Feature Papers on "Hybrid and Composite Crystalline Materials" 2023–2024

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Hybrid and Composite Crystalline Materials".

Deadline for manuscript submissions: closed (31 December 2024) | Viewed by 17477

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1. N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, 119991 Moscow, Russia
2. Chemistry Department, Moscow State University, Leninskie Gory 1, Bldg. 3, 119992 Moscow, Russia
3. Institute of Ecology and Engineering, National Science and Technology University MISiS, Leninsky Prospect 4, 119071 Moscow, Russia
Interests: catalysis; nanomaterials; renewables; green chemistry
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Dear Colleague,

This Special Issue entitled “Feature Papers on ‘Hybrid and Composite Crystalline Materials’ 2023–2024” covers topics related to the chemistry and structure of diverse hybrid and composite crystalline materials, the design and engineering of these materials, and their applications. Hybrid and composite crystalline materials include, inter alia, coordination polymers; metal–organic frameworks; covalent organic frameworks; hierarchical zeolites and zeolite-like materials; organic–inorganic hybrids; composites based on graphene, carbon nitride, or layered sulfides; and composites based on metal, metal oxide, metal chalcogenide, or metal pnictide nanoparticles stabilized with organic ligands or polymers (such nanoparticles can be either unsupported or supported onto appropriate matrices). Other topics related to the design and application of hybrid and composite crystalline materials are welcome. For example, coordination chemistry, the influence of intermolecular interactions on the geometry and arrangement of species constituting hybrid and composite crystalline materials, and cooperative and synergistic effects will all be considered.

For this Special Issue, we aim to publish high-quality articles within the field of hybrid and composite crystalline materials. A discount on the article processing charge will be available for published papers. Please feel free to contact Jocelyn Bai (jocelyn.bai@mdpi.com) if you would like to contribute to this Special Issue.

Prof. Dr. Leonid Kustov
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Keywords

  • hybrid materials
  • composite materials
  • intermolecular interactions
  • molecular crystals
  • coordination polymers
  • metal–organic frameworks
  • covalent organic frameworks
  • hierarchical zeolites
  • zeolite-like materials
  • organic–inorganic hybrids
  • graphene
  • carbon nitride
  • layered sulfides
  • metal nanoparticles
  • metal oxide nanoparticles
  • metal chalcogenide nanoparticles
  • metal pnictide nanoparticles

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Published Papers (11 papers)

