Comparison of CO2 Reduction Performance with NH3 and H2O between Cu/TiO2 and Pd/TiO2

The aim of this study is to clarify the effect of doped metal type on CO₂ reduction characteristics of TiO₂ with NH₃ and H₂O. Cu and Pd have been selected as dopants for TiO₂. In addition, the impact of molar ratio of CO₂ to reductants NH₃ and H₂O has been investigated. A TiO₂ photocatalyst was prepared by a sol-gel and dip-coating process, and then doped with Cu or Pd fine particles by using the pulse arc plasma gun method. The prepared Cu/TiO₂ film and Pd/TiO₂ film were characterized by SEM, EPMA, TEM, STEM, EDX, EDS and EELS. This study also has investigated the performance of CO₂ reduction under the illumination condition of Xe lamp with or without ultraviolet (UV) light. As a result, it is revealed that the CO₂ reduction performance with Cu/TiO₂ under the illumination condition of Xe lamp with UV light is the highest when the molar ratio of CO₂/NH₃/H₂O = 1:1:1 while that without UV light is the highest when the molar ratio of CO₂/NH₃/H₂O = 1:0.5:0.5. It is revealed that the CO₂ reduction performance of Pd/TiO₂ is the highest for the molar ratio of CO₂/NH₃/H₂O = 1:1:1 no matter the used Xe lamp was with or without UV light. The molar quantity of CO per unit weight of photocatalyst for Cu/TiO₂ produced under the illumination condition of Xe lamp with UV light was 10.2 μmol/g, while that for Pd/TiO₂ was 5.5 μmol/g. Meanwhile, the molar quantity of CO per unit weight of photocatalyst for Cu/TiO₂ produced under the illumination condition of Xe lamp without UV light was 2.5 μmol/g, while that for Pd/TiO₂ was 3.5 μmol/g. This study has concluded that Cu/TiO₂ is superior to Pd/TiO₂ from the viewpoint of the molar quantity of CO per unit weight of photocatalyst as well as the quantum efficiency.     

Reductive leaching of low-grade manganese ore with pre-processed cornstalk

Cornstalk is usually directly used as a reductant in reductive leaching manganese. However, low utilization of cornstalk makes low manganese dissolution ratio. In the research, pretreatment for cornstalk was proposed to improve manganese dissolution ratio. Cornstalk was preprocessed by a heated sulfuric acid solution (1.2 M of sulfuric acid concentration) for 10 min at 80°C. Thereafter, both the pretreated solu-tion and the residue were used as a reductant for manganese leaching. This method not only exhibited superior activity for hydrolyzing corn-stalk but also enhanced manganese dissolution. These effects were attributed to an increase in the amount of reductive sugars resulting from lignin hydrolysis. Through acid pretreatment for cornstalk, the manganese dissolution ratio was improved from 50.14%to 83.46%. The pre-sent work demonstrates for the first time the effective acid pretreatment of cornstalk to provide a cost-effective reductant for manganese leaching.     

Study on aqueous polymerizations of vinyl monomers initiated by metal oxidant–chelating agent redox initiators

In this study, a series of chelating type reductants containing redox pairs were tested as the initiator for aqueous polymerizations. The redox pairs consist of Ce(IV) or several first-row transition metals coupled with chelating agents of amino acids, dibasic acids, or diamine. The initial rates and limiting conversions of acrylamide polymerization initiated by those redox pairs were determined. The reductive reactivity of the chelating agents with Ce(IV) and the oxidative half-wave potential of Ce(III)-chelating agent/Ce(IV)-chelating agent were measured to evaluate the feasibility of these redox pairs as initiators. After the evaluation, the redox pairs other than Ce(IV)-amino acid type chelating agent were precluded to be promising initiators for aqueous polymerizations. Those Ce(IV)-amino acid type chelating agent redox pairs which could form at least two five- or six-membered rings were found to be potential initiators. The Ce(IV)-NTA pair was the most promising one. The mechanism of initiation of the redox pairs was proposed and further confirmed by the ¹³C- and ¹H-NMR spectra of NTA-terminated polyacrylamide. The complex formation constants (K) and disproportionation constants (k_d) of the Ce(IV)-amino acid type chelating agent redox initiators for acrylamide polymerization were evaluated. The factors governing the parameters of chelated complexes and the performance of polymerizations were discussed. These redox pairs were also used as the initiators for aqueous polymerizations of acrylic acid and acrylonitrile. © 1993 John Wiley & Sons, Inc.     

