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Dr. Andrey Bukhtiyarov
Boreskov Institute of Catalysis SB RAS

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0 Catalysis
0 Scanning Tunneling Microscopy
0 X-ray Photoelectron Spectroscopy (XPS)
0 Bimetallic catalysts based on Pd
0 Bimetallic catalysts

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X-ray Photoelectron Spectroscopy (XPS)
Scanning Tunneling Microscopy
Bimetallic catalysts
Catalysis

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Journal article
Published: 20 July 2021 in Catalysts
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We explored the photoreforming of rice and corn starch with simultaneous hydrogen production over a Cd0.7Zn0.3S-based photocatalyst under visible light irradiation. The photocatalyst was characterized by UV–vis diffuse reflectance spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The influence of starch pretreatment conditions, such as hydrolysis temperature and alkaline concentration, on the reaction rate was studied. The maximum rate of H2 evolution was 730 μmol·h−1·g−1, with AQE = 1.8% at 450 nm, in the solution obtained after starch hydrolysis in 5 M NaOH at 70 °C. The composition of the aqueous phase of the suspension before and after the photocatalytic reaction was studied via high-performance liquid chromatography, and such products as glucose and sodium gluconate, acetate, formate, glycolate, and lactate were found after the photocatalytic reaction.

ACS Style

Anna Kurenkova; Tatiana Medvedeva; Nikolay Gromov; Andrey Bukhtiyarov; Evgeny Gerasimov; Svetlana Cherepanova; Ekaterina Kozlova. Sustainable Hydrogen Production from Starch Aqueous Suspensions over a Cd0.7Zn0.3S-Based Photocatalyst. Catalysts 2021, 11, 870 .

AMA Style

Anna Kurenkova, Tatiana Medvedeva, Nikolay Gromov, Andrey Bukhtiyarov, Evgeny Gerasimov, Svetlana Cherepanova, Ekaterina Kozlova. Sustainable Hydrogen Production from Starch Aqueous Suspensions over a Cd0.7Zn0.3S-Based Photocatalyst. Catalysts. 2021; 11 (7):870.

Chicago/Turabian Style

Anna Kurenkova; Tatiana Medvedeva; Nikolay Gromov; Andrey Bukhtiyarov; Evgeny Gerasimov; Svetlana Cherepanova; Ekaterina Kozlova. 2021. "Sustainable Hydrogen Production from Starch Aqueous Suspensions over a Cd0.7Zn0.3S-Based Photocatalyst." Catalysts 11, no. 7: 870.

Journal article
Published: 18 July 2021 in Catalysts
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A series of oxidative treatments of PdIn-supported intermetallic nanoparticles at different temperatures were performed. The bulk and surface structure of catalyst during phase transformation was investigated by bulk- and surface-sensitive techniques (in situ XAFS, DRIFTS of adsorbed CO). It was found that comparison of palladium and indium fractions in bulk and on the surface suggests the formation of a «core-shell» structure. According to obtained results, the core consists of In-depleted intermetallic compound or inhomogeneous bimetallic phase with the inner core of metallic Pd, when a mixture of indium oxide, metallic palladium and small part of PdIn is present on the surface.

ACS Style

Nadezhda Smirnova; Evgeny Khramov; Galina Baeva; Pavel Markov; Andrey Bukhtiyarov; Yan Zubavichus; Aleksander Stakheev. An Investigation into the Bulk and Surface Phase Transformations of Bimetallic Pd-In/Al2O3 Catalyst during Reductive and Oxidative Treatments In Situ. Catalysts 2021, 11, 859 .

AMA Style

Nadezhda Smirnova, Evgeny Khramov, Galina Baeva, Pavel Markov, Andrey Bukhtiyarov, Yan Zubavichus, Aleksander Stakheev. An Investigation into the Bulk and Surface Phase Transformations of Bimetallic Pd-In/Al2O3 Catalyst during Reductive and Oxidative Treatments In Situ. Catalysts. 2021; 11 (7):859.

Chicago/Turabian Style

Nadezhda Smirnova; Evgeny Khramov; Galina Baeva; Pavel Markov; Andrey Bukhtiyarov; Yan Zubavichus; Aleksander Stakheev. 2021. "An Investigation into the Bulk and Surface Phase Transformations of Bimetallic Pd-In/Al2O3 Catalyst during Reductive and Oxidative Treatments In Situ." Catalysts 11, no. 7: 859.

Journal article
Published: 19 April 2021 in Nanomaterials
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In this study, various solid uranium oxycompounds and TiO2-supported materials based on nanocrystalline anatase TiO2 are synthesized using uranyl nitrate hexahydrate as a precursor. All uranium-contained samples are characterized using N2 adsorption, XRD, UV–vis, Raman, TEM, XPS and tested in the oxidation of a volatile organic compound under visible light of the blue region to find correlations between their physicochemical characteristics and photocatalytic activity. Both uranium oxycompounds and TiO2-supported materials are photocatalytically active and are able to completely oxidize gaseous organic compounds under visible light. If compared to the commercial visible-light TiO2 KRONOS® vlp 7000 photocatalyst used as a benchmark, solid uranium oxycompounds exhibit lower or comparable photocatalytic activity under blue light. At the same time, uranium compounds contained uranyl ion with a uranium charge state of 6+, exhibiting much higher activity than other compounds with a lower charge state of uranium. Immobilization of uranyl ions on the surface of nanocrystalline anatase TiO2 allows for substantial increase in visible-light activity. The photonic efficiency of reaction over uranyl-grafted TiO2, 12.2%, is 17 times higher than the efficiency for commercial vlp 7000 photocatalyst. Uranyl-grafted TiO2 has the potential as a visible-light photocatalyst for special areas of application where there is no strict control for use of uranium compounds (e.g., in spaceships or submarines).