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Research

16 pages, 2537 KiB  
Article
Performance of Pico-Second Laser-Designed Silicon/Gold Composite Nanoparticles Affected by Precision of Focus Position
by Yury V. Ryabchikov, Antonin Kana and Inam Mirza
Crystals 2025, 15(2), 132; https://doi.org/10.3390/cryst15020132 - 25 Jan 2025
Viewed by 620
Abstract
Pulsed laser ablation in liquids is one of the most versatile and widespread techniques for the easy synthesis of different types of nanoparticles with controllable properties. A huge amount of energy compressed into one pulse that is directed onto a solid target leads [...] Read more.
Pulsed laser ablation in liquids is one of the most versatile and widespread techniques for the easy synthesis of different types of nanoparticles with controllable properties. A huge amount of energy compressed into one pulse that is directed onto a solid target leads to the ejection of materials into surrounding liquid. However, the precision of the focus of laser irradiation can play a crucial role in the synthesis of nanomaterials and, hence, significantly affect their physico-chemical properties. In this paper, we investigated the influence of the focus position of the laser spot on the optical properties of single- and double-element composite silicon/gold nanoparticles, as well as on their structure and chemical composition. Deepening of the focus to 0.5 mm inside the bulk material led to better chemical stability of the colloidal solutions and increased the particle and mass concentrations of the generated nanoparticles. This larger amount of materials led to a stronger absorbance, and resulted in slightly better photoluminescence excitation efficiencies for all nanostructures. Silicon-based nanoparticles had a remarkable photoluminescence peak at ~430 nm upon xenon lamp excitation, which was the most pronounced for pure silicon nanoparticles synthesized at the F+0.5 focus position. This position also led to the best laser-induced heating (~0.85 °C/min) of the colloidal solutions. All nanocomposites revealed amorphous silicon structures with some Si(111) and Au(111), suggesting the formation of gold silicide with different stoichiometries. The observed findings can help in choosing appropriate experimental conditions to achieve the best performance of laser-synthesized colloidal solutions of composite silicon/gold nanostructures. Full article
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14 pages, 9251 KiB  
Article
Synergistic Integration of Mesocarbon Microbeads, Graphitic Nanofibers, and Mesoporous Carbon for Advanced Supercapacitor Electrodes
by Palanisamy Rajkumar, Vediyappan Thirumal, Kisoo Yoo and Jinho Kim
Crystals 2025, 15(1), 64; https://doi.org/10.3390/cryst15010064 - 10 Jan 2025
Viewed by 551
Abstract
In this study, a novel multiscale carbon architecture was developed by integrating mesocarbon microbeads (MCMBs), graphitic nanofibers (GNFs), and mesoporous carbon, aimed at enhancing the performance of symmetric supercapacitors. The unique combination of spherical MCMB particles, conductive GNF nanofibers, and mesoporous carbon sheets [...] Read more.
In this study, a novel multiscale carbon architecture was developed by integrating mesocarbon microbeads (MCMBs), graphitic nanofibers (GNFs), and mesoporous carbon, aimed at enhancing the performance of symmetric supercapacitors. The unique combination of spherical MCMB particles, conductive GNF nanofibers, and mesoporous carbon sheets resulted in a highly effective electrode material, offering improved conductivity, increased active sites for charge storage, and enhanced structural stability. The fabricated MCMB/GNF/MC architecture demonstrated a remarkable specific capacitance of 393 F g−1 at 1 A g−1 in a three-electrode system, significantly surpassing the performance of individual MCMBs and MCMB/GNF electrodes. Furthermore, the architecture was incorporated into a symmetric supercapacitor (SSC) device, where it achieved a capacitance of 86 F g−1 at 1 A g−1. The device exhibited excellent cycling stability, retaining 92% of its initial capacitance after 10,000 charge–discharge cycles, with an outstanding coulombic efficiency of 99%. At optimal operating conditions, the SSC device delivered an energy density of 11 Wh kg−1 at a power density of 500 W kg−1, making it a promising candidate for high-performance energy-storage applications. This multiscale carbon architecture represents a significant advancement in the design of electrode materials for symmetric supercapacitors, offering a balance of high energy and power density, long-term stability, and excellent scalability for practical applications. This work not only contributes to the development of high-performance electrode materials but also paves the way for scalable, long-lasting supercapacitors for future energy-storage technologies. Full article
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22 pages, 6414 KiB  
Article
Experimental Investigation and Machine Learning Modeling of Tribological Characteristics of AZ31/B4C/GNPs Hybrid Composites
by Dhanunjay Kumar Ammisetti, Bharat Kumar Chigilipalli, Baburao Gaddala, Ravi Kumar Kottala, Radhamanohar Aepuru, T. Srinivasa Rao, Seepana Praveenkumar and Ravinder Kumar
