Nitrate and nitrite reduction of a sulphide-rich environment

A sulphide-rich anaerobic sludge acclimated with a molasses wastewater was used to carry out studies on nitrate and nitrite reductions in continuously stirred batch reactors. It was shown that a COD/N-NO_x ratio as high as 65·6 mg mg⁻¹ did not promote dissimilatory reduction of nitrogen oxides to ammonia. Denitrification was characterized by a probable accumulation of gaseous intermediates, nitric oxide (NO) and nitrous oxide (N₂O), by sulphide consumption with concomitant elemental sulphur production and by an increase of the redox potential. In addition, sulphate reducers were completely inhibited by nitrogenous oxides. Cultures performed without any carbon source proved that denitrifiers were able to use sulphides as electron donors. Furthermore, while a lag phase preceded nitrate denitrification, nitrite was consumed immediately. Chemical reduction of nitrite by ferrous iron (Fe²⁺) was considered to be responsible for this difference. Evidence of such a chemodenitrification has been presented by using a sterilized sludge which kept its ability to reduce nitrite while it lost its capacity to use nitrate. Moreover, this chemical activity was favoured by Fe²⁺ addition. Finally, it has been suggested that during the cultures performed with non-sterilized sludge, a biological reduction of the ferric ions (Fe³⁺) would be coupled to nitrite chemodenitrification and would allow a regeneration of Fe²⁺. © 1998 SCI     

Exhaustive oxidation/reduction of nitrite, nitrate and hydrazine using a square wave potential regime

Exhaustive oxidation–reduction of nitrite, nitrate and hydrazine was achieved by application of a square wave potential regime to a platinum electrode. The parameters of the square wave were chosen after investigation of the adsorption behaviour of the three compounds. The three compounds were found to adsorb and desorb at a platinum electrode in the potential window from –0.2 V to 1.3 V and hence the lower potential of the square wave was –0.2 V while the upper potential was 1.3 V. The square wave was applied to a solution containing the test compound for 10 h. The results of analysis indicated a decrease in the concentration of the tested compounds with respect to the control sample. The optimal frequencies for the conversion were 10, 50 and 10 for nitrite, nitrate and hydrazine, respectively. Analysis of solutions for possible products of the exhaustive oxidation gave negative tests for NO^–₂, NO^–₃, and NH₃ leaving the possibility of conversion to nitrogen as the end product.     

Preparation of novel Pt-based nanoparticles by double potential step electrolysis and their electrocatalytic activity for oxygen reduction reaction

We have developed a novel preparation method for Pt-based nanoparticles by means of double potential step electrolysis (DPSE), in which Pt-Ni alloy deposited at the first step and Ni dissolved at the following step. A cycle of the DPSE in a nickel plating bath containing PtCl₆²⁻ led to the formation of the Pt-Ni nanoparticles with size of about 5.4 ± 1.5 nm, which gradually grew up with repeating the DPSE process, and surface Ni content of the particles by XPS was controllable by changing some parameters of the DPSE. The Pt-Ni nanoparticles deposited by the DPSE were covered with a Pt skin layer, which influence the improvement of both catalytic activity for oxygen reduction reaction (ORR) and corrosion resistance. The Pt-Ni nanoparticles by the DPSE exhibit ca. two times higher electrocatalytic activity for ORR than Pt nanoparticles, and further, of which catalytic activity was maintained high even with more than 1000 cycles of potential cycling test in H₂SO₄ solution, showing good corrosion resistance.     

Chemoenzymatic synthesis of branched oligo- and polysaccharides as potential substrates for starch active enzymes

Oligo- and polysaccharides embodying the alpha-maltotriosyl-6(II)-maltotetraosyl structure were readily synthesized by transglycosylation of maltosyl fluoride onto panose and pullulan catalysed by the bacterial transglycosylase cyclodextrin glycosyltransferase (CGTase). The two products obtained proved useful for increasing the knowledge of substrate binding and processing at the active site of barley limit dextrinase that is involved in the metabolism of amylopectin by acting upon its branch points.     

Electrocatalytic hydrogenation processes controlled potential—1. The electrocatalytic reduction of nitric acid

Methods are described to control the catalyst potential during the electrocatalytic hydrogenation of nitric acid in a slurry electrode cell. The influence of traces of GeO₂ on the hydrogenation reaction is studied with a platinum electrode. Deposition of Ge on the platinum surface limits the amount of adsorbed hydrogen and enhances the nitric acid reduction. This changes the mixed potential of the hydrogen-nitric acid system on the platinum (catalyst) surface. A similar potential change occurs, when the partial hydrogen pressure in the system is altered.     