ACS Style

Mikhail Lyulyukin; Tikhon Filippov; Svetlana Cherepanova; Maria Solovyeva; Igor Prosvirin; Andrey Bukhtiyarov; Denis Kozlov; Dmitry Selishchev. Synthesis, Characterization and Visible-Light Photocatalytic Activity of Solid and TiO2-Supported Uranium Oxycompounds. Nanomaterials 2021, 11, 1036 .

AMA Style

Mikhail Lyulyukin, Tikhon Filippov, Svetlana Cherepanova, Maria Solovyeva, Igor Prosvirin, Andrey Bukhtiyarov, Denis Kozlov, Dmitry Selishchev. Synthesis, Characterization and Visible-Light Photocatalytic Activity of Solid and TiO2-Supported Uranium Oxycompounds. Nanomaterials. 2021; 11 (4):1036.

Chicago/Turabian Style

Mikhail Lyulyukin; Tikhon Filippov; Svetlana Cherepanova; Maria Solovyeva; Igor Prosvirin; Andrey Bukhtiyarov; Denis Kozlov; Dmitry Selishchev. 2021. "Synthesis, Characterization and Visible-Light Photocatalytic Activity of Solid and TiO2-Supported Uranium Oxycompounds." Nanomaterials 11, no. 4: 1036.

Research article
Published: 10 February 2021 in Inorganic Chemistry
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A series of salts (R4N)2[Pd(NO3)4] (R = CH3, C2H5, n-C3H7; 1–3) were synthesized in high yield from a nitric acid solution of palladium. The salts were characterized by a combination of physicochemical methods, and their crystal structures were determined by X-ray diffraction. The conformation of the [Pd(NO3)4]2– anion was studied in detail using crystal structure data and density functional theory calculations. A combination of nonhygroscopicity and stability under normal conditions, together with thermolability, high solubility in various solvents, and the lability of nitrato ligands, makes salts 1–3 valuable starting materials for the synthesis of Pd compounds and the preparation of Pd-containing catalysts. In this work, these applications were illustrated by the synthesis of heteroleptic Pd(II) nitrato complexes with N-donor ligands and the preparation of Pd0.1Ni0.9/SiO2 catalysts, which worked well in H2 generation from hydrazine hydrate. Generally, it was shown that up to several weight percent of Pd can be deposited on various oxide/hydroxide supports using a straightforward chemisorption procedure from acetone solutions of 1–3.

ACS Style

Danila Vasilchenko; Polina Topchiyan; Semen Berdyugin; Pavel Plyusnin; Vladimir Shayapov; Iraida Baidina; Vladislav Komarov; Andrey Bukhtiyarov; Evgeny Gerasimov. Tetranitratopalladate(II) Salts with Tetraalkylammonium Cations: Structural Aspects, Reactivity, and Applicability toward Palladium Deposition for Catalytic Applications. Inorganic Chemistry 2021, 60, 2983 -2995.

AMA Style

Danila Vasilchenko, Polina Topchiyan, Semen Berdyugin, Pavel Plyusnin, Vladimir Shayapov, Iraida Baidina, Vladislav Komarov, Andrey Bukhtiyarov, Evgeny Gerasimov. Tetranitratopalladate(II) Salts with Tetraalkylammonium Cations: Structural Aspects, Reactivity, and Applicability toward Palladium Deposition for Catalytic Applications. Inorganic Chemistry. 2021; 60 (5):2983-2995.

Chicago/Turabian Style

Danila Vasilchenko; Polina Topchiyan; Semen Berdyugin; Pavel Plyusnin; Vladimir Shayapov; Iraida Baidina; Vladislav Komarov; Andrey Bukhtiyarov; Evgeny Gerasimov. 2021. "Tetranitratopalladate(II) Salts with Tetraalkylammonium Cations: Structural Aspects, Reactivity, and Applicability toward Palladium Deposition for Catalytic Applications." Inorganic Chemistry 60, no. 5: 2983-2995.

Journal article
Published: 01 February 2021 in Nanomaterials
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A series of solid solutions of cadmium and manganese sulfides, Cd1-xMnxS (x = 0–0.35), and composite photocatalysts, CdS-β-Mn3O4-MnOOH, were synthesized by precipitation with sodium sulfide from soluble cadmium and manganese salts with further hydrothermal treatment at 120 °C. The obtained photocatalysts were studied by the X-ray diffraction method (XRD), UV-vis diffuse reflectance spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and N2 low temperature adsorption. The photocatalysts were tested in hydrogen production using a Na2S/Na2SO3 aqueous solution under visible light (λ = 450 nm). It was shown for the first time that both kinds of photocatalysts possess high activity in hydrogen evolution under visible light. The solid solution Cd0.65Mn0.35S has an enhanced photocatalytic activity due to its valence and conduction band position tuning, whereas the CdS-β-Mn3O4-MnOOH (40–60 at% Mn) samples were active due to ternary heterojunction formation. Further, the composite CdS-β-Mn3O4-MnOOH photocatalyst had much higher stability in comparison to the Cd0.65Mn0.35S solid solution. The highest activity was 600 mmol g−1 h−1, and apparent quantum efficiency of 2.9% (λ = 450 nm) was possessed by the sample of CdS-β-Mn3O4-MnOOH (40 at% Mn).