Crystals 2024, 14(12), 1007; https://doi.org/10.3390/cryst14121007 - 21 Nov 2024
Viewed by 964
Abstract
In this study, the AZ31 hybrid composites reinforced with boron carbide (B4C) and graphene nano-platelets (GNPs) are prepared by the stir casting method. The main aim of the study is to study the effect of various wear parameters (reinforcement percentage (R), [...] Read more.
In this study, the AZ31 hybrid composites reinforced with boron carbide (B4C) and graphene nano-platelets (GNPs) are prepared by the stir casting method. The main aim of the study is to study the effect of various wear parameters (reinforcement percentage (R), applied load (L), sliding distance (D), and velocity (V)) on the wear characteristics (wear rate (WR)) of the AZ91/B4C/GNP composites. Experiments are designed using the Taguchi technique, and it was determined that load (L) is the most significant parameter affecting WR, followed by D, R, and V. The wear mechanisms under conditions of maximum and minimum wear rates are examined using SEM analysis of the worn-out surfaces of the specimens. From the result analysis on the WR, the ideal conditions for achieving the lowest WR are R = 4 wt.%, L = 15 N, V = 3 m/s, and D = 500 m. Machine learning (ML) models, including linear regression (LR), polynomial regression (PR), random forest (RF), and Gaussian process regression (GPR), are implemented to develop a reliable prediction model that forecasts output responses in accordance with input variables. A total of 90% of the experimental data points were used to train and 10% to evaluate the models. The PR model exceeded the accuracy of other models in predicting WR, with R2 = 0.953, MSE = 0.011, RMSE = 0.103, and COF with R2 = 0.937, MSE = 0.013, and RMSE = 0.114, respectively. Full article
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12 pages, 2952 KiB  
Article
3D Hierarchical Composites of Hydrotalcite-Coated Carbon Microspheres as Catalysts in Baeyer–Villiger Oxidation Reactions
by Marta Estrada-Ruiz, Daniel Cosano, Dolores Esquivel, Francisco J. Romero-Salguero and José Rafael Ruiz
Crystals 2024, 14(10), 878; https://doi.org/10.3390/cryst14100878 - 5 Oct 2024
Cited by 1 | Viewed by 1126
Abstract
The use of heterogeneous catalysts is fundamental in the search for sustainable chemical processes. Research on hierarchical materials is a growing field aimed at optimizing the synthesis of catalysts. In this work, layered materials with metals of different cationic ratios and three-dimensional hierarchical [...] Read more.
The use of heterogeneous catalysts is fundamental in the search for sustainable chemical processes. Research on hierarchical materials is a growing field aimed at optimizing the synthesis of catalysts. In this work, layered materials with metals of different cationic ratios and three-dimensional hierarchical structures have been synthesized in a simple and easy way using carbon spheres as support. All materials were characterized with various techniques such as XRF, elemental analysis XRD, FT-IR, SEM, and TEM to study their composition and structure. Finally, these materials were used in the Baeyer–Villiger reaction, which was carried out under optimized conditions. The results showed that the metal ratio was an important factor in the coating process, affecting the catalytic capacity of the materials. Full article
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12 pages, 1877 KiB  
Article
Characterization of Chromium Cations in CrAPO-5 Metal Aluminophosphate
by Sergei A. Zubkov, Elena D. Finashina, Valery N. Zakharov and Leonid Kustov
Crystals 2024, 14(9), 758; https://doi.org/10.3390/cryst14090758 - 26 Aug 2024
Viewed by 680
Abstract
Chromium-substituted aluminophosphate (CrAPO-5) with the AFI crystal structure was prepared for the first time by using microwave conditions at the stage of gel formation and crystallization. This approach allowed the reduction of the time required for the synthesis of CrAPO-5 from 60–70 h [...] Read more.
Chromium-substituted aluminophosphate (CrAPO-5) with the AFI crystal structure was prepared for the first time by using microwave conditions at the stage of gel formation and crystallization. This approach allowed the reduction of the time required for the synthesis of CrAPO-5 from 60–70 h to 6 h. CrAPO-5 metal aluminophosphate prepared by microwave-assisted synthesis is studied by UV-visible and IR spectroscopy and X-ray photoelectron spectroscopy. The material is characterized by the presence of Cr3+ and Cr2+ ions in the framework with predominating Cr3+ ions introduced via isomorphous substitution, as well as some minor amounts of extra-framework Cr3+ species, which are present presumably in the state of α-Cr2O3. The latter species can be partially reduced to Cr2+ species in the presence of CO or H2. XPS study of CrAPO-5 revealed the presence of Cr3+ ions in the framework. A TPR experiment showed that the reduction of chromium starts at about 450–500 °C. Full article
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12 pages, 3922 KiB  
Article
A New Type of Acidic OH-Groups in the LTL Zeolite
by Alessandro Contini, Martin Jendrlin and Vladimir Zholobenko
