Effect of the Modification of Catalysts on the Catalytic Performance

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Catalytic Materials".

Deadline for manuscript submissions: closed (31 August 2022) | Viewed by 25713

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Guest Editor
Romanian Academy, “Ilie Murgulescu” Physical Chemistry Institute, Bucharest, Romania
Interests: catalytic and photocatalytic reaction; mono and bimetallic nanoparticles synthesis by alkaline polyol method; oxidation of C1-C4 aliphatic hydrocarbons on simple and doped oxides; oxidative coupling of methane on rare earth oxides; selective catalytic reduction of nitrates and nitrites in the liquid phase; catalytic oxidation of ammonia nitrogen with ozone in water; modified catalysts and their fractal properties
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Guest Editor
Romanian Academy, “Ilie Murgulescu” Physical Chemistry Institute, Bucharest, Romania
Interests: catalysis; kinetics of gas-solid interaction; catalytic synthesis; lower olefin (C3–C4) oxidation on multicomponent oxide catalysts; semiconductor properties of oxide catalysts; AC in situ electrical conductivity measurements on catalytic systems; dynamics of the lattice oxygen in oxide catalysts for selective oxidation catalysis; synthesis of well-defined mono/bimetallic nanoparticles supported; photocatalytic degradation of organic compounds in water
Special Issues, Collections and Topics in MDPI journals

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Guest Editor
Romanian Academy, “Ilie Murgulescu” Physical Chemistry Institute, Bucharest, Romania
Interests: surface science; fractal theory; adsorption mechanism; modelling gases adsorption and desorption from metal-supported catalysts; applying fractal theory to characterize surfaces; modelling adsorption on fractal surfaces; computing fractal dimension from micrographs (TEM, SEM, AFM, STM); growth surfaces and computing the time and spatial scaling exponents using the variable scaling method
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

A great challenge in the field of catalysis is the synthesis of catalysts with enhanced catalytic activity, selectivity, and durability. The structural and compositional complexity of the catalytic system requires a strong systematic approach to elucidate the nature of the catalyst’s active sites. A catalytic active site is a mono- or polyatomic entity with a specific electronic surface configuration, able to generate a catalytic act (adsorption, dissociation of reactant molecules, and desorption of reaction products).                                 

In-depth knowledge of the composition, structure, and nature of the active sites provides the possibility of tailoring the catalytic properties in order to improve catalytic performance (activity and selectivity). Such properties that can be targeted by synthesis are controlled porosity, sintering, resistance, large specific surface area, optimal acid–base properties, lattice vacancies, metal–support interaction, catalyst design, conductivity, etc.

Therefore, the change in catalyst properties leads to modified kinetic parameters (reaction rate, activation energy) and the reaction mechanism.

Improving catalytic performance by modifying catalysts should play an important role in the current global situation by reducing the negative impact on the environment and supporting the sustainable use of natural resources.

The purpose of this Issue is to present state-of-the-art strategies for modifying catalysts, aiming to provide an important contribution to the development of research in this area from both practical and theoretical perspectives.

We aim to gain a better understanding of catalytic systems, facilitating the establishment of the correlations between composition and physical-chemical properties and performance.

Original research papers and topical reviews are welcome in this Special Issue of Catalysts. Submit your paper and select the Journal “Catalysts” and the Special Issue “Effect of the Modification of Catalysts on the Catalytic Performance” via: MDPI submission system. Please contact the Guest Editor or the journal editor () for any queries. Our papers will be published on a rolling basis and we will be pleased to receive your submission once you have finished it.

Dr. Florica Papa
Dr. Anca Vasile
Dr. Gianina Dobrescu
Guest Editors

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

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Keywords

  • catalytic performance
  • catalyst
  • synergetic effect
  • modification of catalysts
  • selectivity
  • catalyst synthesis
  • reaction mechanism
  • catalytic activity

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Published Papers (11 papers)

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Editorial

Jump to: Research, Review

4 pages, 469 KiB  
Editorial
Effect of the Modification of Catalysts on the Catalytic Performance
by Florica Papa, Anca Vasile and Gianina Dobrescu
Catalysts 2022, 12(12), 1637; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12121637 - 14 Dec 2022
Cited by 1 | Viewed by 1436
Abstract
Changing the composition and structure of a catalyst to obtain a positive impact on its performance is challenging [...] Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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Research