Investigation of Simultaneous Generation of Arsenic,Bismuth and Antimony Hydrides Using Inductively Coupled Plasma Optical Emission Spectrometry

Hydride generation from solution containing As(III), Bi(III), and Sb(III) by means of different borane reductants and acids using inductively coupled plasma optical emission spectrometry as a detection system was investigated. The As, Bi, Sb, B, C, H, and N lines as well as the OH and CN molecules were recorded. Their intensities in relation to hydride formation conditions were measured. Effects of the HCl, CH₃COOH, and C₆H₈O₇ acids as well as the NaBH₄, H₃B-NH(CH₃)₂, and H₃B-NH₂C(CH₃)₃ reductants on efficiency of the As, Sb, and Bi hydride generation were investigated and discussed. Influence of hydride generation conditions on plasma was studied.     

Redox Reactions on Tetrachlorohydrdquinone and Tetrachloroquinone Columns

Abstract

Experimental conditions of acidity and pH have been studied for the determination of several oxidants and reductants on tetrachlorohydroquinone (TCHQ) and tetrachloroquinone (TCQ) columns.     

Solid-phase reducing agents as alternative for reducing disulfide bonds in proteins

Disulfide reduction of Kluyveromyces lactis and Aspergillus oryzae β-galactosidases and β-lactoglobulin was assessed. Reduction was performed using one of two thiol-containing agents: dithiothreitol (DTT) or thiopropyl-agarose with a high degree of substitution (1000 μmol of SH groups/g of dried gel). Both reductants allowed an increase of three- (for K. lactis β-galactosidase) and fourfold (for A. oryzae β-galactosidase) in the initial content of SH groups in the lactases. Nearly sevenfold fewer micromoles of SH groups per milligram of protein were needed to perform the reduction of K. lactis β-galactosidase with thiopropyl-agarose than for the same reduction with DTT. However, for A. oryzae β-galactosidase, nearly twice as many micromoles of SH groups per milligram of protein were needed with thiopropylagarose than with DTT. Disulfide bonds in β-lactoglobulin were not accessible to thiopropyl-agarose, since this reduction was only possible in the presence of 6 M urea. These results proved that highly substituted thiopropyl-agarose is as good a reducing agent as DTT, for the reduction of disulfide bonds in proteins. Moreover, excess reducing agent was very simply separated from the reduced protein by filtration, making it easier to control the reaction and providing reduced protein solutions free of reductant. All these advantages substantially cut down the time required and therefore the cost of the overall process.     

Upconversion of Reductants

The many applications of photon upconversion—conversion of low‐energy photons into high‐energy photons—raises the question of the possibility of “electron upconversion”. In this Review, we illustrate how the reduction potential can be increased by using the free energy of exergonic chemical reactions. Electron (reductant) upconversion can produce up to 20–25 kcal mol^?1 of additional redox potential, thus creating powerful reductants under mild conditions. We will present the two common types of electron‐upconverting systems—dissociative (based on unimolecular fragmentations) and associative (based on the bimolecular formation of three‐electron bonds). The possible utility of reductant upconversion encompasses redox chain reactions in electrocatalytic processes, photoredox cascades, design of peroxide‐based medicines, firefly luminescence, and reductive repair of DNA photodamage.     

鲕状赤铁矿生物质低温磁化焙烧

对生物质磁化鲕状赤铁矿石进行研究,包括磁化温度、磁化时间、生物质用量以及赤铁矿石粒度对磁化效果的影响.在磁化温度为600℃,赤铁矿石与生物质的质量比为10：2的情况下,利用生物质热解产生的气体和焦油在30 min内可以完全磁化粒度为0.074 mm (>72.5%)的赤铁矿石,验证了生物质替代煤基还原剂进行磁化焙烧具有一定的可行性.此外,矿石粒度对磁化焙烧还原度的影响比较大,矿石粒度越大,完全磁化所需时间越长.根据生物质还原剂的特点,适当地减小矿石粒度可以有效改善赤铁矿石的磁化性能.     

Pushing the Limits of Neutral Organic Electron Donors: A Tetra(iminophosphorano)‐Substituted Bispyridinylidene

A new ground‐state organic electron donor has been prepared that features four strongly π‐donating iminophosphorano substituents on a bispyridinylidene skeleton. Cyclic voltammetry reveals a record redox potential of ?1.70 V vs. saturated calomel electrode (SCE) for the couple involving the neutral organic donor and its dication. This highly reducing organic compound can be isolated (44 %) or more conveniently generated in situ by a deprotonation reaction involving its readily prepared pyridinium ion precursor. This donor is able to reduce a variety of aryl halides, and, owing to its redox potential, was found to be the first organic donor to be effective in the thermally induced reductive S? N bond cleavage of N,N‐dialkylsulfonamides, and reductive hydrodecyanation of malonitriles.