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Special Issue "Advances in Heterogeneous Catalysts"

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: 31 March 2024 | Viewed by 2501

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Dr. Yurii V. Larichev

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Guest Editor

1. Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2. Department of Physics, Novosibirsk State University, 1 Pirogov Street, Novosibirsk 630090, Russia
Interests: supported catalysts; porous materials; nanocomposites; sols; nanoparticles; crude oils; methods characterization

Special Issue Information

Dear Colleagues,

Heterogeneous catalysts are one of the oldest and most important branches in the science of catalysis. Large-tonnage processes such as petroleum industry, fertilizers and polymers production and other chemicals make great use of heterogeneous catalysts. Therefore, industrially significant reactions constantly need new generations of heterogeneous catalysts with ever-higher performance compared to their predecessors. Ensuring the progress of their development often requires knowledge from different areas which, at first sight, are loosely related to each other—for example, the stability of colloidal metal nanoparticles in solution and the formation of ordered porous oxide materials with a high specific surface area; segregation processes in various alloys and partial oxidation reactions of hydrocarbons; and the formation of defects in the structure of solids and the adsorption processes on the different types of metal faces. Using different relationships from various areas of knowledge, researchers are able to both improve existing catalytic systems and create completely new catalysts for new reactions. In addition, the development of physical methods for nanomaterials investigation makes it possible to better understand the fine details of various structural and electronic interactions within them, which can be very important for tuning their catalytic properties. On this basis, this Special Issue titled “Advances in Heterogeneous Catalysts” is devoted to the preparation of heterogeneous catalysts, their study using physical methods, as well as the search for various relationships that affect the structure of materials and their catalytic properties. Non-standard and unusual systems are welcome, as well as methods and approaches for interpreting data.

Dr. Yurii V. Larichev
Guest Editor

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Keywords

metal catalysts
oxide catalysts
catalytic reactions
functional materials
nanoparticles
defect structure
methods characterization
sol–gel
in situ

Published Papers (4 papers)

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Research

14 pages, 6152 KiB

Open AccessArticle

XPS and HR TEM Elucidation of the Diversity of Titania-Supported Single-Site Ir Catalyst Performance in Spin-Selective Propene Hydrogenation

and

Valerii I. Bukhtiyarov

Int. J. Mol. Sci. 2023, 24(21), 15643; https://doi.org/10.3390/ijms242115643 - 27 Oct 2023

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Abstract

Immobilized [Ir(COD)Cl]₂-Linker/TiO₂ catalysts with linkers containing Py, P(Ph)₂ and N(CH₃)₂ functional groups were prepared. The catalysts were tested via propene hydrogenation with parahydrogen in a temperature range from 40 °C to 120 °C which was monitored via NMR. The catalytic behavior of [Ir(COD)Cl]₂-Linker/TiO₂ is explained on the basis of quantitative and qualitative XPS data analysis performed for the catalysts before and after the reaction at 120 °C. It is shown that the temperature dependence of propene conversion and the enhancement of the NMR signal are explained via a combination of the stabilities of both the linker and immobilized [Ir(COD)Cl]₂ complex. It is demonstrated that the N(CH₃)₂-linker is the most stable at the surface of TiO₂ under used reaction conditions. As a result, only this sample shows a rise in the enhancement of the NMR signal in the 100–120 °C temperature range. Full article

(This article belongs to the Special Issue Advances in Heterogeneous Catalysts)

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9 pages, 1672 KiB

Open AccessArticle

Using the Colloidal Method to Prepare Au Catalysts for the Alkylation of Aniline by Benzyl Alcohol

and

Int. J. Mol. Sci. 2023, 24(19), 14779; https://doi.org/10.3390/ijms241914779 - 30 Sep 2023

