Search Results (153)

The development of cost-effective and scalable air/oxygen electrode materials is crucial for the advancement of Zn–air batteries (ZABs). Porous carbon materials doped with heteroatoms have attracted considerable attention in energy and environmental fields because of their tunable nanoporosity and high electrical conductivity. In this work, we report the synthesis of a three-dimensional (3D) N and P co-doped porous carbon (PA@pDC-1000), derived from a conjugated polyaniline–phytic acid polymer. The cross-linked, rigid conjugated polymeric framework plays a crucial role in maintaining the integrity of micro- and mesoporous structures and promoting graphitization during carbonization. As a result, the material exhibits a hierarchical pore structure, a high specific surface area (1045 m² g⁻¹), and a large pore volume (1.02 cm³ g⁻¹). The 3D N, P co-doped PA@pDC-1000 catalyst delivers a half-wave potential of 0.80 V (vs. RHE) and demonstrates a higher current density compared to commercial Pt/C. A primary ZAB utilizing this material achieves an open-circuit voltage of 1.51 V and a peak power density of 217 mW cm⁻². This metal-free, self-templating presents a scalable route for the generating and producing of high-performance oxygen reduction reaction catalysts for ZABs. Full article

This study investigates the coupled effects of waste rock-to-tailings ratio (WTR) and curing temperature on the pore structure and mechanical performance of cemented tailings waste rock backfill (CTRB). Four WTRs (6:4, 7:3, 8:2, 9:1) and curing temperatures (20–50 °C) were tested. Low-field nuclear magnetic resonance (NMR) was used to characterize pore size distributions and derive fractal dimensions ($D_a$, $D_b$, $D_c$) at micropore, mesopore, and macropore scales. Uniaxial compressive strength (UCS) and elastic modulus (E) were also measured. The results reveal that (1) the micropore structure complexity was found to be a key indicator of structural refinement, while excessive temperature led to pore coarsening and strength reduction. $D_a$ = 2.01 reaches its peak at WTR = 7:3 and curing temperature = 40 °C; (2) at this condition, the UCS and E achieved 20.5 MPa and 1260 MPa, increasing by 45% and 38% over the baseline (WTR = 6:4, 20 °C); (3) when the temperature exceeded 40 °C, $D_a$ dropped significantly (e.g., to 1.51 at 50 °C for WTR = 7:3), indicating thermal over-curing and micropore coarsening; (4) correlation analysis showed strong negative relationships between total pore volume and mechanical strength ($R$ = −0.87 for ${\mathsf{\delta }}_a\mathrm{v}\mathrm{s}.\mathrm{U}\mathrm{C}\mathrm{S}),$ and a positive correlation between $D_a$ and UCS (R = 0.43). (5) multivariate regression models incorporating pore volume fractions, $T_2$ relaxation times, and fractal dimensions predicted $\mathrm{U}\mathrm{C}\mathrm{S}$ and E with R² > 0.98; (6) the hierarchical sensitivity of fractal dimensions follows the order micro-, meso-, macropores. This study provides new insights into the microstructure–mechanical performance relationship in CTRB and offers a theoretical and practical basis for the design of high-performance backfill materials in deep mining environments. Full article

Sn-based anodes for lithium-ion batteries (LIBs) offer high capacity and low cost; however, significant volume changes during lithiation/delithiation cause mechanical degradation, limiting their practical applications. Microstructural control is a key approach to mitigating these volume changes. This study reports the fabrication of core (Sn rod)-shell (mesoporous Sn-oxide layer) structures through electrodeposition followed by anodization, and their applications to anode active materials for LIBs. First, micro-Sn rods with controlled lengths and diameters were fabricated under various electrodeposition conditions. The electrodeposited Sn exhibited a dendritic structure with short secondary rods branching from a long primary rod. While the primary Sn rod diameters remained constant, the secondary rod diameters varied depending on electrodeposition parameters. Notably, rod coarsening due to secondary rod agglomeration occurred at higher currents and longer deposition durations during galvanostatic electrodeposition. In contrast, potentiostatic electrodeposition prevented agglomeration and increased the quantity of Sn rods with voltage. Subsequently, the core-shell structures were fabricated by anodizing Sn rods, forming mesoporous Sn-oxide layers with different pore sizes and pore wall thicknesses. Electrochemical characterization revealed that the core-shell anode performance for LIBs varied with the Sn-oxide shell’s microstructure. These findings provide insights into optimal core-shell structures to improve anode performance for LIBs. Full article

