离子交换树脂固载金属纳米粒子:可持续化学的有效、多功能催化剂平台（英文）

This paper reviews the recent achievements in the immobilization of metal nanoparticles on ion-exchange resins and the related catalytic application. The focus is on the production processes for fine and commodity chemicals for which a low environmental impact has been demonstrated. The most significant papers that appeared in the literature from January 2010 to July 2014 have been covered. Their uses in unselective processes, bulk chemicals production, fuel cells components, as well as the use of metal-free ion-exchange resins in acid / base-catalysed reactions, were not included.     

Decontamination of spent ion-exchange resins contaminated with cesium radionuclides

Possible causes of the occurrence of radioactive contamination irremovable by acid–base regeneration of ion-exchange resins used in treatment of process media and liquid radioactive waste have been studied. It has been found that most of the irremovable cesium radionuclides are bound to inorganic deposits on the surface and in the bulk of ion-exchange resin granules. The nature of inorganic inclusions has been investigated on real and model spent ion-exchange resins (SIER). A method has been proposed for decontaminating SIER using resorcinol–formaldehyde resins selective to cesium radionuclides. Such an approach has been shown to be promising for deep decontamination of SIER.     

Local structures of ions at ion-exchange resin/solution interface

The local structures of Cl- and Br- in anion-exchange resins have been studied by X-ray absorption fine structure (XAFS), and separation selectivity is discussed on the basis of results. When two different anion-exchange resins having trimethylammonium and dimethylammonium groups as anion-exchange groups are employed for ion-exchange experiments, slightly higher Br- selectivity has been obtained with the former. XAFS has indicated that the average hydration numbers for a given anion is not affected by the structure of the ion-exchange group, but that the extent of ion-association between the anion and the ion-exchange groups depends on the type of the ion-exchange group. Shorter interaction distance (and in turn stronger ion-association) has been confirmed for the dimethylammonium-type resin, and is consistent with lower Br- selectivity of this resin.     

Sulfoacylated poly(styrene-divinylbenzene) copolymers as resins for cation chromatography. Comparison with sulfonated, dynamically coated and silica gel cation exchangers

Most important properties of an ion chromatographic resin are influenced by the resin matrix, the type of functional group and the ion-exchange capacity. Highly crosslinked PS-DVB resins of 5 microm diameter have been functionalized by sulfoacylation, by sulfonation and by dynamic coating over a wide range of exchange capacities. These materials allow a study of the influence of different ion-exchange sites and capacities. The influence of the degree of functionalization on resin performance is completely reverse for sulfoacylated and sulfonated resins. The HETP values for all observed analytes (Cu, Pb, Zn, Ni, Co, Cd, Mn, Ca, Mg) in a tartaric acid elution system decrease for sulfoacylated resins with increasing capacity, for sulfonated resins with decreasing capacity. The performance of sulfoacylated exchangers is better than for dynamically coated ones and far better than for sulfonated resins. The performance of silica gel based cation-exchangers such as BioSil CAT is in most cases better than observed for sulfoacylated resins.     

Kinetics Characterization of Ion Release under Dynamic and Batch Conditions. I. Weak Acid and Weak Base Ion Exchange Resins

The aim of the present work is concerned with a study of the kinetics of release of both Ca²⁺ and F⁻ from the corresponding loaded ion-exchange resins (weak acid and weak base character for Ca²⁺ for F⁻, respectively), using both dynamic and batch experimental conditions with an artificial saliva solution as the ion-exchange media at 293 and 310 K. The influence of resin particle size and the temperature were evaluated by the kinetics parameters for the effective rate of release (B) and diffusion coefficient (D). The rate of ion release increases with temperature and decreases with particle size. The experimental data were well fitted by models based on intraparticle diffusion-controlled processes. In dynamic studies, the linear dependence of −log ₁₀(B) with the diameter of the resin particles can be applied for the estimation of B values when resins of low particle size are considered. In batch processes, although resins of low particle size can be studied, a linear relationship was only attained for the case of slow ion-exchange kinetic systems.     