Size-dependent electrocatalytic reduction of nitrite at nanostructured films of hollow polyaniline spheres and polyaniline–polystyrene core–shells

Nanostructured films of the conducting polymer polyaniline (PANI) were prepared by its potentiostatic polymerization in the presence of thin polystyrene (PS) nanoparticle templates. Two sizes of PS nanoparticles were used (50 and 100 nm) and electron microscopic analysis showed that core–shell composite films of PANI (PANI–PS₅₀ and PANI–PS₁₀₀) and, following removal of the PS, hollow structures (PANI₅₀ and PANI₁₀₀) were formed due to the growth mechanism of PANI around the PS templates. The electrochemical behaviour of the PANI-modified electrodes was studied by cyclic voltammetry, chronocoulometry and amperometry in the presence of nitrite and it was found that nitrite reduction was enhanced by the nanostructuring of the films. The electrocatalysis was dependent on the size of the template, being more pronounced at 50 nm than at 100 nm. The hollow PANI₅₀ film was also a better catalyst than PANI–PS₅₀, whereas for structures based on 100 nm templates, the composite film was better. Such behaviour could be explained in terms of larger surface area and surface concentration of PANI₅₀ and PANI–PS₅₀ films on the electrodes and by higher differential capacitance of those films.     

Chemical synthesis of a dual branched malto-decaose: a potential substrate for alpha-amylases

A convergent block strategy for general use in efficient synthesis of complex alpha-(1-->4)- and alpha-(1-->6)-malto-oligosaccharides is demonstrated with the first chemical synthesis of a malto-oligosaccharide, the decasaccharide 6,6'-bis(alpha-maltosyl)-maltohexaose, with two branch points. Using this chemically defined branched oligosaccharide as a substrate, the cleavage pattern of seven different alpha-amylases were investigated. Alpha-amylases from human saliva, porcine pancreas, barley alpha-amylase 2 and recombinant barley alpha-amylase 1 all hydrolysed the decasaccharide selectively. This resulted in a branched hexasaccharide and a branched tetrasaccharide. Alpha-amylases from Asperagillus oryzae, Bacillus licheniformis and Bacillus sp. cleaved the decasaccharide at two distinct sites, either producing two branched pentasaccharides, or a branched hexasaccharide and a branched tetrasaccharide. In addition, the enzymes were tested on the single-branched octasaccharide 6-alpha-maltosyl-maltohexaose, which was prepared from 6,6'-bis(alpha-maltosyl)-maltohexaose by treatment with malt limit dextrinase. A similar cleavage pattern to that found for the corresponding linear malto-oligosaccharide substrate was observed.     

One-step chemical reduction of graphene oxide with oligothiophene for improved electrocatalytic oxygen reduction reactions

Oligothiophene (nTP, n = 1, 2, 3) has been used as the reductant for the first time in the preparation of graphene by the reduction of graphene oxide (GO). A simple single-step chemical approach has been developed to reduce and/or functionalize GO with nTP. The reaction takes place at room temperature under stirring of a suspension of GO and nTP in MeCN. The nTP has been grafted onto the surface of GO by reacting epoxy groups together with the reduced graphene oxide (rGO). It was observed that increasing the thiophene ring (hereafter, thiophene is referred to as TP; 2,2′ bithiophene as 2TP; and 2,2′:5′,2″ terthiophene as 3TP) can enhance the reduction reaction. All instrumental experiments have confirmed that nTP not only covalently bonded to the GO but also partly restored the conjugate structure of GO, as a reducing agent. The resultant rGO with 3TP (rGO3TP) has been demonstrated to show remarkable electrocatalytic activity toward oxygen reduction reaction (ORR) compared to typical rGO. The observed ORR electrocatalytic activity induced by the intermolecular charge-transfer provides a general approach to various carbon-based metal-free ORR catalysts.     

Stability and electrocatalytic activity for oxygen reduction in WC + Ta catalyst

Tantalum (Ta)-added tungsten carbide (WC) (WC+Ta) was examined in order to obtain surperior characteristics in stability and electrocatalytic activity for the oxygen reduction reaction (ORR) in acid electrolyte. The stability and the electrocatalytic activity of the WC+Ta catalyst were electrochemically investigated and compared to the pure WC. It was proved that the stability of the tungsten carbide was significantly increased by the addition of tantalum compared to the pure WC. The enhanced stability might be due to the formation of the W-Ta alloy in the WC+Ta catalyst. The reduction current of the WC+Ta catalyst for the ORR was observed at a potential of 0.8 V (versus dynamin hydrogen eletrode (DHE)) or less noble potential. This value was about 0.35 V higher than that of the pure WC. The enhanced electrocatalytic activity for the ORR might be caused by the presence of tungsten carbide, which exists on the surface and/or sub-surface.     