ACS Style

Ksenia O. Potapenko; Anna Yu. Kurenkova; Andrey V. Bukhtiyarov; Evgeny Yu. Gerasimov; Svetlana V. Cherepanova; Ekaterina A. Kozlova. Comparative Study of the Photocatalytic Hydrogen Evolution over Cd1−xMnxS and CdS-β-Mn3O4-MnOOH Photocatalysts under Visible Light. Nanomaterials 2021, 11, 355 .

AMA Style

Ksenia O. Potapenko, Anna Yu. Kurenkova, Andrey V. Bukhtiyarov, Evgeny Yu. Gerasimov, Svetlana V. Cherepanova, Ekaterina A. Kozlova. Comparative Study of the Photocatalytic Hydrogen Evolution over Cd1−xMnxS and CdS-β-Mn3O4-MnOOH Photocatalysts under Visible Light. Nanomaterials. 2021; 11 (2):355.

Chicago/Turabian Style

Ksenia O. Potapenko; Anna Yu. Kurenkova; Andrey V. Bukhtiyarov; Evgeny Yu. Gerasimov; Svetlana V. Cherepanova; Ekaterina A. Kozlova. 2021. "Comparative Study of the Photocatalytic Hydrogen Evolution over Cd1−xMnxS and CdS-β-Mn3O4-MnOOH Photocatalysts under Visible Light." Nanomaterials 11, no. 2: 355.

Journal article
Published: 07 January 2021 in Nanomaterials
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Structure of model bimetallic PdAu nanoparticles is analyzed aiming to find Pd:Au ratios optimal for existence of Pd1 single-atom surface sites inside outer Au atomic shell. The analysis is performed using density-functional theory (DFT) calculations and topological approach based on DFT-parameterized topological energy expression. The number of the surface Pd1 sites in the absence of adsorbates is calculated as a function of Pd concentration inside the particles. At low Pd contents none of the Pd atoms emerge on the surface in the lowest-energy chemical orderings. However, surface Pd1 sites become stable, when Pd content inside a Pd-Au particle reaches ca. 60%. Further Pd content increase up to almost pure Pd core is accompanied by increased concentration of surface Pd atoms, mostly as Pd1 sites, although larger Pd ensembles as dimers and linear trimers are formed as well. Analysis of the chemical orderings inside PdAu nanoparticles at different Pd contents revealed that enrichment of the subsurface shell by Pd with predominant occupation of its edge positions precedes emergence of Pd surface species.

ACS Style

Mikhail Mamatkulov; Ilya V. Yudanov; Andrey V. Bukhtiyarov; Konstantin M. Neyman. Pd Single-Atom Sites on the Surface of PdAu Nanoparticles: A DFT-Based Topological Search for Suitable Compositions. Nanomaterials 2021, 11, 122 .

AMA Style

Mikhail Mamatkulov, Ilya V. Yudanov, Andrey V. Bukhtiyarov, Konstantin M. Neyman. Pd Single-Atom Sites on the Surface of PdAu Nanoparticles: A DFT-Based Topological Search for Suitable Compositions. Nanomaterials. 2021; 11 (1):122.

Chicago/Turabian Style

Mikhail Mamatkulov; Ilya V. Yudanov; Andrey V. Bukhtiyarov; Konstantin M. Neyman. 2021. "Pd Single-Atom Sites on the Surface of PdAu Nanoparticles: A DFT-Based Topological Search for Suitable Compositions." Nanomaterials 11, no. 1: 122.

Journal article
Published: 01 December 2020 in Review of Scientific Instruments
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Atmospheric pressure reactions on model catalysts are typically performed in so-called high-pressure cells, with product analysis performed by gas chromatography (GC) or mass spectrometry (MS). However, in most cases, these cells have a large volume (liters) so that the reactions on catalysts with only cm2 surface area can be carried out only in the (recirculated) batch mode to accumulate sufficient product amounts. Herein, we describe a novel small-volume (milliliters) catalytic reactor that enables kinetic studies under atmospheric pressure flow conditions. The cell is located inside an ultrahigh vacuum chamber that is deliberately limited to basic functions. Model catalyst samples are mounted inside the reactor cell, which is locked to an oven for external heating and closed by using an extendable/retractable gas dosing tube. Reactant and product analyses are performed by both micro-GC and MS. The functionality of the new design is demonstrated by catalytic ethylene (C2H4) hydrogenation on polycrystalline Pt and Pd foils.

ACS Style

Thomas Haunold; Christoph Rameshan; Andrey V. Bukhtiyarov; Günther Rupprechter. An ultrahigh vacuum-compatible reaction cell for model catalysis under atmospheric pressure flow conditions. Review of Scientific Instruments 2020, 91, 125101 .

AMA Style

Thomas Haunold, Christoph Rameshan, Andrey V. Bukhtiyarov, Günther Rupprechter. An ultrahigh vacuum-compatible reaction cell for model catalysis under atmospheric pressure flow conditions. Review of Scientific Instruments. 2020; 91 (12):125101.

Chicago/Turabian Style

Thomas Haunold; Christoph Rameshan; Andrey V. Bukhtiyarov; Günther Rupprechter. 2020. "An ultrahigh vacuum-compatible reaction cell for model catalysis under atmospheric pressure flow conditions." Review of Scientific Instruments 91, no. 12: 125101.

