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    XPS and XANES study of layered mineral valleriite
/ Y. L. Mikhlin [et al.] // J. Struct. Chem. - 2017. - Vol. 58, Is. 6. - P. 1137-1143, DOI 10.1134/S0022476617060105. - Cited References: 26 . - ISSN 0022-4766

Кл.слова (ненормированные):
valleriite -- high energy X-ray photoelectron spectroscopy -- TEY XANES

Аннотация: Mineral valleriite of the Talnakh deposit, which consists of alternating copper-iron sulfide layers and brucite-like layers of magnesium-aluminium hydroxide is studied for the first time by XPS at photon excitation energies ranging from 1.253 keV to 6 keV and CuL FeL, SL, AlL, MgK, and OK edge TEY XANES using synchrotron radiation. The comparison of the XPS and XANES spectra of valleriite and chalcopyrite, in particular, demonstrates that in the sulfide layers of valleriite, Cu+ and Fe3+ are in a tetrahedral coordination, however, a local positive charge on both cations is slightly lower than that in chalcopyrite, apparently, due to a structure disorder. The concentration of oxygen-bound iron decreases with an increase in the depth of the analyzed layer even after ion etching; probably, Fe does not enter into the brucite-like layer, but mainly forms its own surface structures.

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Держатели документа:
Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russian Federation
Kirensky Institute of Physics, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russian Federation
Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russian Federation

Доп.точки доступа:
Mikhlin, Y. L.; Romanchenko, A. S.; Tomashevich, E. V.; Volochaev, M. N.; Волочаев, Михаил Николаевич; Laptev, Y. V.

    Valleriite, a natural two-dimensional composite: X-ray absorption, photoelectron, and Mossbauer spectroscopy, and magnetic characterization
/ Y. L. Mikhlin, M. N. Likhatski, O. A. Bayukov [et al.] // ACS Omega. - 2021. - Vol. 6, Is. 11. - P. 7533-7543, DOI 10.1021/acsomega.0c06052. - Cited References: 92. - This research was supported by the Russian Science Foundation, project 18-17-00135. The authors thank Dr. Y. Laptev for providing valleriite samples, the ESRF for allocating beamtime and the BM23 staff for their help during the experiments. Facilities of the Krasnoyarsk Regional Research Equipment Centre of SB RAS were employed in the work . - ISSN 2470-1343
   Перевод заглавия: Исследование валлерита - природного двумерного соединения: поглощение рентгеновских лучей, фотоэлектронная и Мёссбауровская спектроскопия, магнитные свойства

Аннотация: Valleriite is of interest as a mineral source of basic and precious metals and as an unusual material composed of two-dimensional (2D) Fe-Cu sulfide and magnesium hydroxide layers, whose characteristics are still very poorly understood. Here, the mineral samples of two types with about 50% of valleriites from Noril'sk ore provenance, Russia, were examined using Cu K- and Fe K-edge X-ray absorption fine structure (XAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), 57Fe Mossbauer spectroscopy, and magnetic measurements. The Cu K X-ray absorption near-edge structures (XANES) spectra resemble those of chalcopyrite, however, with a higher electron density at Cu+ centers and essentially differ from those of bornite Cu5FeS4; the Fe K-edge was less informative because of accompanying oxidized Fe-containing phases. The post-edge XANES and extended XAFS (EXAFS) analysis reveal differences in the bond lengths, e.g., additional metal-metal distances in valleriites as compared with chalcopyrite. The XPS spectra confirmed the Cu+ and Fe3+ state in the sulfide sheets and suggest that they are in electron equilibrium with (Mg, Al) hydroxide layers. Mossbauer spectra measured at room temperature comprise central doublets of paramagnetic Fe3+, which decreased at 78 K and almost disappeared at 4.2 K, producing a series of hyperfine Zeeman sextets due to internal magnetic fields arising in valleriites. Magnetic measurements do not reveal antiferromagnetic transitions known for bornite. The specific structure and properties of valleriite are discussed in particular as a platform for composites of the 2D transition metal sulfide and hydroxide (mono)layers stacked by the electrical charges, promising for a variety of applications.