Viewed by 396

Abstract

Using the colloidal method, attempts were made to deposit Au NPs on seven different material supports (TiO₂, α and γ-Al₂O₃, HFeO₂, CeO₂, C, and SiO₂). The deposition between 0.8 and 1 wt% of Au NPs can be generally achieved, apart for SiO₂ (no deposition) and α-alumina (0.3 wt%). The resultant sizes of the Au NPs were dependent on the nature as well as the surface area of the support. The catalytic activity and selectivity of the supported Au catalysts were then compared in the alkylation of aniline by benzyl alcohol. Correlations were made between the nature of the support, the size of the Au NP, and the H-binding energy. A minimum H-binding energy of 1100 μV K⁻¹ was found to be necessary for high selectivity for the secondary amine. Comparisons of the TEM images of the pre- and post-reaction catalysts also revealed the extent of Au NP agglomeration under the reaction conditions. Full article

(This article belongs to the Special Issue Advances in Heterogeneous Catalysts)

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17 pages, 9060 KiB

Open AccessArticle

Synthesis of α-Diimine Complex Enabling Rapidly Covalent Attachment to Silica Supports and Application of Homo-/Heterogeneous Catalysts in Ethylene Polymerization

and

Int. J. Mol. Sci. 2023, 24(17), 13645; https://doi.org/10.3390/ijms241713645 - 04 Sep 2023

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Abstract

For covalent attachment-supported α-diimine catalysts, on the basis of ensuring the thermal stability and activity of the catalysts, the important problem is that the active group on the catalyst can quickly react with the support, anchoring it firmly on the support, shortening the loading time, reducing the negative impact of the support on the active centers, and further improving the polymer morphology, which makes them suitable for use in industrial polymerization temperatures. Herein, we synthesized a α-diimine nickel(II) catalyst bearing four hydroxyl substituents. The hydroxyl substituents enable the catalyst to be immobilized firmly on silica support by covalent linkage in 5–10 min. Compared with the toluene solvent system, the homogeneous catalysts show high activity and thermal stability in hexane solvent at the same conditions. Compared with homogeneous catalysts, heterogeneous catalysis leads to improvements in catalyst lifetime, polymer morphology control, catalytic activity, and the molecular weight of polyethylene (up to 679 kg/mol). The silica-supported catalysts resulted in higher melting temperatures as well as lower branching densities in polyethylenes. Even at 70 °C, the polyethylene prepared by S-CatA-2 still exhibits dispersed particle morphology, and there is no phenomenon of reactor fouling, which is suitable for industrial polymerization processes. Full article

(This article belongs to the Special Issue Advances in Heterogeneous Catalysts)

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27 pages, 13491 KiB

Open AccessArticle

Dry Reforming of Methane over 5%Ni/Ce_1-xTi_xO₂ Catalysts Obtained via Synthesis in Supercritical Isopropanol

and

Int. J. Mol. Sci. 2023, 24(11), 9680; https://doi.org/10.3390/ijms24119680 - 02 Jun 2023

Viewed by 672

Abstract

A series of 5%Ni/Ce_1-xTi_xO₂ catalysts was prepared with nickel impregnation of mixed Ce–Ti oxides obtained via synthesis in supercritical isopropanol. All oxides have a cubic fluorite phase structure. Ti is incorporated into the fluorite structure. Small amounts of impurities of TiO₂ or mixed Ce–Ti oxides appear with Ti introduction. Supported Ni is presented as the NiO or NiTiO₃ perovskite phase. Ti introduction increases total samples reducibility and results in stronger interaction of supported Ni with the oxide support. The fraction of rapidly replaced oxygen and the average tracer diffusion coefficient also increase. The number of metallic nickel sites decreased with increasing Ti content. All catalysts except Ni-CeTi0.45 demonstrate close activity in tests of dry reforming of methane. The lower activity of Ni-CeTi0.45 can be connected to Ni decoration with species of the oxide support. The incorporation of Ti prevents detachment of Ni particles from the surface and their sintering during dry reforming of methane. Full article

(This article belongs to the Special Issue Advances in Heterogeneous Catalysts)

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