Research article
Published: 10 November 2020 in The Journal of Physical Chemistry C
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The reductive exsolution of metallic Ru from fluorite-type solid solutions Ln2Ru0.2Ce1.8O7 (Ln = Sm, Nd, La) leads to materials with metal–support interactions that influence the electronic state and the catalytic activity of Ru. In situ X-ray absorption spectroscopy at the Ru K-edge identified that with increasing temperature, the exsolution of Ru from Sm2Ru0.2Ce1.8O7 in a H2 atmosphere proceeds via an intermediate Ruδ+ state, that is, Ru4+→Ruδ+→Ru0. X-ray photoelectron spectroscopy (XPS) established that, in parallel (H2 atmosphere at ca. 500 °C), also Ce4+ ions reduce to Ce3+, which is accompanied by an electron transfer from the reduced host oxide to the exsolved Ru0 clusters, creating Ruδ− states. Low-temperature diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) using CO as a probe molecule reveals a red shift of the CO adsorption bands by ca. 18 cm–1 when increasing the temperature during the H2 treatment from 300 to 500 °C, consistent with an increased π-backdonation from more electron-rich Ru species to CO. However, at a lower reduction temperature of ca. 100 °C, a blue-shifted CO band is observed that is explained by a Lewis-acidic Ruδ+–CO adduct. Nuclear magnetic resonance (NMR) signal enhancement in parahydrogen-induced polarization experiments was used as a structure-sensitive probe and revealed a decreasing propene hydrogenation rate with increasing exsolution temperature, accompanied by a notable enhancement of propane hyperpolarization (ca. 3-fold higher at 500 °C than at 300 °C). These data suggest that the exsolved, subnanometer-sized Ru species are more active in propene hydrogenation but less selective for the pairwise addition of p-H2 to propene than Ruδ− sites engaged in a strong metal–support interaction.

ACS Style

Muhammad A. Naeem; Dudari B. Burueva; Paula M. Abdala; Nikolai S. Bushkov; Dragos Stoian; Andrey V. Bukhtiyarov; Igor P. Prosvirin; Valerii I. Bukhtiyarov; Kirill V. Kovtunov; Igor V. Koptyug; Alexey Fedorov; Christoph R. Müller. Deciphering the Nature of Ru Sites in Reductively Exsolved Oxides with Electronic and Geometric Metal–Support Interactions. The Journal of Physical Chemistry C 2020, 124, 25299 -25307.

AMA Style

Muhammad A. Naeem, Dudari B. Burueva, Paula M. Abdala, Nikolai S. Bushkov, Dragos Stoian, Andrey V. Bukhtiyarov, Igor P. Prosvirin, Valerii I. Bukhtiyarov, Kirill V. Kovtunov, Igor V. Koptyug, Alexey Fedorov, Christoph R. Müller. Deciphering the Nature of Ru Sites in Reductively Exsolved Oxides with Electronic and Geometric Metal–Support Interactions. The Journal of Physical Chemistry C. 2020; 124 (46):25299-25307.

Chicago/Turabian Style

Muhammad A. Naeem; Dudari B. Burueva; Paula M. Abdala; Nikolai S. Bushkov; Dragos Stoian; Andrey V. Bukhtiyarov; Igor P. Prosvirin; Valerii I. Bukhtiyarov; Kirill V. Kovtunov; Igor V. Koptyug; Alexey Fedorov; Christoph R. Müller. 2020. "Deciphering the Nature of Ru Sites in Reductively Exsolved Oxides with Electronic and Geometric Metal–Support Interactions." The Journal of Physical Chemistry C 124, no. 46: 25299-25307.

Journal article
Published: 16 October 2020 in ACS Applied Materials & Interfaces
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An efficient method for the deposition of ionic platinum species PtO x onto a TiO2 surface was developed on the basis of light-induced activation of the [Pt(NO3)6]2- anion. The deposited PtO x species with an effective Pt oxidation state between +4 and +2 have an oxygen-made environment and include single ion centers {PtO n } and polyatomic ensembles {Pt n O m } connected to a TiO2 surface with Pt-O-Ti bonds. The resulting PtO x /TiO2 materials were tested as photocatalysts for the hydrogen evolution reaction (HER) from a water ethanol mixture and have shown uniquely high activity with the rate of H2 evolution achieving 11 mol h-1 per gram of Pt, which is the highest result for such materials reported to date. A combination of spectral methods shows that, under HER conditions, reduction of the supported PtO x species leads to the formation of well-dispersed nanoparticles of metallic platinum attached on the surface of TiO2 by Ti-O-Pt bonds. The high activity of the PtO x /TiO2 materials is believed to result from a combination of uniform distribution of small platinum nanoparticles over the titania surface and their close interaction with TiO2.

ACS Style

Danila Vasilchenko; Polina Topchiyan; Alphiya Tsygankova; Tatyana Asanova; Boris Kolesov; Andrey Bukhtiyarov; Anna Kurenkova; Ekaterina Kozlova. Photoinduced Deposition of Platinum from (Bu4N)2[Pt(NO3)6] for a Low Pt-Loading Pt/TiO2 Hydrogen Photogeneration Catalyst. ACS Applied Materials & Interfaces 2020, 12, 48631 -48641.

AMA Style

Danila Vasilchenko, Polina Topchiyan, Alphiya Tsygankova, Tatyana Asanova, Boris Kolesov, Andrey Bukhtiyarov, Anna Kurenkova, Ekaterina Kozlova. Photoinduced Deposition of Platinum from (Bu4N)2[Pt(NO3)6] for a Low Pt-Loading Pt/TiO2 Hydrogen Photogeneration Catalyst. ACS Applied Materials & Interfaces. 2020; 12 (43):48631-48641.

Chicago/Turabian Style

Danila Vasilchenko; Polina Topchiyan; Alphiya Tsygankova; Tatyana Asanova; Boris Kolesov; Andrey Bukhtiyarov; Anna Kurenkova; Ekaterina Kozlova. 2020. "Photoinduced Deposition of Platinum from (Bu4N)2[Pt(NO3)6] for a Low Pt-Loading Pt/TiO2 Hydrogen Photogeneration Catalyst." ACS Applied Materials & Interfaces 12, no. 43: 48631-48641.