Ion-exchange resin catalysts in the liquid-phase hydrazinolysis of cinnamic acid

The catalytic activity of a synthetic ion-exchange resins has been studied in the reaction of cinnamic acid with hydrazine (aqueous medium, 363 K, 1.0–2.5 h) yielding the corresponding hydrazide. Efficient catalysts for the process are the anion-exchange resins AV-17-8 and AN-31. The modifying effect of the substrate—hydrazine hydrate—on the catalytic properties of the ion-exchange systems has been demonstrated. On the basis of IR spectroscopic studies, a plausible process mechanism was suggested. It involves polymer-bound quaternary ammonium ions of the anion exchanger.     

Separation of U(IV) and U(VI) species by means of ion-exchange resins of the DGA-, TEVA- and UTEVA-type

The present paper deals with the retention of U(IV) and U(VI) species, both individually and in 1 :1 mixtures, on some ion-exchange resins of the normal DGA (N,N’,N’-tetra-n-octyldiglycolamide), TEVA- [trialkyl methyl-ammonium nitrate (or chloride)] and UTEVA-type (dipentyl pentylphosphonate), in different experimental conditions. The degree of retention, distribution constant, as well as enthalpy and entropy values which characterize the adsorption of uranium ions on these resins were calculated. By means of Langmuir relation, taking into account the experimental data, the maximum adsorption capacity, Langmuir constant and Gibbs free energy values for the studied processes are established.     

Etherification of glycerol with tert-butyl alcohol catalysed by ion-exchange resins

The reaction of glycerol with tert-butyl alcohol in the liquid phase on acid Amberlyst-type ion-exchange resins was studied. The influence of temperature, mole ratio n(TBA)/n(G), water and swelling of gel, and macroreticular type of polymer catalysts on etherification reaction was investigated. The most favourable reaction temperature is 75°C. The conversion of glycerol and yield of glycerol tert-butyl ethers has increased with the mole ratio n(TBA)/n(G). Dry form of macroreticular catalysts provided the best results. Etherification reaction of glycerol with isobutylene in non-aqueous conditions gives the highest yield of desired ethers. The influence of water was studied. The gel forms of ion-exchange resins have very low catalytic activity. It can be concluded that water has an inhibition effect on ion-exchange resins. By comparing the gel and macroreticular forms of Amberlyst ion-exchange resins it can be concluded that very acid forms of macroreticular ion-exchange resins with a high degree of crosslinking are more active catalysts for the studied reaction due to their pores which are sufficiently large so that the voluminous tert-butyl ethers of glycerol can be formed. It was estimated that tert-butyl alcohol as tert-butylation agent is not suitable for etherification of glycerol with the formation of di-and triethers.     

Uricase-like catalytic activity of ion-exchange resins modified with metalloporphyrins

The uricase-like catalytic activity of the ion-exchange resins modified with metalloporphyrins has been investigated through the oxidation of uric acid. The anion-exchange resins modified with Mn(3+)-tetrakis(sulfophenyl)porphine and the cation-exchange resin modified with Mn(3+)-tetrakis(1-methylpyridinium-4-yl)porphine exhibited the highest uricase-like activity among the modified resins tested. The fact that these resins accelerated the oxidation of uric acid even after ten cycles of use indicates that the modified resins act as catalysts in the reaction catalysed by uricase. Some of the modified resins may be effectively used for the determination of uric acid in place of uricase.     