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28 pages, 7813 KiB  
Article
Band-Gap Engineering of Layered Perovskites by Cu Spacer Insertion as Photocatalysts for Depollution Reaction
by Monica Raciulete, Crina Anastasescu, Florica Papa, Irina Atkinson, Corina Bradu, Catalin Negrila, Diana-Ioana Eftemie, Daniela C. Culita, Akane Miyazaki, Veronica Bratan, Jeanina Pandele-Cusu, Cornel Munteanu, Gianina Dobrescu, Alexandra Sandulescu and Ioan Balint
Catalysts 2022, 12(12), 1529; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12121529 - 27 Nov 2022
Cited by 4 | Viewed by 1950
Abstract
A multi-step ion-exchange methodology was developed for the fabrication of Cu(LaTa2O7)2 lamellar architectures capable of wastewater depollution. The (001) diffraction line of RbLaTa2O7 depended on the guest species hosted by the starting material. SEM and [...] Read more.
A multi-step ion-exchange methodology was developed for the fabrication of Cu(LaTa2O7)2 lamellar architectures capable of wastewater depollution. The (001) diffraction line of RbLaTa2O7 depended on the guest species hosted by the starting material. SEM and TEM images confirmed the well-preserved lamellar structure for all intercalated layered perovskites. The UV–Vis, XPS, and photocurrent spectroscopies proved that Cu intercalation induces a red-shift band gap compared to the perovskite host. Moreover, the UV–Vis spectroscopy elucidated the copper ions environment in the Cu-modified layered perovskites. H2-TPR results confirmed that Cu species located on the surface are reduced at a lower temperature while those from the interlayer occur at higher temperature ranges. The photocatalytic degradation of phenol under simulated solar irradiation was used as a model reaction to assess the performances of the studied catalysts. Increased photocatalytic activity was observed for Cu-modified layered perovskites compared to RbLaTa2O7 pristine. This behavior resulted from the efficient separation of photogenerated charge carriers and light absorption induced by copper spacer insertion. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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19 pages, 2684 KiB  
Article
Au/Ti Synergistically Modified Supports Based on SiO2 with Different Pore Geometries and Architectures
by Gabriela Petcu, Elena Maria Anghel, Elena Buixaderas, Irina Atkinson, Simona Somacescu, Adriana Baran, Daniela Cristina Culita, Bogdan Trica, Corina Bradu, Madalina Ciobanu and Viorica Parvulescu
Catalysts 2022, 12(10), 1129; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12101129 - 28 Sep 2022
Cited by 6 | Viewed by 1894
Abstract
New photocatalysts were obtained by immobilization of titanium and gold species on zeolite Y, hierarchical zeolite Y, MCM-48 and KIT-6 supports with microporous, hierarchical and mesoporous cubic structure. The obtained samples were characterized by X-ray diffraction (XRD), N2-physisorption, scanning and transmission [...] Read more.
New photocatalysts were obtained by immobilization of titanium and gold species on zeolite Y, hierarchical zeolite Y, MCM-48 and KIT-6 supports with microporous, hierarchical and mesoporous cubic structure. The obtained samples were characterized by X-ray diffraction (XRD), N2-physisorption, scanning and transmission electron microscopy (SEM/TEM), diffuse reflectance UV–Vis spectroscopy (DRUV-Vis), X-ray photoelectron spectroscopy (XPS), Raman and photoluminescence spectroscopy. The photocatalytic properties were evaluated in degradation of amoxicillin (AMX) from water, under UV (254 nm) and visible light (532 nm) irradiation. The higher degradation efficiency and best apparent rate constant were obtained under UV irradiation for Au-TiO2-KIT-6, while in the visible condition for the Au-TiO2-MCM-48 sample containing anatase, rutile and the greatest percent of Au metallic clusters were found (evidenced by XPS). Although significant values of amoxicillin degradation were obtained, total mineralization was not achieved. These results were explained by different reaction mechanisms, in which Au species act as e trap in UV and e generator in visible light. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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19 pages, 7170 KiB  
Article
Iron-Modified Titanate Nanorods for Oxidation of Aqueous Ammonia Using Combined Treatment with Ozone and Solar Light Irradiation
by Silviu Preda, Polona Umek, Maria Zaharescu, Crina Anastasescu, Simona Viorica Petrescu, Cătălina Gîfu, Diana-Ioana Eftemie, Razvan State, Florica Papa and Ioan Balint
Catalysts 2022, 12(6), 666; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12060666 - 17 Jun 2022
Cited by 4 | Viewed by 1596
Abstract
Sodium titanate nanorods were synthesized by a hydrothermal method and subsequently modified with an iron precursor. For comparison, Fe2O3 nanocubes were also obtained through a similar hydrothermal treatment. Pristine, Fe-modified nanorods and Fe2O3 nanocubes were suspended in [...] Read more.