Journal article
Published: 15 May 2020 in Applied Catalysis A: General
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A series of bimetallic Pd–Ag catalysts supported on the carbon material Sibunit was synthesized for selective liquid-phase acetylene hydrogenation. Using XRD and EXAFS it was shown that palladium and silver in the 0.5% Pd–Ag/Sibunit can form bimetallic PdxAg(1−x) nanoparticles with the composition depending on the Pd:Ag ratio. The active component of Pd–Ag(1:0.25)/Sibunit, Pd–Ag(1:1)/Sibunit and Pd–Ag(1:4)/Sibunit is represented by the particles of Pd0.74Ag0.26, Pd0.60Ag0.40 and Pd0.41Ag0.59 nanoalloys, respectively. An increase of the quantity of silver decreases the catalyst activity. The XPS study revealed that this phenomenon is caused by a decrease in the surface concentration of palladium (geometrical effect) and an increase in the degree of palladium electronic modification with silver (electronic effect). The latter exerts a beneficial effect on the reaction selectivity: as the Pd:Ag molar ratio is raised to 1:2, selectivity to ethylene increases to 81% (X > 97%), which exceeds 2.7-fold the selectivity of Pd/Sibunit.

ACS Style

Daria V. Glyzdova; Tatyana N. Afonasenko; Evgeny V. Khramov; Natalya N. Leont’Eva; Igor P. Prosvirin; Andrey V. Bukhtiyarov; Dmitry A. Shlyapin. Liquid-phase acetylene hydrogenation over Ag-modified Pd/Sibunit catalysts: Effect of Pd to Ag molar ratio. Applied Catalysis A: General 2020, 600, 117627 .

AMA Style

Daria V. Glyzdova, Tatyana N. Afonasenko, Evgeny V. Khramov, Natalya N. Leont’Eva, Igor P. Prosvirin, Andrey V. Bukhtiyarov, Dmitry A. Shlyapin. Liquid-phase acetylene hydrogenation over Ag-modified Pd/Sibunit catalysts: Effect of Pd to Ag molar ratio. Applied Catalysis A: General. 2020; 600 ():117627.

Chicago/Turabian Style

Daria V. Glyzdova; Tatyana N. Afonasenko; Evgeny V. Khramov; Natalya N. Leont’Eva; Igor P. Prosvirin; Andrey V. Bukhtiyarov; Dmitry A. Shlyapin. 2020. "Liquid-phase acetylene hydrogenation over Ag-modified Pd/Sibunit catalysts: Effect of Pd to Ag molar ratio." Applied Catalysis A: General 600, no. : 117627.

Journal article
Published: 29 April 2020 in Applied Surface Science
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Bimetallic Pd-In/HOPG model catalysts have been prepared and investigated using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) techniques. The spontaneous formation of intermetallic Pd-In nanoparticles or at least partial In diffusion into Pd particles with emergence of In-Pd surface alloy already at the step of In deposition onto monometallic Pd/HOPG sample has been revealed. An additional cycle of oxidation-reduction treatment is necessary in order to form the uniform Pd-In alloy species. For a series of Pd-In/HOPG model catalysts, we demonstrate that the reversible RedOx transformation Pd-Inintermet ↔ Pd° + InOx can be efficiently used to deliberately tune the nanoparticles surface composition/structure and respective catalytic characteristics.

ACS Style

A.V. Bukhtiyarov; M.A. Panafidin; I.A. Chetyrin; I.P. Prosvirin; I.S. Mashkovsky; N.S. Smirnova; P.V. Markov; Y.V. Zubavichus; A.Yu. Stakheev; V.I. Bukhtiyarov. Intermetallic Pd-In/HOPG model catalysts: Reversible tuning the surface structure by O2-induced segregation. Applied Surface Science 2020, 525, 146493 .

AMA Style

A.V. Bukhtiyarov, M.A. Panafidin, I.A. Chetyrin, I.P. Prosvirin, I.S. Mashkovsky, N.S. Smirnova, P.V. Markov, Y.V. Zubavichus, A.Yu. Stakheev, V.I. Bukhtiyarov. Intermetallic Pd-In/HOPG model catalysts: Reversible tuning the surface structure by O2-induced segregation. Applied Surface Science. 2020; 525 ():146493.

Chicago/Turabian Style

A.V. Bukhtiyarov; M.A. Panafidin; I.A. Chetyrin; I.P. Prosvirin; I.S. Mashkovsky; N.S. Smirnova; P.V. Markov; Y.V. Zubavichus; A.Yu. Stakheev; V.I. Bukhtiyarov. 2020. "Intermetallic Pd-In/HOPG model catalysts: Reversible tuning the surface structure by O2-induced segregation." Applied Surface Science 525, no. : 146493.

Paper
Published: 30 January 2020 in Faraday Discussions
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We report a catalyst with the highest selectivity toward pairwise hydrogen addition of 7% among supported metal catalysts, found as a result of variation of Rh/TiO2 catalyst preparation procedures.

ACS Style

Ekaterina V. Pokochueva; Dudari B. Burueva; Larisa M. Kovtunova; Andrey V. Bukhtiyarov; Alexei Yu. Gladky; Kirill V. Kovtunov; Igor V. Koptyug; Valerii I. Bukhtiyarov. Mechanistic in situ investigation of heterogeneous hydrogenation over Rh/TiO2 catalysts: selectivity, pairwise route and catalyst nature. Faraday Discussions 2020, 229, 161 -175.

