A bi-continuous structure of nanoporous iron was synthesized by the high-temperature electrochemical dealloying of Fe0.5Mn0.5 in a molten LiCl-KCl eutectic. It was found that the characteristic bi-continuous structure of pores and ligaments of the order of 100 nm is formed at the lower temperature of 400 °C. At 500 °C another morphology of dendrite-like structure is formed since the number of ligaments decreases due to coarse-graining during processing. Surprisingly, at 600 °C, the formation of a new bi-continuous structure with “ginger-root-like” ligaments of several microns was observed.
High-temperature dealloying in molten alkali chlorides has been demonstrated and nanoporous coherent structures consisting of the intermetallic compounds Pd2In and Pd3In in a ratio of 2 : 1 have been observed.
Исследованы образцы частично окисленного микро- и нанопористого железа, полученного методом высокотемпературного деаллоинга железо-марганцевого сплава в солевом расплаве. При помощи электронной микроскопии получены данные о морфологии образцов и составе их поверхности, установлено, что уже после отмывки при комнатной температуре на воздухе образовались оксидные фазы железа в виде вискеров толщиной порядка 10 нм. В ходе получения образцов достигалось количественное удаление марганца из исходного сплава. Оценена каталитическая активность полученных образцов в гетерогенной реакции Фентона по окислению красителя метилового оранжевого пероксидом водорода. На первом этапе протекания реакции, описываемой уравнением реакции первого порядка, ее скорость определялась наиболее активной расходуемой частью образцов, далее реакция переходила в стационарный режим. Более высокой каталитической активностью обладали нанопористые образцы. The samples of partially oxidized micro- and nanoporous iron obtained by high-temperature dealloing of an iron-manganese alloy in a molten salt were investigated. The data concerning the structure of the samples and the composition of their surface were obtained by electron microscopy; it was found that after washing at room temperature in air the oxide phases of iron were formed as whiskers with a thickness of about 10 nm. During the preparation of the samples a quantitative removal of manganese from the initial alloy was achieved. The catalytic activity of the obtained samples in the heterogeneous Fenton reaction was estimated by oxidation of methyl orange by hydrogen peroxide. The rate of the first stage of the reaction, which was described by the first-order equation, was determined by the most active spent part of the samples, and then the reaction passed into the stationary mode. The nanoporous samples possessed a higher catalytic activity.
Показана каталитическая активность в реакции водно-эмульсионной полимеризации скипидара нескольких наноструктурированных материалов: нанокластерный полиоксометаллат кеплератного типа MoFe, нанопористое железо и нанопористый композит интерметаллидов PdIn@PdIn, полученные деаллоингом эквиатомных сплавов Fe - Mn и Pd - In. Выход чистых политерпеновых смол при использовании инициирования персульфатом калия зависит от характера контактирования катализаторов и субстратов: жидкое-жидкое или твердое-жидкое-жидкое: для растворов полиоксометаллата и нанопористых металлических образцов, соответственно. В качестве реакционной среды для сравнения была взята система, не содержавшая катализаторы. На основе полученных данных о температуре размягчения определена молекулярная масса образцов смолы. Для идентификации полученных продуктов использован метод инфракрасной спектроскопии. В реакционной среде (преимущественно водной) после выделения политерпеновых смол при помощи хроматографического анализа обнаружены такие ценные продукты как альфа-терпинеол, используемый как полупродукт для получения ароматизаторов и флотагент. We have revealed the catalytic activity for initiating the water-emulsion turpentine polymerization of some nanostructured materials such as Keplerate type MoFe nanocluster polyoxometalate, nanoporous iron and nanoporous composite of intermetallic compounds PdIn@PdIn obtained by dealloying of equiatomic alloys Fe - Mn and Pd - In. For polyoxometalate solutions and nanoporous metal samples, respectively, the yield of sufficiently pure polyterpene resins when using the potassium persulphate initiation depends on the nature of the contact between the catalysts and substrates: solid-liquid-liquid or liquid-liquid. A system that did not contain catalysts was taken as the reaction medium for comparison. Based on the obtained data on the softening point, the molecular weight of the resin samples was determined. Infrared spectroscopy was used to identify the obtained products. In the reaction medium (mainly aqueous) after the isolation of polyterpene resins, chromatographic analysis revealed so valuable products as alpha-terpineol, which is used as an intermediate for obtaining flavors and flotation agents.
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