The development of carbonaceous materials such as biochar has triggered a hot spot in materials application. In this study, a new type of char carbon was developed from raw cigarette filter rods (CFRs) via a carbonization process under moderate conditions (T = 550 °C; t_res = 1 h) (CFR char carbon). The produced char was characterized by ATR-FTIR (Attenuated total reflectance—Fourier-transform infrared) spectroscopy, XRD (X-ray diffraction) analysis, GC-MS (Gas Chromatography–Mass Spectrometry), FESEM-EDS (Field-Emission Scanning Electron Microscopy—Energy-dispersive X-ray spectroscopy) technique, XPS (X-ray photoelectron spectroscopy), and N₂ adsorption/desorption (BET) measurements. The obtained carbon material is rich in oxygen-containing functional groups (i.e., C=O, C–O, –C(=O)–CH₃, C–O–C, C–OH, and O=C–O, with chemisorbed oxygen), containing significant amounts of calcium (that originates from CaCO₃) and silicon (Si), generated by reduction of SiO₂. It was found that the formation of char(C)/n-alkane composite material makes that CFR char have a high compressive strength improvement. Moderate carbonization has contributed to the creation of such material that has a fairly high specific surface area (320.93 m²/g), exhibiting a complex hierarchical structure that was characterized by composite Type I/IV(a) isotherm, associated with micro-/mesoporous carbon material. In addition, more directional extensions of this research for future work were proposed, including the implementation of electrochemical research. Full article

The aim of this paper was to obtain activated biocarbons from the natural biomass of horse chestnut seeds (Aesculus hippocastanum) by physical activation with two different activating agents, carbon dioxide and water vapor, and to evaluate their structural and adsorption properties. The effect of the pyrolysis atmosphere on the surface development and porosity as well as the structure and adsorption properties of the materials in relation to the selected organic adsorbates (tetracycline (TC), naproxen (NPX), and methyl orange (MO)), which may constitute a potential contamination of the aquatic environment, was evaluated. Activated biocarbons were characterized using N₂ low-temperature adsorption/desorption, Raman and FT-IR spectroscopy, and thermogravimetric analysis (TGA). The nature of the surface (pH_pzc and Boehm titration) was also studied. Micro/mesoporous biocarbons were obtained with an S_BET area in the range of ~534 to 646 m²/g, in which micropores constituted ~70%. It was proved that the obtained materials are characterized by high adsorption values (~120 mg/g, ~150 mg/g, and ~252 mg/g) and removal rates %R (~80%, ~95%, and ~75%) for TC, NPX, and MO, respectively. The results indicate that chestnut-derived activated biocarbons are a promising, cost-effective and environmentally friendly alternative for removing organic contaminants from aqueous solutions. Future research should focus on optimizing activation parameters and assessing the long-term performance of adsorbents. Full article

The wastewater of the “Rubizhanskyi” storage facility at the chemical enterprise “Rubizhanskyi Krasitel” (Ukraine) is a complex multicomponent system. The concentration of colored organic substances in the highly mineralized wastewater significantly exceeds the established norms. This work shows the possibility of an almost complete purification of the multicomponent wastewater using a carbon sorbent. The treatment of wastewater was carried out using the sorption method with carbon adsorbents KARBON™ (Institute for Sorption and Problems of Endoecology, Kyiv, Ukraine) and ZL-302, which are micro-mesoporous materials, with specific surface areas of 1730 and 1523 m²/g, respectively. The purification efficiency of the wastewater containing aromatic compounds by the carbon adsorbents KARBON™ and ZL-302 achieved 99.99% and 94.4%, respectively. The adsorption capacity of the carbon adsorbent KARBON™ with respect to aniline was 0.47 g/g, and that of commercial coal ZL-302 was 0.45 g/g. Therefore, the carbon adsorbent KARBON™ is a promising material for the successful purification of wastewater from chemical enterprises contaminated with aromatic compounds. Full article