AMA Style

Ekaterina V. Pokochueva, Dudari B. Burueva, Larisa M. Kovtunova, Andrey V. Bukhtiyarov, Alexei Yu. Gladky, Kirill V. Kovtunov, Igor V. Koptyug, Valerii I. Bukhtiyarov. Mechanistic in situ investigation of heterogeneous hydrogenation over Rh/TiO2 catalysts: selectivity, pairwise route and catalyst nature. Faraday Discussions. 2020; 229 ():161-175.

Chicago/Turabian Style

Ekaterina V. Pokochueva; Dudari B. Burueva; Larisa M. Kovtunova; Andrey V. Bukhtiyarov; Alexei Yu. Gladky; Kirill V. Kovtunov; Igor V. Koptyug; Valerii I. Bukhtiyarov. 2020. "Mechanistic in situ investigation of heterogeneous hydrogenation over Rh/TiO2 catalysts: selectivity, pairwise route and catalyst nature." Faraday Discussions 229, no. : 161-175.

Original paper
Published: 02 January 2020 in Topics in Catalysis
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The bimetallic Pd–Pt/Al2O3 supported catalysts with different Pd/Pt ratios have been prepared and studied in methane oxidation reaction. Comparison of their catalytic properties with those of monometallic Pd/Al2O3 and Pt/Al2O3 samples has shown that the bimetallic catalysts with a relatively low Pt loading (less than 0.4 mol%) are more active than the monometallic ones indicating the synergy effect. An increase in Pt loading above 0.5 mol% decreases the catalytic activity, so that these catalysts become less active than the monometallic Pd/Al2O3 catalysts, but still keep an activity higher than that of the least active monometallic Pt/Al2O3 sample. The chemical states of the palladium and platinum for all the catalysts produced depending on the reaction conditions have been investigated with in situ XPS. It has been shown that even at room temperature the reaction mixture affects the surface composition of the catalysts, which does not change much at higher reaction temperatures. The data have led us to suggestion that activity in the total methane oxidation is promoted by formation of Pd2+, surface fraction of which depends on Pt content in the bimetallic catalysts.

ACS Style

Igor A. Chetyrin; Andrey V. Bukhtiyarov; Igor P. Prosvirin; Alexander K. Khudorozhkov; Valerii I. Bukhtiyarov. In Situ XPS and MS Study of Methane Oxidation on the Pd–Pt/Al2O3 Catalysts. Topics in Catalysis 2020, 63, 66 -74.

AMA Style

Igor A. Chetyrin, Andrey V. Bukhtiyarov, Igor P. Prosvirin, Alexander K. Khudorozhkov, Valerii I. Bukhtiyarov. In Situ XPS and MS Study of Methane Oxidation on the Pd–Pt/Al2O3 Catalysts. Topics in Catalysis. 2020; 63 (1-2):66-74.

Chicago/Turabian Style

Igor A. Chetyrin; Andrey V. Bukhtiyarov; Igor P. Prosvirin; Alexander K. Khudorozhkov; Valerii I. Bukhtiyarov. 2020. "In Situ XPS and MS Study of Methane Oxidation on the Pd–Pt/Al2O3 Catalysts." Topics in Catalysis 63, no. 1-2: 66-74.

Originalpaper
Published: 01 January 2020 in Catalysis in Industry
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The selectivity toward products is studied for the industrially important process of NO hydrogenation in a H2SO4 solution as a function of process parameters: the hourly space velocity of the NO + H2 gas mixture through the reactor, the speed of stirring and the concentration of the Pt catalyst/graphite suspension, and the temperature. It is found that the first or zero order with respect to the catalyst can be observed for this process in the regime of external diffusion limitation for the gas reagents, depending on the concentration of the catalyst in the suspension, and the selectivity toward solid products (hydroxylamine sulfate (HAS) and ammonium sulfate) is greatest in the region of transition. It is shown that the selectivity towards HAS can be improved by functionalizing graphite surface with nitrogen-containing groups that modify the adsorption and catalytic properties of supported platinum nanoparticles. Some views are presented on specific features of the functioning of platinum catalysts in concentrated suspensions with a limited supply of the reaction gases.

ACS Style

A. N. Bobrovskaya; P. A. Simonov; R. I. Kvon; A. V. Bukhtiyarov; A. V. Romanenko. Synthesis of Hydroxylamine Sulfate via NO Hydrogenation over Pt/Graphite Catalysts, Part 2: Effect of the Reaction Conditions and the Physicochemical State of a Catalyst on the Yield of Products. Catalysis in Industry 2020, 12, 16 -28.

AMA Style

A. N. Bobrovskaya, P. A. Simonov, R. I. Kvon, A. V. Bukhtiyarov, A. V. Romanenko. Synthesis of Hydroxylamine Sulfate via NO Hydrogenation over Pt/Graphite Catalysts, Part 2: Effect of the Reaction Conditions and the Physicochemical State of a Catalyst on the Yield of Products. Catalysis in Industry. 2020; 12 (1):16-28.

Chicago/Turabian Style

A. N. Bobrovskaya; P. A. Simonov; R. I. Kvon; A. V. Bukhtiyarov; A. V. Romanenko. 2020. "Synthesis of Hydroxylamine Sulfate via NO Hydrogenation over Pt/Graphite Catalysts, Part 2: Effect of the Reaction Conditions and the Physicochemical State of a Catalyst on the Yield of Products." Catalysis in Industry 12, no. 1: 16-28.

Journals
Published: 21 November 2019 in Catalysis Science & Technology
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Glass tube reactors with Pd, Pt, Rh or Ir nanoparticles dispersed on a thin layer of TiO2, CeO2, SiO2 or Al2O3 provided mechanistic insight into the hydrogenation of 1,3-butadiene using parahydrogen.