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Держатели документа:
Institute of Chemistry and Chemical Technology, Krasnoyarsk Science Center, The Siberian Branch, The Russian Academy of Sciences, Akademgorodok, 50/24, Krasnoyarsk, 660036, Russian Federation
Kirensky Institute of Physics, Krasnoyarsk Science Center, The Siberian Branch, The Russian Academy of Sciences, Akademgorodok 50/38, Krasnoyarsk, 660036, Russian Federation
Reshetnev Siberian State University of Science and Technology, 31, Krasnoyarsky Rabochy Av., Krasnoyarsk, 660037, Russian Federation
Siberian Federal University, Svobodny pr. 79, Krasnoyarsk, 660041, Russian Federation
European Synchrotron Radiation Facility, 6 Rue Jules Horowitz, Grenoble, F-38042, France

Доп.точки доступа:
Mikhlin, Y. L.; Likhatski, M. N.; Bayukov, O. A.; Баюков, Олег Артемьевич; Knyazev, Yu. V.; Князев, Юрий Владимирович; Velikanov, D. A.; Великанов, Дмитрий Анатольевич; Tomashevich, Y. V.; Romanchenko, A. S.; Vorobyev, S. A.; Volochaev, M. N.; Волочаев, Михаил Николаевич; Zharkov, S. M.; Жарков, Сергей Михайлович; Meira, D. M.

    Valleriite-containing ore from Kingash deposit (Siberia, Russia): Mossbauer and X-ray photoelectron spectroscopy characterization, thermal and interfacial properties
/ Y. L. Mikhlin, M. N. Likhatski, A. S. Romanchenko [et al.] // J. Sib. Fed. Univ. Chem. - 2022. - Vol. 15, Is. 3. - P. 303-317 ; Журн. СФУ. Химия, DOI 10.17516/1998-2836-0294. - Cited References: 25. - This research was funded by the Russian Foundation for Basic Research, Krasnoyarsk Territory Science Foundation and Krasnoyarsk Territory Administration, grant number 20-43-242903. Facilities of the Krasnoyarsk Regional Center of Research Equipment of Federal Research Center «Krasnoyarsk Science Center SB RAS» were employed in the work . - ISSN 1998-2836
   Перевод заглавия: Валлериитсодержащая руда Кингашского месторождения (Сибирь, Россия): Мессбауэровская и рентгенофотоэлектронная спектроскопия, термические и межфазные свойства
Аннотация: Valleriite, (Cu,Fe)S2×n(Mg,Al,Fe)(OH)2, and related layered minerals are of interest due to their unusual two-dimensional structure, formation mechanisms, physical and chemical properties, and potential involvement into mineral processing and materials science applications. Here, we have studied Kingash Cu-Ni ore samples containing 10-25% of valleriite in association with serpentines (lizardite and chrysotile) and magnetite using scanning electron microscopy and electron microprobe analysis, Mössbauer spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal analysis and zeta potential measurement. The data are compared with those for Al-doped valleriite synthesized via a hydrothermal route. It was found that the Kingash valleriite contains excessive iron relative to CuFeS2 stoichiometry, which mainly occurs, leaving aside magnetite, as Fe3+-OH species in hydroxide layers of valleriite and minor Fe centers in serpentines. Thermal dehydroxylation of hydroxide layers of valleriites occurs near 500oC in inert atmosphere; in air, sulfide sheets oxidize with an exothermal peak at 447oC, and sulfur oxides don't volatilize but react with hydroxide groups of valleriite rather than serpentines. Zeta potential measurements of coarse ore particles using the flow potential technique suggested that the surface of valleriite is negatively charged in a wide pH range while the positive values at low pHs for fine particles are inflicted by serpentine. The findings demonstrate close resemblance of the natural and synthetic Al-doped valleriites, and the key role of valleriite, despite its moderate content, for the interfacial characteristics of the valleriite-bearing ores.
Валлериит, (Cu, Fe)S2×n(Mg, Al, Fe)(OH)2 и родственные ему слоистые минералы представляют интерес в связи с их необычной двумерной структурой, механизмами образования, физическими и химическими свойствами и возможностью применения в процессах переработки полезных ископаемых и материаловедения. В настоящей работе с помощью сканирующей электронной микроскопии и электронного микрозондового анализа, мессбауэровской спектроскопии, рентгеновской фотоэлектронной спектроскопии (РФЭС), термического анализа и измерения дзета-потенциала нами были изучены образцы медно-никелевых руд Кингашского месторождения, содержащие 10–25 % валлериита в ассоциации с серпентинами (лизардит и хризотил) и магнетитом. Было проведено сравнение полученных данных с результатами измерений легированного алюминием валлериита, синтезированного гидротермальным способом. Установлено, что валлериит Кингашского месторождения содержит избыточное железо по отношению к стехиометрии CuFeS2, которое представлено в основном, не считая магнетита, в виде центров Fe3+-OH, расположенных в гидроксидных слоях валлериита и небольшого числа примесей Fe в серпентинах. Термическое дигидроксилирование гидроксидных слоев валлериитов происходит около 500 °C в инертной атмосфере; на воздухе сульфидные слои окисляются с экзотермическим пиком при 447 °C, а оксиды серы не улетучиваются, а реагируют скорее с гидроксидными группами валлериита, чем с серпентинами. Измерения дзета-потенциала крупных частиц руды с использованием метода потенциала протекания показали, что поверхность валлериита отрицательно заряжена в широком диапазоне рН, в то время как положительные показатели при низких значениях рН для более мелких частиц обусловлены присутствием серпентина. Полученные данные демонстрируют близкое сходство природного и синтетического валлериитов, легированного алюминием, и его ключевую роль для межфазных характеристик валлериитсодержащих руд, даже при его умеренном содержании.