Hierarchical zeolites with micro- and mesoporous frameworks can overcome diffusional limitations of microporous systems. This study investigates the post-synthetic modification of Beta zeolite using different porogeneous agents (NaOH, NH₄OH, NH₄F) under identical conditions to compare their efficiency in generating mesopores. The effect of treatment time was also examined for NH₄OH and NH₄F. The modified materials were characterized using physicochemical techniques and evaluated for catalytic performance in acetic acid esterification with alcohols of different sizes and adsorption of methylene blue. All the modifications increased mesoporosity but reduced acidity. NaOH produced the highest mesoporosity but significantly reduced acidity, while NH₄F retained the most acidity. Catalytic activity in esterification with methanol depended on acidity, but for larger alcohols (n-butanol, benzyl alcohol), activity was influenced by both acidity and mesoporosity. The NH₄OH- and NH₄F-modified materials, with lower mesoporosity but higher acidity, exhibited better performance with larger alcohols. In MB adsorption, the adsorption equilibrium rates increased with mesoporosity. The NaOH-modified sample reached equilibrium the fastest due to its superior mesoporosity, while the NH₄F-modified sample demonstrated the highest adsorption efficiency owing to its abundant Brønsted acid sites. These findings demonstrate that the choice of modifier affects mesoporosity, acidity, and functional performance, offering insights into tailoring hierarchical zeolites for specific applications. Full article

Background: Mesoporous titanium dioxide nanoparticles (mTiNPs) are known for their chemical stability, non-toxicity, antimicrobial and anticancer effects, as well as for their photocatalytic properties. When this material is subjected to UV radiation, its electronic structure shifts, and during that process, reactive oxygen species are generated, which in turn exert apoptotic events on the cancer cells. Objectives: We evaluated the cytotoxic effects of UV-irradiated mTiNPs on prostate cancer (PCa) cell line PC3 with the aim of demonstrating that the interaction between UV-light and mTiNPs positively impacts the nanomaterial’s cytotoxic efficiency. Moreover, we assessed the differential expression of key oncomiRs and tumor suppressor (TS) miRNAs, as well as their associated target genes, in cells undergoing this treatment. Methods: PBS-suspended mTiNPs exposed to 290 nm UV light were added at different concentrations to PC3 cells. Cell viability was determined after 24 h with a crystal violet assay. Then, the obtained IC₅₀ concentration of UV-nanomaterial was applied to a new PC3 cell culture, and the expression of a set of miRNAs and selected target genes was evaluated via qRT-PCR. Results: The cells exposed to photo-activated mTiNPs required 4.38 times less concentration of the nanomaterial than the group exposed to non-irradiated mTiNPs to achieve the half-maximal inhibition, demonstrating an improved cytotoxic performance of the UV-irradiated mTiNPs. Moreover, the expression of miR-18a-5p, miR-21-5p, and miR-221-5p was downregulated after the application of UV-mTiNPs, while TS miR-200a-5p and miR-200b-5p displayed an upregulated expression. Among the miRNA target genes, PTEN was found to be upregulated after the treatment, while BCL-2 and TP53 were underexpressed. Conclusions: Our cytotoxic outcomes coincided with previous reports performed in other cancer cell lines, strongly suggesting UV-irradiated mTiNPs as a promising nano-therapeutic approach against PCa. On the other hand, to the best of our knowledge, this is the first report exploring the impact of UV-irradiated mTiNPs on key onco- and TS microRNAs in PCa cells. Full article