Sodium titanate nanorods were synthesized by a hydrothermal method and subsequently modified with an iron precursor. For comparison, Fe2O3 nanocubes were also obtained through a similar hydrothermal treatment. Pristine, Fe-modified nanorods and Fe2O3 nanocubes were suspended in diluted ammonia solutions (20 ppm) and exposed to ozone and simulated light irradiation. Ammonia abatement, together with the resulting nitrogen-containing products (NO3), was monitored by ion chromatography measurements. The generation of reactive oxygen species (·OH and O2) in the investigated materials and their photoelectrochemical behaviour were also investigated. Morphological and structural characterizations (SEM, XRD, XRF, UV–Vis, H2-TPR, NH3-TPD, PL, PZC) of the studied catalysts were correlated with their activity for ammonia degradation with ozone- and photo-assisted oxidation. An increase in ammonia conversion and a decreasing amount of NO3 were achieved by combining the above-mentioned processes. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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17 pages, 11545 KiB  
Article
Highly Efficient and Sustainable ZnO/CuO/g-C3N4 Photocatalyst for Wastewater Treatment under Visible Light through Heterojunction Development
by Md. Abu Hanif, Jeasmin Akter, Young Soon Kim, Hong Gun Kim, Jae Ryang Hahn and Lee Ku Kwac
Catalysts 2022, 12(2), 151; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12020151 - 25 Jan 2022
Cited by 14 | Viewed by 3363
Abstract
Dye-containing pollutants are currently a threat to the environment, and it is highly challenging to eliminate these dyes photocatalytically under visible light. Herein, we designed and prepared a ZnO/CuO/g-C3N4 (ZCG) heterostructure nanocomposite by a co-crystallization procedure and applied it to [...] Read more.
Dye-containing pollutants are currently a threat to the environment, and it is highly challenging to eliminate these dyes photocatalytically under visible light. Herein, we designed and prepared a ZnO/CuO/g-C3N4 (ZCG) heterostructure nanocomposite by a co-crystallization procedure and applied it to eliminate pollutants from wastewater via a photocatalytic scheme. The structural and morphological features of the composite confirmed the formation of a ZCG nanocomposite. The photocatalytic capability of the ZCG photocatalyst was investigated via the decomposition of methylene blue dye. The outstanding activity level of 97.46% was reached within 50 min. In addition, the proficiency of the ZCG composite was 753%, 392%, 156%, and 130% higher than photolysis, g-C3N4, CuO, and ZnO, respectively. Furthermore, the photodeterioration activity on Congo red was also evaluated and found to be excellent. The enhanced catalytic achievement is attributed to the construction of heterojunctions among the constituent compounds. These properties boost the charge transfer and decrease the recombination rate. Moreover, the reusability of the ZCG product was explored and a negligible photoactivity decline was detected after six successful runs. The outcomes suggest the as-prepared nanocomposite can be applied to remove pollutants, which opens a new door to practical implementation. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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13 pages, 4732 KiB  
Article
Bimetallic PdCo Nanoparticles Loaded in Amine Modified Polyacrylonitrile Hollow Spheres as Efficient Catalysts for Formic Acid Dehydrogenation
by Yulin Li, Ping She, Rundong Ding, Da Li, Hongtan Cai, Xiufeng Hao and Mingjun Jia
Catalysts 2022, 12(1), 33; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12010033 - 29 Dec 2021
Cited by 4 | Viewed by 1858
Abstract
Polyacrylonitrile hollow nanospheres (HPAN), derived from the polymerization of acrylonitrile in the presence of polystyrene emulsion (as template), were modified by surface amination with ethylenediamine (EDA), and then used as support for loading Pd or PdCo nanoparticles (NPs). The resultant bimetallic catalyst (named [...] Read more.
Polyacrylonitrile hollow nanospheres (HPAN), derived from the polymerization of acrylonitrile in the presence of polystyrene emulsion (as template), were modified by surface amination with ethylenediamine (EDA), and then used as support for loading Pd or PdCo nanoparticles (NPs). The resultant bimetallic catalyst (named PdCo0.2/EDA-HPAN) can efficiently catalyze the additive-free dehydrogenation of formic acid with very high activity, selectivity and recyclability, showing turnover frequencies (TOF) of 4990 h−1 at 333 K and 915 h−1 at 303 K, respectively. The abundant surface amino groups and cyano group as well as the hollow structure of the support offer a suitable environment for achieving high dispersion of the Pd-based NPs on the surface of EDA-HPAN, thus generating ultra-small bimetallic NPs (bellow 1.0 nm) with high stability. The addition of a small portion of Co may adjust the electronic state of Pd species to a certain extent, which can further improve their capability for the dehydrogenation of formic acid. In addition, the surface amino groups may also play an important role in synergistically activating formic acid to generate formate, thus leading to efficient conversion of formic acid to hydrogen at mild conditions. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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15 pages, 3027 KiB  