Hollow Fe2O3 polyhedrons: One-pot synthesis and their use as electrochemical material for nitrite sensing

In this paper, hollow hematite nano-polyhedrons (Fe-HNPs) were synthesized via a facile solution route. The abundance of high indexed facets was demonstrated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD) analysis. A new electrochemical biosensor for nitrite determination was then proposed by using the hematite hollow nanopolyhedron as the sensing layer. Electrochemical tests showed that the Fe-HNPs could act as efficient enzyme-like electron mediators for nitrite oxidation. As a result, the Fe₂O₃ modified biosensor exhibited excellent performance for the determination of nitrite with a response time of <10 s, linear range between 0.009 and 3 mM, and sensitivity as 19.83 μA mM^?1. A high selectivity and long-term stability toward nitrite oxidation in the presence of glucose and l-ascorbic (AA) was also observed at their maximum physiological concentrations, which made this novel Fe₂O₃ nanomaterial bounded with high indexed facets promising for sensing applications in medicine, biotechnology and environmental chemistry.     

Kinetics and electrocatalytic activity of nanostructured Ir-V/C for oxygen reduction reaction

Active, carbon-supported Ir-V nanoparticle catalysts have been synthesized by an ethylene glycol reduction method under controlled conditions at pH 10-13 and 120 °C, then further reduced at elevated temperature from 150 to 500 °C using IrCl₃ and NH₄VO₃ as the Ir and V precursors. The nanostructured catalysts have been characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (TEM). Ir nanoparticles, after modification with V, show a narrow particle size distribution in the range 0.5-4.5 nm, centered at 1.8 nm, and are uniformly dispersed on Vulcan XC-72. No particle agglomeration was observed, not even at high V loadings (V:Ir = 4:1 in atomic ratio). Investigation of the catalytic activity of the Ir-V/C by means of cyclic voltammetry (CV) and linear sweep voltammetry (LSV) employing a rotating disk electrode (RDE) has revealed that the presence of V may suppress the electrochemical oxidation of Ir and stabilize the Ir active centers. About six times higher kinetic current density was obtained for Ir-V/C compared to that of the pure Ir/C catalyst at 0.8 V versus RHE for the oxygen reduction reaction (ORR). The ORR in acid solution proceeds by an approximately four-electron pathway, through which molecular oxygen is directly reduced to water. The performance of a membrane electrode assembly (MEA) prepared with the most active 40% Ir-10% V/C as the cathode catalyst in a single proton-exchange membrane fuel cell (PEMFC) generated a maximum power density of 517 mW cm⁻² at 0.431 V and 70 °C, and 100 h of stable cell operation due to no loss of catalyst sites on the cathode.     

电催化还原水中NO_3~-的研究进展

主要综述了目前国内外电催化还原脱除NO_3~-技术的研究进展,阐述了NO_3~-电催化还原的主要反应路径及相应的中间产物,并着重介绍了几种一元/二元金属阴极催化剂,及相应的催化效率优化手段和调控原理。综述可为高效催化剂的设计和合成提供思路和参考,推动电催化还原脱除NO_3~-技术在环境污染修复等领域的应用和推广。     

电催化还原水中NO_3~-的研究进展

主要综述了目前国内外电催化还原脱除NO_3^-技术的研究进展,阐述了NO_3-技术的研究进展,阐述了NO_3^-电催化还原的主要反应路径及相应的中间产物,并着重介绍了几种一元/二元金属阴极催化剂,及相应的催化效率优化手段和调控原理。综述可为高效催化剂的设计和合成提供思路和参考,推动电催化还原脱除NO_3-电催化还原的主要反应路径及相应的中间产物,并着重介绍了几种一元/二元金属阴极催化剂,及相应的催化效率优化手段和调控原理。综述可为高效催化剂的设计和合成提供思路和参考,推动电催化还原脱除NO_3^-技术在环境污染修复等领域的应用和推广。     

[As8W48O184], a new crown-shaped heteropolyanion: Electrochemistry and electrocatalytic properties towards reduction of nitrite