This review analyzes the current practices in the data-driven characterization, design and optimization of disordered nanoporous materials with pore sizes ranging from angstroms (active carbon and polymer membranes for gas separation) to tens of nm (aerogels). While the machine learning (ML)-based prediction and screening of crystalline, ordered porous materials are conducted frequently, materials with disordered porosity receive much less attention, although ML is expected to excel in the field, which is rich with ill-posed problems, non-linear correlations and a large volume of experimental results. For micro- and mesoporous solids (active carbons, mesoporous silica, aerogels, etc.), the obstacles are mostly related to the navigation of the available data with transferrable and easily interpreted features. The majority of published efforts are based on the experimental data obtained in the same work, and the datasets are often very small. Even with limited data, machine learning helps discover non-evident correlations and serves in material design and production optimization. The development of comprehensive databases for micro- and mesoporous materials with low-level structural and sorption characteristics, as well as automated synthesis/characterization protocols, is seen as the direction of efforts for the immediate future. This paper is written in a language readable by a chemist unfamiliar with the data science specifics. Full article

Carbon is predominantly used in zinc-ion hybrid capacitors (ZIHCs) as an electrode material. Nitrogen doping and strategic design can enhance its electrochemical properties. Melamine formaldehyde resin, serving as a hard carbon precursor, synthesizes nitrogen-doped porous carbon after annealing. Incorporating transition metal catalysts like Ni, Co, and Fe alters the morphology, pore structure, graphitization degree, and nitrogen doping types/proportions. Electrochemical tests reveal a superior capacitance of 159.5 F g⁻¹ at a scan rate of 1 mV s⁻¹ and rate performance in Fe-catalyzed N-doped porous carbon (Fe-NDPC). Advanced analysis shows Fe-NDPC’s high graphitic nitrogen content and graphitization degree, boosting its electric double-layer capacitance (EDLC) and pseudocapacitance. Its abundant micro- and mesopores increase the surface area fourfold compared to non-catalyzed samples, favoring EDLC and fast electrolyte transport. This study guides catalyst application in carbon materials for supercapacitors, illuminating how catalysts influence nitrogen-doped porous carbon structure and performance. Full article

Due to the unique properties of titanium dioxide (TiO₂), titanium oxide catalysts hold significant potential for photo-oxidative processes involving organic substances in liquid media. The current research has focused on developing new preparation methods that enable the manipulation of the properties, structure, and geometric shape of catalysts to enhance their efficiency in targeted reactions. This study developed a method for preparing Ag-SiO₂-TiO₂/TiO₂-Ag layered structures with a spherical shape, featuring particle diameters ranging from 232 to 653 μm and mesopores of 2–20 nm. This was achieved by combining sol–gel and template synthesis methods. A comprehensive analysis of the obtained materials was conducted using methods such as X-ray phase analysis, micro-X-ray spectral analysis, X-ray microanalysis, and scanning electron spectroscopy. The photocatalytic properties were assessed by measuring the degree of decomposition of methyl orange in a model oxidation reaction under light radiation. The obtained spherical Ag-SiO₂-TiO₂/TiO₂-Ag layered structures demonstrated high efficiency in the photooxidation of methyl orange in the model reaction. Full article

Currently, materials with specific, strictly defined functional properties are becoming increasingly important. A promising strategy for achieving these properties involves developing methods that facilitate the formation of hierarchical porous materials that combine micro-, meso-, and macropores in their structure. Macropores facilitate effective mass transfer of substances to the meso- and micropores, where further adsorption or reaction processes can occur. Aerogels represent a promising class of materials for implementing this approach. The formation of hierarchical porous structures in aerogels can be achieved using soft and hard templating methods or by foaming techniques. This paper presents a comprehensive study of three methods for forming hierarchical porous structures in alginate aerogels: (1) employing surfactants (Pluronic F-68), (2) using zein as a pore-forming component, and (3) foaming in a carbon dioxide medium. The results of micro-CT showed that each of the methods contributes to the formation of macropores within the structure of the resulting aerogels. Size distribution curves of the detected macropores were obtained, showing the presence of macropores ranging from 16 to 323 μm in size for samples obtained using surfactants, from 5 to 195 μm for samples obtained using zein, and from 20 μm to 3 mm for samples obtained by foaming in a carbon dioxide medium. The SEM images demonstrated the macro- and mesoporous fibrous structure of the obtained materials. The nitrogen porosimetry results indicated that samples obtained using surfactants and zein are characterized by a high specific surface area (592–673 m²/g), comparable to the specific surface area for an alginate-based aerogel obtained without the use of pore-forming components. However, the use of the developed methods for the formation of a hierarchical porous structure contributes to an increase in the specific mesopores volume (up to 17.7 cm³/g). The materials obtained by foaming in a carbon dioxide medium are characterized by lower specific surface areas (112–239 m²/g) and specific mesopores volumes (0.6–2.1 cm³/g). Thus, this paper presents a set of methods for forming hierarchical porous structures that can obtain delivery systems for active substances with a controlled release profile and highly efficient platforms for cell culturing. Full article