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Держатели документа:
Institute of Chemistry and Chemical Technology, Krasnoyarsk Science Center of the Siberian Branch, The Russian Academy of Sciences, Krasnoyarsk, Russian Federation
Kirensky Institute of Physics, Krasnoyarsk Science Center of the Siberian Branch, The Russian Academy of Sciences, Krasnoyarsk, Russian Federation
Krasnoyarsk Science Center of the Siberian Branch, The Russian Academy of Sciences, Krasnoyarsk, Russian Federation

Доп.точки доступа:
Mikhlin, Y. L.; Likhatski, M. N.; Romanchenko, A. S.; Vorobyev, S. A.; Tomashevich, Y. V.; Fetisova, O. Yu.; Bayukov, O. A.; Баюков, Олег Артемьевич; Knyazev, Yu. V.; Князев, Юрий Владимирович; Nemtsev, I. V.; Karasev, S. V.; Karacharov, A. A.; Borisov, R. V.


    Modification of synthetic valleriite surface with gold nanoparticles: The roles of specific adsorption and zeta potential
/ A. A. Karacharov, M. N. Likhatski, R. V. Borisov [et al.] // Colloid J. - 2024. - Vol. 86, Is. 1. - P. 40-51, DOI 10.1134/S1061933X23601075. - Cited References: 69. - This work was supported by the Russian Science Foundation project no. 22-13-00321 . - ISSN 1061-933X. - ISSN 1608-3067
Аннотация: Layered two-dimensional materials, whose properties dramatically differ from their bulk precursors, are of great theoretical and applied importance. Recently, a layered 2D material, an analog of a natural mineral, valleriite, in which quasi-monoatomic Cu−Fe−S sheets alternate with brucite-like ones, has been prepared using a simple hydrothermal synthesis procedure. The features of the electronic structure of these materials make it possible to propose them as new materials for a wide field of applications such as (electro)photocatalysis, high-capacity batteries, etc. In this work, nanocomposite materials have been prepared via immobilization of gold nanoparticles (AuNPs) from citrate hydrosols on the surface of the synthesized valleriites having different compositions of hydroxide layers, which control the surface charge density. According to X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), energy-dispersive X-ray microanalysis (EDX), and selected area electron diffraction (SAED) data, AuNPs are immobilized on valleriite nanoflakes, which have lateral sizes of 150–200 nm and thicknesses of several tens of nanometers, as isolated metal nanoparticles with an average diameter of 11 nm. A small amount of aggregates indicates a high affinity of AuNPs for the valleriite surface. The amounts of immobilized gold are the same on all studied valleriites (~0.2%). This finding may be related to the simultaneous sorption of free citrate ions from the AuNP hydrosols, with these ions, according to zeta potential measurements, charging the surfaces of all studied valleriite samples to nearly the same negative value of –40 mV. According to the XPS data, the AuNPs immobilization markedly decreases the magnesium and oxygen contents on the surfaces of the synthesized valleriites due to the partial degradation/dissolution of the brucite layer. In addition, the amount of Fe3+ ions bound to OH groups decreases with a simultaneous increase in the fraction of Fe3+–O species. The TEM data have confirmed the preservation of the layered structure of valleriites after the immobilization of AuNPs.

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Держатели документа:
Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences, Federal Research Center “Krasnoyarsk Scientific Center, Siberian Branch, Russian Academy of Sciences”, 660036, Akademgorodok, Krasnoyarsk, Russia
Kirensky Institute of Physics, Siberian Branch, Russian Academy of Sciences, Federal Research Center “Krasnoyarsk Scientific Center, Siberian Branch, Russian Academy of Sciences”, 660036, Akademgorodok, Krasnoyarsk, Russia
Siberian Federal University, 660041, Krasnoyarsk, Russia

Доп.точки доступа:
Karacharov, A. A.; Likhatski, M. N.; Borisov, R. V.; Tomashevich, E. V.; Vorobyev, S. A.; Zharkov, S. M.; Жарков, Сергей Михайлович