ACS Style

Alexandra Svyatova; Elizaveta S. Kononenko; Kirill V. Kovtunov; Dmitry Lebedev; Evgeniy Yu. Gerasimov; Andrey V. Bukhtiyarov; Igor P. Prosvirin; Valerii I. Bukhtiyarov; Christoph Rüdiger Müller; Alexey Fedorov; Igor V. Koptyug. Spatially resolved NMR spectroscopy of heterogeneous gas phase hydrogenation of 1,3-butadiene with parahydrogen. Catalysis Science & Technology 2019, 10, 99 -104.

AMA Style

Alexandra Svyatova, Elizaveta S. Kononenko, Kirill V. Kovtunov, Dmitry Lebedev, Evgeniy Yu. Gerasimov, Andrey V. Bukhtiyarov, Igor P. Prosvirin, Valerii I. Bukhtiyarov, Christoph Rüdiger Müller, Alexey Fedorov, Igor V. Koptyug. Spatially resolved NMR spectroscopy of heterogeneous gas phase hydrogenation of 1,3-butadiene with parahydrogen. Catalysis Science & Technology. 2019; 10 (1):99-104.

Chicago/Turabian Style

Alexandra Svyatova; Elizaveta S. Kononenko; Kirill V. Kovtunov; Dmitry Lebedev; Evgeniy Yu. Gerasimov; Andrey V. Bukhtiyarov; Igor P. Prosvirin; Valerii I. Bukhtiyarov; Christoph Rüdiger Müller; Alexey Fedorov; Igor V. Koptyug. 2019. "Spatially resolved NMR spectroscopy of heterogeneous gas phase hydrogenation of 1,3-butadiene with parahydrogen." Catalysis Science & Technology 10, no. 1: 99-104.

Journal article
Published: 01 November 2019 in Kinetics and Catalysis
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The regularities of formation of alloyed Pd–Cu bimetallic particles deposited on highly oriented pyrolytic graphite (HOPG) were studied by STM and synchrotron-radiation-based XPS. Their chemical composition, structure, and the ranges of thermal stability under ultrahigh vacuum were determined. The Pd–Cu/HOPG model catalysts, as well as the Pd–Ag/HOPG samples whose preparation procedure was tested earlier, exhibited catalytic activity in CO and methanol oxidations at pressures typical of in situ XPS experiments and were stable at the temperatures of the catalytic reaction.

ACS Style

M. A. Panafidin; A. V. Bukhtiyarov; A. Yu. Klyushin; I. P. Prosvirin; I. A. Chetyrin; V. I. Bukhtiyarov. Pd–Cu/HOPG and Pd–Ag/HOPG Model Catalysts in CO and Methanol Oxidations at Submillibar Pressures. Kinetics and Catalysis 2019, 60, 832 -841.

AMA Style

M. A. Panafidin, A. V. Bukhtiyarov, A. Yu. Klyushin, I. P. Prosvirin, I. A. Chetyrin, V. I. Bukhtiyarov. Pd–Cu/HOPG and Pd–Ag/HOPG Model Catalysts in CO and Methanol Oxidations at Submillibar Pressures. Kinetics and Catalysis. 2019; 60 (6):832-841.

Chicago/Turabian Style

M. A. Panafidin; A. V. Bukhtiyarov; A. Yu. Klyushin; I. P. Prosvirin; I. A. Chetyrin; V. I. Bukhtiyarov. 2019. "Pd–Cu/HOPG and Pd–Ag/HOPG Model Catalysts in CO and Methanol Oxidations at Submillibar Pressures." Kinetics and Catalysis 60, no. 6: 832-841.

Journal article
Published: 01 January 2019 in Journal of Structural Chemistry
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Metal redistribution and alloy formation in bimetallic model catalysts M–Au/HOPG (M = Pd, Ag, Cu) are studied using X-ray photoelectron spectroscopy with synchrotron radiation in a wide temperature range (25–500 °C) in ultrahigh vacuum. The composition, structure, and electronic properties of bimetallic particles are determined from the obtained spectral data at all stages of their formation. Thus, the work demonstrates the possibility of using photoelectron spectroscopy with synchrotron radiation to develop the methods of preparing supported bimetallic particles of various composition with controlled distribution of metals over their volumes.

ACS Style

A. V. Bukhtiyarov; I. P. Prosvirin; I. A. Chetyrin; V. I. Bukhtiyarov. Using Sr-XPS to Study the Preparation Features of M-Au/HOPG Model Catalysts (M = Pd, Ag, Cu). Journal of Structural Chemistry 2019, 60, 45 -52.

AMA Style

A. V. Bukhtiyarov, I. P. Prosvirin, I. A. Chetyrin, V. I. Bukhtiyarov. Using Sr-XPS to Study the Preparation Features of M-Au/HOPG Model Catalysts (M = Pd, Ag, Cu). Journal of Structural Chemistry. 2019; 60 (1):45-52.

Chicago/Turabian Style

A. V. Bukhtiyarov; I. P. Prosvirin; I. A. Chetyrin; V. I. Bukhtiyarov. 2019. "Using Sr-XPS to Study the Preparation Features of M-Au/HOPG Model Catalysts (M = Pd, Ag, Cu)." Journal of Structural Chemistry 60, no. 1: 45-52.