Article
Promotion Effect of the Keggin Structure on the Sulfur and Water Resistance of Pt/CeTi Catalysts for CO Oxidation
by Tong Zhang, Wenge Qiu, Hongtai Zhu, Xinlei Ding, Rui Wu and Hong He
Catalysts 2022, 12(1), 4; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12010004 - 22 Dec 2021
Cited by 7 | Viewed by 2733
Abstract
Developing a catalyst with high SO2 and H2O resistance to achieve high-performance CO oxidation for specific industrial applications is highly desirable. Here, three catalysts were prepared using cerium titanium composite oxide (CeTi), molybdophosphate with Keggin structure-modified CeTi (Keg-CeTi), and molybdophosphate [...] Read more.
Developing a catalyst with high SO2 and H2O resistance to achieve high-performance CO oxidation for specific industrial applications is highly desirable. Here, three catalysts were prepared using cerium titanium composite oxide (CeTi), molybdophosphate with Keggin structure-modified CeTi (Keg-CeTi), and molybdophosphate without Keggin structure-modified CeTi (MoP-CeTi) as supports, and their sulfur and water resistance in CO oxidation were tested. The characterization of XRD, BET, SO2/H2O-DRIFTS, XPS, TEM, SEM, NH3/SO2-TPD, H2-TPR, and ICP techniques revealed that the high SO2 and H2O resistance of Pt/Keg-CeTi in CO oxidation was related to its stronger surface acidity, better reduction of surface cerium and molybdenum species, and lower SO2 adsorption and transformation compared to Pt/CeTi and Pt/MoP-CeTi. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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18 pages, 3491 KiB  
Article
Enhanced Catalytic Hydrogen Peroxide Production from Hydroxylamine Oxidation on Modified Activated Carbon Fibers: The Role of Surface Chemistry
by Wei Song, Ran Zhao, Lin Yu, Xiaowei Xie, Ming Sun and Yongfeng Li
Catalysts 2021, 11(12), 1515; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11121515 - 13 Dec 2021
Cited by 2 | Viewed by 2140
Abstract
Herein, direct production of hydrogen peroxide (H2O2) through hydroxylamine (NH2OH) oxidation by molecular oxygen was greatly enhanced over modified activated carbon fiber (ACF) catalysts. We revealed that the higher content of pyrrolic/pyridone nitrogen (N5) and carboxyl-anhydride oxygen [...] Read more.
Herein, direct production of hydrogen peroxide (H2O2) through hydroxylamine (NH2OH) oxidation by molecular oxygen was greatly enhanced over modified activated carbon fiber (ACF) catalysts. We revealed that the higher content of pyrrolic/pyridone nitrogen (N5) and carboxyl-anhydride oxygen could effectively promote the higher selectivity and yield of H2O2. By changing the volume ratio of the concentrated H2SO4 and HNO3, the content of N5 and surface oxygen containing groups on ACF were selectively tuned. The ACF catalyst with the highest N5 content and abundant carboxyl-anhydride oxygen containing groups was demonstrated to have the highest activity toward catalytic H2O2 production, enabling the selectivity of H2O2 over 99.3% and the concentration of H2O2 reaching 123 mmol/L. The crucial effects of nitrogen species were expounded by the correlation of the selectivity of H2O2 with the content of N5 from X-ray photoelectron spectroscopy (XPS). The possible reaction pathway over ACF catalysts promoted by N5 was also shown. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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14 pages, 32850 KiB  
Article
Improvement of Alkali Metal Resistance for NH3-SCR Catalyst Cu/SSZ-13: Tune the Crystal Size
by Zexiang Chen, Meiqing Shen, Chen Wang, Jianqiang Wang, Jun Wang and Gurong Shen
Catalysts 2021, 11(8), 979; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11080979 - 16 Aug 2021
Cited by 7 | Viewed by 2621
Abstract
To improve the alkali metal resistance of commercial catalyst Cu/SSZ-13 for ammonia selective catalytic reduction (NH3-SCR) reaction, a simple method to synthesize Cu/SSZ-13 with a core–shell like structure was developed. Compared with smaller-sized counterparts, Cu/SSZ-13 with a crystal size of 2.3 [...] Read more.
To improve the alkali metal resistance of commercial catalyst Cu/SSZ-13 for ammonia selective catalytic reduction (NH3-SCR) reaction, a simple method to synthesize Cu/SSZ-13 with a core–shell like structure was developed. Compared with smaller-sized counterparts, Cu/SSZ-13 with a crystal size of 2.3 μm exhibited excellent resistance to Na poisoning. To reveal the influence of the crystal size on Cu/SSZ-13, physical structure characterization (XRD, BET, SEM, NMR) and chemical acidic distribution (H2-TPR, UV-Vis, Diethylamine-TPD, pyridine-DRIFTs, EDS) were investigated. It was found that the larger the crystal size of the molecular sieve, the more Cu is distributed in the crystal core, and the less likely it was to be replaced by Na to generate CuO. Therefore, a 2.3 μm sized Cu/SSZ-13 well-controlled the reactivity of the side reaction NH3 oxidation and the generation of N2O. The result was helpful to guide the extension of the service life of Cu/SSZ-13. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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Review

