Search Results (274)

In this work, Cu/TiO₂ catalysts were prepared by several high-energy ball milling strategies (dry and semi-wet milling) using different copper reagents and compared with a sample synthesized by a conventional impregnation method. Crystal structures were identified by means of X-ray Diffraction (XRD), including anatase, rutile, high-pressure TiO₂ (II) and W species due to mill vial erosion at some conditions, highlighting the effect of a copper precursor on the rate of titania polymorphic transformation. Specific Surface Area (S_BET) values were calculated from N₂ physisorption, showing a correlation between the energy supplied to the powder and the milling conditions. Moreover, Scanning Electron Microscopy (SEM) was able to display the morphologies while a semi-quantification of present elements could be performed by Electron Dispersive X-ray Spectroscopy (EDS). Catalysts obtained through this green and one-pot process could be suitable for a variety of reactions, including CO₂ hydrogenation and glycerol valorization. Full article

Zinc oxide (ZnO) is a widely studied photocatalyst for the degradation of organic pollutants in water, yet its conventional sol–gel synthesis often suffers from low yield and produces materials with low specific surface area. In this study, we tackled these limitations by synthesizing ZnO nanoparticles using a supercritical-CO₂-assisted sol–gel method (ZnO-scCO₂). The influence of the calcination temperature, precursor concentration, and solvent type on the synthesis of ZnO was systematically investigated, and the materials were characterized with a combination of techniques (XRD, SEM, N₂ physisorption, UV-Vis-DRS spectroscopy). The photocatalytic performance of the ZnO-scCO₂ materials was evaluated in the degradation of two probe pollutants (phenol and rhodamine B, 200 ppm), under UV and visible radiation. The scCO₂-assisted method in ethanol as the solvent allowed achieving at least a four-fold higher ZnO yield and two-fold higher surface area compared to the materials prepared with a conventional sol–gel route without scCO₂. These ZnO-scCO₂ nanoparticles consistently showed enhanced photocatalytic activity in the removal of phenol and rhodamine B compared to their counterparts synthesized without scCO₂ and compared to commercial ZnO. Among the screened synthetic parameters, the solvent in which ZnO was prepared proved to be the one with the strongest influence in determining the ZnO yield and its photocatalytic activity. The optimum results were obtained using 0.50 M zinc acetate as the precursor in 1-butanol as the solvent, and calcination at 300 °C. Full article

The continuous tightening of emission regulations and the escalating costs of palladium (Pd) and rhodium (Rh) have renewed interest in platinum (Pt)-based three-way catalysts (TWCs) as cost-effective alternatives for gasoline aftertreatment. However, despite extensive studies on Pt/CeO₂ and Pt/Ba-based formulations, the cooperative roles of Ba and Ce and, in particular, the fundamental influence of the Ba/Ce ratio on oxygen mobility, NO_x storage behavior, and Pt–support interactions remain poorly understood. In this work, we address this gap by systematically tuning the Ba/Ce molar ratio in a series of Pt–Ba–Ce/Al₂O₃ catalysts prepared from Ba(CH₃COO)₂ and CeO₂ precursors, and evaluating their structure–function relationships in both fresh and hydrothermally aged states. Through comprehensive characterization (N₂ physisorption, XRD, XPS, H₂-TPR, NO_x-TPD, SEM, CO pulse adsorption, and dynamic light-off testing), we establish previously unrecognized correlations between Ba/Ce ratio–dependent structural evolution and TWC performance. The results reveal that the Ba/Ce ratio exerts a decisive control over catalyst textural properties, Pt dispersion, and interfacial Pt–CeO₂ oxygen species. Low Ba/Ce ratios uniquely promote Pt–Ce interfacial oxygen and O₂ spillover—providing a new mechanistic basis for enhanced low-temperature oxidation and reduction reactions—while higher Ba loading selectively drives BaCO₃ formation and boosts NO_x storage capacity. A clear volcano-type dependence of NO_x storage on the Ba/Ce ratio is demonstrated for the first time. Hydrothermal aging at 850 °C induces PtO_x decomposition, BaCO₃–Al₂O₃ solid-state reactions forming inactive BaAl₂O₄, and Pt sintering, collectively suppressing Pt–Ce interactions and reducing TWC activity. Importantly, an optimized Ba/Ce ratio is shown to mitigate these degradation pathways, offering a new design principle for thermally durable Pt-based TWCs. Overall, this study provides new mechanistic insight into Ba–Ce cooperative effects, establishes the Ba/Ce ratio as a critical and previously overlooked parameter governing Pt–support interactions and NO_x storage, and presents a rational strategy for designing cost-effective, hydrothermally robust Pt-based alternatives to Pd/Rh commercial TWCs. Full article