Environmentally benign chemical fixation of CO2 catalyzed by the functionalized ion-exchange resins

Basic ion-exchange resins, one kind of polystyryl-supported tertiary amine, were demonstrated to be highly efficient and recyclable catalysts for the fixation of carbon dioxide with aziridines under mild conditions, leading to the formation of 5-aryl-2-oxazolidinone with excellent regio-selectivities. Notably, neither solvents nor any additives were required, and the catalyst could be recovered by simple filtration and directly reused at least five times without significant loss of catalytic activity and selectivity. The present protocol has been applied to reactions of epoxides/propargyl amines with CO₂/CS₂. This solvent-free process thus represents environmentally friendly catalytic conversion of CO₂ into value-added chemicals and may have potential in various continuous flow reactors in industry.     

Comparison of variously pretreated ion-exchange resins for131I separation from aqueous solutions

Preliminary results of experimental testing and comparison of¹³¹I separation efficiency from model solutions on ion-exchange resins pretreated in some special ways are presented. Strongly basic and strongly acidic resins were pretreated chemically and used for the separation of radioiodine by means of isotopic-exchange, ion-exchange or chemisorption and their combinations. The sorbents were tested for pI, pH, their stability during storage and selectivity of separation. From the point of view of the efficiency and selectivity of separation the sorbents based on strongly basic resins and with assumed isotopic-exchange mechanism of radioiodine separation appear to be relatively more advantegeous.     

Some chelating ion-exchange resins containing ketoiminocarboxyclic acids as functional groups

A series of ion-exchange resins containing -COCH(2)N[(CH(2))(m)COOH(2)](2) groups has been synthesized. Additional analogues were prepared by means of the reaction of the carbonyl group with phosphorus trichloride or thioglycollic acid. The properties of these resins and the selectivity for different metal ions have also been investigated.     

Integrated utilization of spent ion-exchange resins in wastewater treatment and in polymer composites

The possibility of recovery of contaminants (soaps of resin and fatty acids, Leukanol, and finely dispersed rubber) from spent synthetic ion-exchange resins in the stage of treatment of wastewater formed in production of synthetic rubbers and latexes, which polymer composites obtained, was studied.     

Synthesis and Ion-Exchange Properties of Surface Grafts

The synthesis of ion-exchange resins consisting of an inert nucleus with a thin shell of active material grafted to the surface is described. The shell carrying the exchange function is substantially uncross-linked. The exchange properties of such resins are characterized by fast equilibration. Rate curves and properties for several types of ion-exchange structures are described.     

Expanded-bed adsorption utilizing ion-exchange resin to purify extracellular β-galactosidase

The application of expanded-bed ion-exchange resins allows the elimination of intermediary particulate separation steps like filtration or centrifugation prior to adsorption steps in enzyme-purification processes from crude fermentation broths. This work is concerned with the experimental evaluation data of a process related to the adsorption of an extracellular p-galactosidase from the fungiScopulariopsis. The protein recovery in the ion-exchange resin Accell Plus QMA™ was accomplished using a continuous-monitoring method. The direct adsorption step was followed by a elution step with concentrated NaCl solutions aiming to improve the enzyme-specific activity. Experimental data for fixed and expanded bed were compared     

Calculations of equilibria in the static purification of solutions with ion-exchange resins. Communication 1. Formation of a relatively nondissociated substance

Conclusions Equations were derived permitting a calculation of the necessary amount of an ion-exchange resin (or ion-exchange resins) required for the purification of solutions to a set residual concentration of an impurity ion, if the counter-ion of the ion-exchange resin (or mixture of ion-exchange resins) forms a relatively nondissociated substance in solution with an ion of opposite sign. Satisfactory agreement of the calculated and experimental data was obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 807–811, April, 1972.     