The textural properties of synthetic and natural clays in the sodium form and exchanged with tetramethylammonium cations (TMA⁺) were characterized using N₂ and Ar physisorption isotherms at cryogenic temperatures. Specific surface areas and micro/mesoporous volumes were determined using the BET and the t-plot models. The t-plot analysis requires the use of reference isotherms measured at the same temperature on the surface of non-porous materials with an identical chemical composition. In order to better assess the effects of chemical heterogeneities in the clay particles, reference isotherms representative of silica surfaces were taken into account in the analysis of the t-curve and corrected to account for variations in curvature at the interface of the film adsorbed in the micropores. In addition, high-resolution Ar adsorption isotherms at 87 K were analyzed using the Derivative Isotherm Summation (DIS) method to quantify the energy contributions of adsorption sites and determine the fractions of basal and lateral surfaces of clay particles. The high-energy adsorption sites, identified in the low-pressure range, were attributed to intra-particle microporosity due to stacking defects and/or open inter-layer spaces. These sites were differentiated from those on the lateral and basal surfaces of the particles. A modification of the DIS method was proposed to measure these contributions and improve the fit with the experimental data. The results show that TMA⁺ cation exchange significantly increases the microporosity of clays compared to their sodic form, which can be attributed to the increased contribution of intra-particle adsorption sites due to interlayer expansion. Full article

This paper proposes a method for synthesizing granular ZSM-23 zeolite with a high degree of crystallinity and hierarchical porous structure. This method is based on crystallizing granules composed of powdered ZSM-23 zeolite and a specially prepared amorphous aluminosilicate. It has been shown that these granules have superior mechanical strength compared to granular zeolite-containing materials, which are made from a mixture of ZSM-23 zeolite crystals and Al₂O₃. It has been demonstrated that when 0.5% of Pt granular ZSM-23 zeolite is used, with a high degree of crystallinity and a hierarchical porous structure, it exhibits higher activity and selectivity in the hydroisomerization of n-hexadecane compared to a bifunctional catalyst, which is a mechanical mixture of ZSM-23 zeolite crystals and Al₂O₃, with the metal deposited on the granules. Full article

Polymers with micro- and mesoporous structure are promising as materials for gas storage and separation, encapsulating agents for controlled drug release, carriers for catalysts and sensors, precursors of nanostructured carbon materials, carriers for biomolecular immobilization and cellular scaffolds, as materials with a low dielectric constant, filtering/separating membranes, proton exchange membranes, templates for replicating structures, and as electrode materials for energy storage. Sol–gel technologies, track etching, and template synthesis are used for their production, including in micelles of surfactants and microemulsions and sublimation drying. The listed methods make it possible to obtain pores with variable shapes and sizes of 5–50 nm and achieve a narrow pore size distribution. However, all these methods are technologically multi-stage and require the use of consumables. This paper presents a review of the use of macromolecular architecture in the synthesis of micro- and mesoporous polymers with extremely high surface area and hierarchical porous polymers. The synthesis of porous polymer frameworks with individual functional capabilities, the required chemical structure, and pore surface sizes is based on the unique possibilities of developing the architecture of the polymer matrix. Full article