A comparative study on the adsorption of ciprofloxacin (CIP) and sulfamethoxazole (SMX) onto CO₂-activated biochars derived from leather tannery waste (ABT) and Sargassum brown macroalgae (ABS) is presented. N₂ physisorption revealed that ABS possesses a higher Langmuir surface area (1305 m²/g) and a hierarchical micro–mesoporous structure, whereas ABT exhibits a lower surface area (412 m²/g) and a predominantly microporous texture. CHNS and FTIR analyses confirmed the presence of N-, O-, and S-containing heteroatoms and functional groups on both adsorbents, enhancing surface reactivity. Adsorption isotherms fitted well to the Langmuir model, with ABS showing superior maximum capacities of 256.41 mg/g (CIP) and 256.46 mg/g (SMX) compared to ABT (210.13 and 213.00 mg/g, respectively). Kinetic data followed a pseudo-second-order model (R² > 0.998), with ABS exhibiting faster uptake due to its mesoporosity. Over eight reuse cycles, ABS retained >75% removal efficiency for both antibiotics, while ABT declined to 60–70%. pH-dependent adsorption behavior was governed by the point of zero charge (pH_PZC≈ 9.0 for ABT; ≈7.2 for ABS), influencing electrostatic and non-electrostatic interactions. These findings demonstrate that ABS is a highly effective, sustainable adsorbent for antibiotic removal in water treatment applications. Full article

The increasing atmospheric concentration of CO₂ is a major contributor to global climate change, underscoring the urgent need for effective strategies to convert CO₂ into value-added products. In this sense, a composite was successfully synthesized by combining clinoptilolite zeolite (CZ) with varying amounts of copper oxide (CuO-1% and 10%) for CO₂ photoreduction. The composites were characterized using insightful techniques, including XRD, nitrogen physisorption, DRS, and SEM. The results confirmed the incorporation and dispersion of CuO within the CZ support. The XRD analysis revealed characteristic crystalline CuO peaks. Despite the low surface area (<15 m²·g⁻¹) and macroporous nature of the samples, EDS imaging revealed an effective and homogeneous dispersion of CuO, indicating efficient surface distribution. UV–Vis diffuse reflectance spectroscopy revealed band gap energies of 3.30 eV (CZ), 3.38 eV (1%-CuO/CZ), and 1.75 eV (10%-CuO/CZ), highlighting the pronounced electronic changes resulting from CuO incorporation. Photocatalytic tests conducted under UVC irradiation (λ = 254 nm) revealed that 10%-CuO/CZ exhibited the highest CO and CH₄ production, 35 µmol·g⁻¹ and 3.6 µmol·g⁻¹, respectively. The composite also delivered the highest CO productivity (5.91 µmol·g⁻¹·h⁻¹), approximately 3.5 times that of pristine CZ, in addition to achieving the highest CH₄ productivity (0.60 µmol·g⁻¹·h⁻¹). Furthermore, turnover frequency (TOF) analysis normalized per Cu site revealed that CuO incorporation not only enhances total productivity but also improves the intrinsic catalytic efficiency of the active copper centers. Overall, the synthesized composites demonstrate promising potential for CO₂ photoreduction, driven by synergistic structural, electronic, and morphological features. Full article