Crystals 2024, 14(8), 745; https://doi.org/10.3390/cryst14080745 - 21 Aug 2024
Viewed by 1426
Abstract
Acidic properties of ion-exchanged LTL zeolites have been studied using FTIR spectroscopy, complemented by X-ray powder diffraction, SEM-EDX, XRF and N2 physisorption. Infrared spectra of the ion-exchanged zeolites show the presence of two intense bands of the bridging OH-groups: a narrow band [...] Read more.
Acidic properties of ion-exchanged LTL zeolites have been studied using FTIR spectroscopy, complemented by X-ray powder diffraction, SEM-EDX, XRF and N2 physisorption. Infrared spectra of the ion-exchanged zeolites show the presence of two intense bands of the bridging OH-groups: a narrow band at ~3640 cm−1 that is attributed to Si(OH)Al groups freely vibrating in 12 MR and a broad, intense band at ~3250 cm−1 that is assigned to bridging OH groups forming hydrogen bond with neighbouring oxygen atoms, e.g., in six-membered rings. The former can be selectively removed by caesium or rubidium cations with up to 3 Cs+ or Rb+ per unit cell readily ion-exchanged into the LTL zeolite, replacing an equivalent number of acidic OH-groups or K+ cations within the structure. The cation migration of the larger cation, evaluated by the Rietveld refinement method, occurs mostly via the main 12 MR channels. By contrast, less than 1 Li+ or Na+ cation per unit cell can be introduced under similar conditions. Accordingly, the concentration of Si(OH)Al groups in back-exchanged NH4-K-LTL with smaller cations (Li+, Na+) does not differ considerably from the concentration of Brønsted acid sites in the original NH4-K-LTL. Lower concentrations of acid sites have been detected in the samples back-exchanged with Cs+, Rb+ and K+. In addition, the acidic properties of NH4-LTL samples have been compared with a structurally related NH4-MAZ zeolite. Full article
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13 pages, 4519 KiB  
Article
Mechanical, Electrical, and Glass Transition Behavior of Copper–PMMA Composites
by Victor H. Poblete and Mariela P. Alvarez
Crystals 2023, 13(3), 368; https://doi.org/10.3390/cryst13030368 - 21 Feb 2023
Cited by 3 | Viewed by 2031
Abstract
The mechanical, electrical, and glass transition behaviors (Tg) of polymethylmethacrylate (PMMA)–metal systems have been studied. Considering both the particle size and the metal filler concentration, the electrical conductivity showed a clear dependence on the sample thickness to reach percolation. An increase of up [...] Read more.
The mechanical, electrical, and glass transition behaviors (Tg) of polymethylmethacrylate (PMMA)–metal systems have been studied. Considering both the particle size and the metal filler concentration, the electrical conductivity showed a clear dependence on the sample thickness to reach percolation. An increase of up to 400% of strain-to-failure for the 2% v/v of nanometric filler composites in the mechanical test was observed. Tg analysis showed a decrease in the glass transition temperature when the increase of nanometric metallic filler reached the limit of 2% v/v. Over this concentration, the Tg values showed a tendency to reach the original value of the polymeric matrix without conductive filler. For the 20% v/v micrometric filler composites, the strain-to-failure increased up to 58%, but in the Tg analysis of this composite, no relevant changes were observed when the micrometric metallic filler was increased. Full article
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13 pages, 4071 KiB  
Article
Ion-Beam Synthesis of Structure-Oriented Iron Nanoparticles in Single-Crystalline Rutile TiO2
by Iskander R. Vakhitov, Nikolay M. Lyadov, Vladimir I. Vdovin, Anton K. Gutakovskii, Vladimir I. Nuzhdin, Lenar R. Tagirov and Rustam I. Khaibullin
Crystals 2023, 13(2), 355; https://doi.org/10.3390/cryst13020355 - 18 Feb 2023
Viewed by 1946
Abstract
Magnetic nanoparticles embedded into semiconductors have current perspectives for use in semiconducting spintronics. In this work, 40 keV Fe+ ions were implanted in high fluences of (0.5 ÷ 1.5) × 1017 ion/cm2 into an oxide semiconductor and single-crystalline TiO2 [...] Read more.
Magnetic nanoparticles embedded into semiconductors have current perspectives for use in semiconducting spintronics. In this work, 40 keV Fe+ ions were implanted in high fluences of (0.5 ÷ 1.5) × 1017 ion/cm2 into an oxide semiconductor and single-crystalline TiO2 plates of rutile structure with (100) or (001) face orientations. Microstructure, elemental-phase composition, and magnetic properties of the Fe-ion-implanted TiO2 were studied by scanning and transmission electron microscopies (SEM and TEM), X-ray photoelectron (XPS) and Rutherford backscattering (RBS) spectroscopies, as well as vibrating-sample magnetometry (VSM). The high-fluence ion implantation results in the formation of magnetic nanoparticles of metallic iron beneath the irradiated surface of rutile. The induced ferromagnetism and observed two- or four-fold magnetic anisotropy are associated with the endotaxial growth of Fe nanoparticles oriented along the crystallographic axes of TiO2. Full article
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12 pages, 3362 KiB  
Article