The electrochemical behavior of the new crown-shaped heteropolyanion [As₈W₄₈O₁₈₄]⁴⁰⁻ was investigated. Compared to the analogous complex [P₈W₄₈O₁₈₄]⁴⁰⁻, [As₈W₄₈O₁₈₄]⁴⁰⁻ displayed a close similar behavior. As previously reported for [P₈W₄₈O₁₈₄]⁴⁰⁻, [As₈W₄₈O₁₈₄]⁴⁰⁻ is found to be stable in a large range of pH, roughly from 0 to 8 and found to be slightly more soluble than [P₈W₄₈O₁₈₄]⁴⁰⁻. Comparison between the cyclic voltammetry curves of the two complexes reveals that the potentials of the redox waves of [As₈W₄₈O₁₈₄]⁴⁰⁻ are slightly shifted towards the positive values. Contrary to the high dependence of [P₈W₄₈O₁₈₄]⁴⁰⁻ to buffer capacity of the supporting electrolyte, interestingly, [As₈W₄₈O₁₈₄]⁴⁰⁻ displays less sensitivity. The numerous possibilities for chemical applications opened up by the electrochemistry of this new complex are exemplified here by the good linear relationship between the peak potentials of the redox waves as a function of pH and, by the electrocatalytic reduction of nitrite.     

Synthesis of Pd-Sn nanoparticles by ultrasonic irradiation and their electrocatalytic activity for oxygen reduction

Nanoparticles of Pd-Sn were prepared under various conditions by applying ultrasonic irradiation, and their electrocatalytic activity for oxygen reduction was evaluated in 0.5 M KOH. The average size of Pd-Sn nanoparticles thus prepared was about 3-5 nm. The Pd in Pd-Sn nanoparticles was found to be mostly in the metallic state. The electrocatalytic activity of the Pd-Sn nanoparticles for the oxygen reduction reaction (ORR) is greater than Pt or Pd nanoparticles in alkaline media. The molar ratio of Pd to Sn metal ions in the synthesizing solution, their initial concentrations, the concentration of ethanol, which increases primary hydrogen radicals during sonolysis, and the concentration of citric acid were found to affect the size distribution of the Pd-Sn nanoparticles, and therefore, those factors controlled the electrocatalytic activity for ORR. Particularly, the concentration of citric acid was found to be important for controlling the surface property on Pd-Sn particles to adjust the electrocatalytic activity for ORR.     

Modification of alumina matrices through chemical etching and electroless deposition of nano-Au array for amperometric sensing

Simple nanoporous alumina matrix modification procedure, in which the electrically highly insulating alumina barrier layer at the bottom of the pores is replaced with the conductive layer of the gold beds, was described. This modification makes possible the direct electron exchange between the underlying aluminum support and the redox species encapsulated in the alumina pores, thus, providing the generic platform for the nanoporous alumina sensors (biosensors) with the direct amperometric signal readout fabrication. Electronic supplementary material   Supplementary material is available in the online version of this article at (doi: ) and is accessible for authorized users.     

Synthesis and properties of a new, branched polyhydridocarbosilane as a precursor for silicon carbide

Polymerization of Cl₂Si(CH₃)CH₂Cl with Mg in THF, followed by reduction with LiAlH₄, gave a polycarbosilane with Si-H groups and branches at the Si atoms. The polymer could be cross-linked thermally at 150°C. Pyrolysis of the cross-linked material gave SiC with a yield of 70%.Presented at the XXVIth Silicon-Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

A carbon nanotube/polyvanillin composite film as an electrocatalyst for the electrochemical oxidation of nitrite and its application as a nitrite sensor

We report a simple method for the stable dispersion of multi-walled carbon nanotubes (MWNTs) in water by vanillin and controllable surface addition onto carbon fiber microelectrodes (CFE) via electropolymerization. We have characterized these polyvanillin-carbon nanotube (PVN-MWNT) composite films with techniques including scanning electron microscopy (SEM), infrared spectroscopy (IR) and voltammetry. These investigations showed that the films have a uniform porous nanostructure with a large surface area. This PVN-MWNT composite-modified CFE (PVN-MWNT/CFE) exhibited a sensitive response to the electrochemical oxidation of nitrite. Under optimal working conditions, the oxidation peak current of nitrite linearly increased with its concentration in the range of 0.2 μM-3.1 mM, with the system exhibiting a lower detection limit of 50 nM (S/N = 3). We successfully applied the PVN-MWNT/CFE system to the determination of nitrite from lake water. The efficient recovery of nitrite indicated that this electrode was able to detect nitrite in real samples.