Jump to: Editorial, Research

27 pages, 4922 KiB  
Review
Insights into the Redox and Structural Properties of CoOx and MnOx: Fundamental Factors Affecting the Catalytic Performance in the Oxidation Process of VOCs
by Veronica Bratan, Anca Vasile, Paul Chesler and Cristian Hornoiu
Catalysts 2022, 12(10), 1134; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12101134 - 28 Sep 2022
Cited by 16 | Viewed by 1873
Abstract
Volatile organic compound (VOC) abatement has become imperative nowadays due to their harmful effect on human health and on the environment. Catalytic oxidation has appeared as an innovative and promising approach, as the pollutants can be totally oxidized at moderate operating temperatures under [...] Read more.
Volatile organic compound (VOC) abatement has become imperative nowadays due to their harmful effect on human health and on the environment. Catalytic oxidation has appeared as an innovative and promising approach, as the pollutants can be totally oxidized at moderate operating temperatures under 500 °C. The most active single oxides in the total oxidation of hydrocarbons have been shown to be manganese and cobalt oxides. The main factors affecting the catalytic performances of several metal-oxide catalysts, including CoOx and MnOx, in relation to the total oxidation of hydrocarbons have been reviewed. The influence of these factors is directly related to the Mars–van Krevelen mechanism, which is known to be applied in the case of the oxidation of VOCs in general and hydrocarbons in particular, using transitional metal oxides as catalysts. The catalytic behaviors of the studied oxides could be closely related to their redox properties, their nonstoichiometric, defective structure, and their lattice oxygen mobility. The control of the structural and textural properties of the studied metal oxides, such as specific surface area and specific morphology, plays an important role in catalytic applications. A fundamental challenge in the development of efficient and low-cost catalysts is to choose the criteria for selecting them. Therefore, this research could be useful for tailoring advanced and high-performance catalysts for the total oxidation of VOCs. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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16 pages, 2619 KiB  
Review
Modified Catalysts and Their Fractal Properties
by Gianina Dobrescu, Florica Papa, Razvan State, Monica Raciulete, Daniela Berger, Ioan Balint and Niculae I. Ionescu
Catalysts 2021, 11(12), 1518; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11121518 - 14 Dec 2021
Cited by 6 | Viewed by 2148
Abstract
Obtaining high-area catalysts is in demand in heterogeneous catalysis as it influences the ratio between the number of active surface sites and the number of total surface sites of the catalysts. From this point of view, fractal theory seems to be a suitable [...] Read more.
Obtaining high-area catalysts is in demand in heterogeneous catalysis as it influences the ratio between the number of active surface sites and the number of total surface sites of the catalysts. From this point of view, fractal theory seems to be a suitable instrument to characterize catalysts’ surfaces. Moreover, catalysts with higher fractal dimensions will perform better in catalytic reactions. Modifying catalysts to increase their fractal dimension is a constant concern in heterogeneous catalysis. In this paper, scientific results related to oxide catalysts, such as lanthanum cobaltites and ferrites with perovskite structure, and nanoparticle catalysts (such as Pt, Rh, Pt-Cu, etc.) will be reviewed, emphasizing their fractal properties and the influence of their modification on both fractal and catalytic properties. Some of the methods used to compute the fractal dimension of the catalysts (micrograph fractal analysis and the adsorption isotherm method) and the computed fractal dimensions will be presented and discussed. Full article
(This article belongs to the Special Issue Effect of the Modification of Catalysts on the Catalytic Performance)
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