Journal article
Published: 01 November 2018 in Kinetics and Catalysis
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A series of model bimetallic Pd–Ag catalysts with different ratios of metals and size distributions of supported particles was prepared by successive metal deposition onto a modified surface of highly oriented pyrolytic graphite (HOPG). X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) were used to characterize the structural and electronic properties, as well as the morphology of nanoparticles at all stages of catalyst preparation. The use of the method made it possible to obtain bimetallic particles with various structures: alloyed, core–shell, and those consisting of individual monometallic particles. The XPS method with synchrotron radiation was used to determine the patterns in the formation of alloyed bimetallic particles, their chemical composition, structure, and the ranges of thermal stability under conditions of ultrahigh vacuum.

ACS Style

Maxim Panafidin; A. V. Bukhtiyarov; I. P. Prosvirin; I. A. Chetyrin; V. I. Bukhtiyarov. Model Bimetallic Pd–Ag/HOPG Catalysts: An XPS and STM Study. Kinetics and Catalysis 2018, 59, 776 -785.

AMA Style

Maxim Panafidin, A. V. Bukhtiyarov, I. P. Prosvirin, I. A. Chetyrin, V. I. Bukhtiyarov. Model Bimetallic Pd–Ag/HOPG Catalysts: An XPS and STM Study. Kinetics and Catalysis. 2018; 59 (6):776-785.

Chicago/Turabian Style

Maxim Panafidin; A. V. Bukhtiyarov; I. P. Prosvirin; I. A. Chetyrin; V. I. Bukhtiyarov. 2018. "Model Bimetallic Pd–Ag/HOPG Catalysts: An XPS and STM Study." Kinetics and Catalysis 59, no. 6: 776-785.

Research article
Published: 16 October 2018 in The Journal of Physical Chemistry C
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For bimetallic Pd-Au/HOPG model catalysts the reversible enrichment of surface by Pd under CO oxidation conditions was found using NAP XPS technique. Density functional calculations combined with calculations using topological energy expression method (TOP-method) were applied to reveal the mechanism of this phenomenon and to quantify the stability of different arrangements of metal atoms in bimetallic PdAu nanoparticles in the presence of CO adsorbate. According to results of this computational approach, adsorption of CO already at a rather moderate coverage is sufficient to make energetically feasible segregation of Pd at terraces of PdAu nanoparticles similar in size with experimentally studied ones.

ACS Style

Mikhail Mamatkulov; Ilya V. Yudanov; Andrey V. Bukhtiyarov; Igor P. Prosvirin; Valerii I. Bukhtiyarov; Konstantin M. Neyman. Pd Segregation on the Surface of Bimetallic PdAu Nanoparticles Induced by Low Coverage of Adsorbed CO. The Journal of Physical Chemistry C 2018, 123, 8037 -8046.

AMA Style

Mikhail Mamatkulov, Ilya V. Yudanov, Andrey V. Bukhtiyarov, Igor P. Prosvirin, Valerii I. Bukhtiyarov, Konstantin M. Neyman. Pd Segregation on the Surface of Bimetallic PdAu Nanoparticles Induced by Low Coverage of Adsorbed CO. The Journal of Physical Chemistry C. 2018; 123 (13):8037-8046.

Chicago/Turabian Style

Mikhail Mamatkulov; Ilya V. Yudanov; Andrey V. Bukhtiyarov; Igor P. Prosvirin; Valerii I. Bukhtiyarov; Konstantin M. Neyman. 2018. "Pd Segregation on the Surface of Bimetallic PdAu Nanoparticles Induced by Low Coverage of Adsorbed CO." The Journal of Physical Chemistry C 123, no. 13: 8037-8046.

Journal article
Published: 01 October 2018 in Catalysis in Industry
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The physicochemical state of supported platinum and the surface of the support is studied for a number of industrial 0.5 wt % Pt/graphite (freshly prepared, after the synthesis of hydroxylamine sulfate via NO hydrogenation in sulfuric acid, and regenerated) by scanning electron microscopy (SEM), transmission electron microscopy(TEM), X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and CO chemisorption. It is shown that platinum particles agglomerate in a catalyst during operation, and its regeneration results in finer dispersity of the supported metal. Despite the common opinion that a platinum surface is modified by sulfur during the synthesis or regeneration of such catalysts, no evidence of this is found via XPS. Data showing that the surface nitrogen-containing graphite groups formed during the preparation of a catalyst are responsible for the modification of the absorption properties of platinum particles with respect to CO are obtained for the first time. The latter seems to be one of the factors that influence the catalytic properties of platinum in NO hydrogenation.

ACS Style

A. N. Bobrovskaya; P. A. Simonov; A. V. Bukhtiyarov; R. I. Kvon; N. A. Rudina; A. V. Romanenko; V. M. Khodorchenko. Synthesis of Hydroxylamine Sulfate via NO Hydrogenation over Pt/Graphite Catalysts. I: Physicochemical State of Platinum Particles and the Surface of the Support in the Catalysts. Catalysis in Industry 2018, 10, 279 -287.

AMA Style

A. N. Bobrovskaya, P. A. Simonov, A. V. Bukhtiyarov, R. I. Kvon, N. A. Rudina, A. V. Romanenko, V. M. Khodorchenko. Synthesis of Hydroxylamine Sulfate via NO Hydrogenation over Pt/Graphite Catalysts. I: Physicochemical State of Platinum Particles and the Surface of the Support in the Catalysts. Catalysis in Industry. 2018; 10 (4):279-287.

Chicago/Turabian Style

A. N. Bobrovskaya; P. A. Simonov; A. V. Bukhtiyarov; R. I. Kvon; N. A. Rudina; A. V. Romanenko; V. M. Khodorchenko. 2018. "Synthesis of Hydroxylamine Sulfate via NO Hydrogenation over Pt/Graphite Catalysts. I: Physicochemical State of Platinum Particles and the Surface of the Support in the Catalysts." Catalysis in Industry 10, no. 4: 279-287.