The Role of Intermediate Phases in the Crystallization of Aluminophosphate Sieves on Examples of AlPO-11 and AlPO-41
by Marat R. Agliullin, Aidar V. Fayzullin, Zulfiya R. Fayzullina and Boris I. Kutepov
Crystals 2023, 13(2), 227; https://doi.org/10.3390/cryst13020227 - 27 Jan 2023
Cited by 4 | Viewed by 2056
Abstract
The formation of intermediate phases during aging of the reaction gel composition 1.0Al2O3•1.0P2O5•1.5DPA•40H2O and its subsequent crystallization into molecular sieves AlPO-11 and AlPO-41 was studied in this work. The initial gels and crystallization [...] Read more.
The formation of intermediate phases during aging of the reaction gel composition 1.0Al2O3•1.0P2O5•1.5DPA•40H2O and its subsequent crystallization into molecular sieves AlPO-11 and AlPO-41 was studied in this work. The initial gels and crystallization products were characterized by XRD; MAS NMR 27Al and 31P; scanning electron microscopy (SEM); transmission electron microscopy (TEM); and N2-physical adsorption. It has been found that the nature of the aluminum source used to prepare the gel has a significant effect on the properties of the resulting intermediate phases. It is shown that by changing the chemical and phase composition of the intermediate aluminophosphate, it is possible to control the morphology and characteristics of the secondary porous structure of the AlPO-11 molecular sieve. The formation of the intermediate phases with a layered structure opens the possibility to synthesize high-phase purity AlPO-41 at the di-n-propylamine/Al2O3 ratio = 1.5. The formation mechanisms of AlPO-11 and AlPO-41 are proposed depending on the phase composition of the intermediate phases. Full article
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15 pages, 5539 KiB  
Article
Phosphorus Recovery from Municipal Wastewater: Brucite from MgO Hydrothermal Treatment as Magnesium Source
by Panagiota D. Natsi, Konstantinos-Anastassios Goudas and Petros G. Koutsoukos
Crystals 2023, 13(2), 208; https://doi.org/10.3390/cryst13020208 - 23 Jan 2023
Cited by 6 | Viewed by 2951
Abstract
Crystallization of struvite (MgNH4PO4·6H2O, MAPH) for both N and P recovery from municipal wastewater is an attractive alternative. The low magnesium concentration in municipal wastewater calls for low-cost magnesium sources. In the present work, the precipitation of [...] Read more.
Crystallization of struvite (MgNH4PO4·6H2O, MAPH) for both N and P recovery from municipal wastewater is an attractive alternative. The low magnesium concentration in municipal wastewater calls for low-cost magnesium sources. In the present work, the precipitation of struvite from supersaturated solutions was investigated. The supersaturated solutions were prepared by the addition of either slurry of Mg(OH)2 (brucite) obtained from the hydrothermal treatment of magnesium oxide (MgO) or using the aqueous solution equilibrated with brucite after separation from the solid. In both cases, in the supersaturated solutions prepared by the addition of ammonium dihydrogen phosphate, the Mg:NH4:P ratio was 1:1:1, pH 7.0–11.0. The apparent order for the precipitation suggested that the dominant mechanism was surface diffusion according to the polynuclear model. The apparent rate constant for struvite precipitation was two orders of magnitude smaller for the slurry prepared supersaturated solution in comparison with the respective prepared from the brucite-equilibrated solution. Simulated wastewater (SWW), was supersaturated with respect to struvite, by inoculation with brucite. The apparent rate constant was two orders of magnitude higher than that corresponding to the supersaturated solutions prepared by the addition of solution equilibrated with brucite. The P recovery from SWW reached 70%. Full article
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18 pages, 7663 KiB  
Article
Embracing [XY3]m– and [XY4]m– Anions in Salts of [M(bpy)3]q+
by Edwin C. Constable and Catherine E. Housecroft
Crystals 2023, 13(1), 97; https://doi.org/10.3390/cryst13010097 - 5 Jan 2023
Cited by 2 | Viewed by 2053
Abstract
[M(bpy)3]q+ cations (bpy = 2,2′-bipyridine) are archetypical coordination entities containing chelating bidentate N,N′-donor ligands. Each propeller-shaped cation is chiral, existing as a Δ or Λ enantiomer. The supramolecular chemistry of [M(bpy)3]q+ cations [...] Read more.
[M(bpy)3]q+ cations (bpy = 2,2′-bipyridine) are archetypical coordination entities containing chelating bidentate N,N′-donor ligands. Each propeller-shaped cation is chiral, existing as a Δ or Λ enantiomer. The supramolecular chemistry of [M(bpy)3]q+ cations in the crystal is dominated by cation-anion interactions and, to a lesser extent, weaker non-covalent interactions. Analysis of the data for [M(bpy)3]q+ salts in the Cambridge Structural Database (CSD) reveals a ubiquitous motif in which homochiral sheets of cations generate cavities for the accommodation of anions. A series of related and common motifs in the solid-state structures of [M(bpy)3]q+ salts has been identified. One of the commonest motifs comprises a hexagon of six cations with anions either in the center or lying above and/or below the centroid. Full article
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