DGT (6.7 ± 0.6, 9.2 ± 0.9 and 29.6 ± 2.7% of total above metals) and PA DGT (8.9 ± 0.9 and 16.2 ± 1.1% of total Cu(2+) and Cd(2+)) due to its relatively strong binding affinity with metals.

Effective concentration difference model to study the effect of various factors on the effective diffusion coefficient in the dialysis membrane.

Cellulose acetate dialysis membrane (CDM) has been used in the diffusive gradients in thin films (DGT) technique, where accurate diffusion coefficients are essential for the assessment of the concentrations of labile metal in solution. Effective concentration difference model (ECDM), based on the assumption that the effective diffusion coefficient of metal ion in the dialysis membrane is determined by the effective concentration difference (ΔC(e)) across the dialysis membrane, is proposed and applied to study the effect of ionic strength, binding agent, ligands and Donnan potential on the effective diffusion coefficient. The effective diffusion coefficients of Cd(2+) through the dialysis membrane immersed in receptor solutions with binding agent were almost the same as those in receptor solutions without binding agent at higher ionic strengths (0.01-1 M) but much higher than those at lower ionic strengths (0.001-0.0001 M). The effective diffusion coefficients of Cd(2+) through the dialysis membrane immersed in deionized water receptor solutions with binding agent were not significantly different from those in synthetic receptor solutions (receptor solutions with various ionic strengths) with binding agent. The DGT-labile fractions were measured in synthetic solutions and natural waters, which indicated that the effective diffusion coefficients, through the dialysis membrane immersed in the deionized water solution with binding agent as receptor solution and in the spiked natural water as source solution, were more suitable for DGT application.

Measurement of free copper(II) ions in water samples with polyvinyl alcohol as a binding phase in diffusive gradients in thin-films.

A technique for the selective measurement of diffusive gradients in thin-films (DGT) for free Cu2+ ions was developed using a 0.030 M solution of polyvinyl alcohol (PVA) as the liquid binding phase with the liquid-type DGT devices (PVA DGT). The PVA DGT had a substantial binding capacity at pH 5.6 - 8.6 and concentrations of competitive Na+ up to 0.7 M. The measurements of PVA DGT and cupric ion selective electrode (Cu-ISE) for free Cu2+ in synthetic river water (recovery = 97.51 +/- 2.58% for PVA DGT and recovery = 98.25 +/- 1.46% for Cu-ISE), in spiked river water (recovery = 24.99 +/- 3.55% for PVA DGT and recovery = 26.32 +/- 3.33% for Cu-ISE) and in spiked industrial wastewater (recovery = 4.21 +/- 3.13% for PVA DGT and recovery = 5.10 +/- 2.78% for Cu-ISE) were equivalent. The results showed that PVA DGT could measure selectively the free Cu2+ ion concentrations in water samples.

Sodium polyacrylate as a binding agent in diffusive gradients in thin-films technique for the measurement of Cu2+ and Cd2+ in waters.

An aqueous solution containing sodium polyacrylate (PA, 0.0030M) was used in diffusive gradients in thin-films technique (DGT) to measure DGT-labile Cu(2+) and Cd(2+) concentrations. The DGT devices (PA DGT) were validated in four types of solutions, including synthetic river waters containing metal ions with or without complexing EDTA, natural river water (Hun River, Shenyang, China) spiked with Cu(2+) and Cd(2+), and an industrial wastewater (Shenyang, China). Results showed that only free metal ions were measured by PA DGT, recovery=98.79% for Cu(2+) and recovery=97.80% for Cd(2+) in solutions containing only free metal ions, recovery=51.02% for Cu(2+) and recovery=51.92% for Cd(2+) in solution with metal/EDTA molar ratio of 2:1 and recovery=0 in solutions with metal/EDTA molar ratio of 1:1 and 1:2. These indicated that the complexes of Cu-EDTA and Cd-EDTA were DGT-inert or not DGT-labile. The DGT performance in spiked river water (recovery=8.47% for Cu(2+) and recovery=27.48% for Cd(2+)) and in industrial wastewater (recovery=14.16% for Cd(2+)) were also investigated. Conditional stability constants (logK) of PA-Cu and PA-Cd complexes were determined as 6.98 and 5.61, respectively, indicating strong interaction between PA and the metals.