Conversion of biomass to selected chemical products

This critical review provides a survey illustrated by recent references of different strategies to achieve a sustainable conversion of biomass to bioproducts. Because of the huge number of chemical products that can be potentially manufactured, a selection of starting materials and targeted chemicals has been done. Also, thermochemical conversion processes such as biomass pyrolysis or gasification as well as the synthesis of biofuels were not considered. The synthesis of chemicals by conversion of platform molecules obtained by depolymerisation and fermentation of biopolymers is presently the most widely envisioned approach. Successful catalytic conversion of these building blocks into intermediates, specialties and fine chemicals will be examined. However, the platform molecule value chain is in competition with well-optimised, cost-effective synthesis routes from fossil resources to produce chemicals that have already a market. The literature covering alternative value chains whereby biopolymers are converted in one or few steps to functional materials will be analysed. This approach which does not require the use of isolated, pure chemicals is well adapted to produce high tonnage products, such as paper additives, paints, resins, foams, surfactants, lubricants, and plasticisers. Another objective of the review was to examine critically the green character of conversion processes because using renewables as raw materials does not exempt from abiding by green chemistry principles (368 references).     

Reactivity Ratios for Divinylbenzene and Ethylene Glycol Dimethacrylate Copolymerizations with Styrene and Methyl Methacrylate

The free radical copolymerization of styrene and other vinyl monomers to produce cross-linked, network polymers is of technological importance in the production of ion-exchange resins, packings for gas-liquid and gel permeation chromatography, cross-linked latex polymers, and other products. The principal multifunctional cross-linking monomers which are used in this connection are ethylene glycol dimethacrylate and divinylbenzenes, and accurate values for reactivity ratios in their reactions with bifunctional monomers are essential for the design of copolymerization processes and products.

Wiley and co-workers have reported reactivity ratios for the copolymerizations of these monomers with styrene and with methyl methacrylate [1]. In these studies the reactivity ratios were calculated from the raw data using a graphical “method of intersections” [2]. In this procedure the differential copolymer equation is put into the form     

Detoxification of lignocellulose hydrolysates with ion-exchange resins

Lignocellulose hydrolysates contain fermentation inhibitors causing decreased ethanol production. The inhibitors include phenolic compounds, furan aldehydes, and aliphatic acids. One of the most efficient methods for removing inhibiting compounds prior to fermentation is treatment of the hydrolysate with ion-exchange resins. The performance and detoxification mechanism of three different resins were examined: an anion exchanger, a cation exchanger, and a resin without charged groups (XAD8). A dilute acid hydrolysate of spruce was treated with the resins at pH 5.5 and 10.0 prior to ethanolic fermentation with Saccharomyces cerevisiae. In addition to the experiments with hydrolysate, the effect of the resins on selected model compounds, three phenolics (vanillin, guaiacol, and coniferyl aldehyde) and two furan aldehydes (furfural and hydroxymethyl furfural), was determined. The cation exchanger increased ethanol production, but to a lesser extent than XAD-8, which in turn was less effective than the an ion exchanger. Treatment at pH 10.0 was more effective than at pH 5.5. At pH 10.0, the anion exchanger efficiently removed both anionic and uncharged inhibitors, the latter by hydrophobic interactions. The importance of hydrophobic interactions was further indicated by a substantial decrease in the concentration of model compounds, such as guaiacol and furfural, after treatment with XAD-8.     

Synthesis of Hindered Phenolic Esters over Ion-Exchange Resins

The esterification of 3,5-di-tert-butyl-4-hydroxybenzoic acid with 1-hexadecanol over a series of ion-exchange resins was investigated, in which resin D072 exhibited excellent catalytic performance. The influence of water on the reaction was also investigated, and it was found that water could improve the selectivity and increase the yield of the target product. Treatment of resins with aqueous sodium hydroxide could improve the selectivity of the target product but remarkably decreased the conversion of 3,5-di-tert-butyl-4-hydroxybenzoic acid. This result indicated that strong Brønsted acid sites played an important role in the reaction. Furthermore, D072 was efficiently recycled four runs by simple treatment with mineral acid. Finally, a series of hindered phenolic esters were successfully synthesized under the optimal reaction conditions. Therefore, a simple and versatile method for the synthesis of hindered phenolic esters has been established over ion-exchange resins and the target products were obtained in good yields.