This study demonstrates the complete transformation of almond shell waste into a high-performance carbon material for carbon paste electrode (CPE) fabrication. The biocarbon was synthesized via carbonization at 800 °C and subsequently activated with CO₂, resulting in a semicrystalline structure rich in carbonyl groups—consistent with its lignocellulosic origin (34.25% cellulose, 13.48% hemicellulose, 48.03% lignin). Carbonization increased the total pore volume of carbonized almond (CAR_ALD) by nearly 13-fold and the specific surface area by over two orders of magnitude compared to raw almond (RAW_ALD), while CO₂ activation further enhanced activated almond’s (ACT_ALD) surface area (~19%) and pore volume (~35%). To improve electrochemical performance, Bi₂O₃ doped with Sm was applied as a surface modifier. Comprehensive characterization (N₂ physisorption X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopic Analysis (FTIR), X-Ray Photoelectron Spectroscopic Analysis (XPS), Thermogravimetric and Differential Thermal Analysis (TG-DTA), Cyclic voltammetry (CV), Electrochemical impedance spectroscopy (EIS)) confirmed the material’s structural integrity, graphitic features, and successful modifier incorporation. Electrochemical testing revealed the highest current response (48 µA) for the CPE fabricated from CAR_ALD/Bi₂O₃-Sm, indicating superior electrocatalytic activity and reduced charge transfer resistance. Notably, this is the first report of a fully functional CPE working electrode fabricated entirely from waste material. Full article

The development of cost-effective non-noble metal catalysts for the partial oxidation of methane (POM) remains a key strategy for producing hydrogen-rich syngas while mitigating greenhouse gas emissions. In this study, cobalt-supported alumina (Co/Al₂O₃) catalysts were prepared using 5 wt.% of Co and calcined at 600, 700, and 800 °C. Subsequently, Co/Al₂O₃ catalysts were promoted with 10 wt.% Mg, Si, Ti, and Zr at the optimized calcination temperature. The catalysts were systematically characterized by FT-IR, XRD, N₂ physisorption, H₂-TPR, and XPS analyses. Catalytic activity tests for POM of CH₄ were conducted at 600 °C (CH₄/O₂ = 2 and GHSV = 14,400 mL g⁻¹ h⁻¹). Catalysts calcined at 700 °C (5Co/Al_700) exhibited the highest activity among unpromoted samples, with CH₄ conversion of 43.9% and H₂ yield of 41.8%. The superior performance was attributed to its high surface area and the abundance of reducible Co³⁺ species, generating a greater number of Co⁰ active sites. XPS results confirmed the structural stability of γ-Al₂O₃ and preserved Co–Al interactions across calcination temperatures, while promoters mainly modulated Co dispersion and redox accessibility. Among the promoted catalysts, the activity order followed: 5Co/10ZrAl > 5Co/10MgAl> unpromoted-5Co/Al_700 > 5Co/10SiAl > 5Co/10TiAl. Si and Ti promoted catalysts acquired less concentration of active sites and less activity as well. The concentration of reducible species as well as initial activity towards POM are comparable over Zr and Mg-promoted catalysts. However, earlier one has a higher edge of reducibility and sustained constant activity over time in a stream study. The Zr-promoted catalyst exhibited superior reducibility and remarkable stability, achieving 47.3% CH₄ conversion and 44.4% H₂ yield sustained over 300 min time-on-stream. TEM analysis of spent 5Co/10ZrAl indicated that Zr promotion suppressed graphitic carbon formation. Full article

With the intensifying global climate crisis and the urgent demand for carbon neutrality, carbon dioxide (CO₂) capture technologies have received growing attention as effective strategies for mitigating greenhouse gas emissions. Carbon-based porous materials are widely regarded as promising CO₂ adsorbents due to their tunable porosity, high surface area, and excellent chemical and thermal stability. Among them, biomass-derived porous carbon materials have received growing attention as sustainable, low-cost alternatives to fossil-based adsorbents. This review provides a comprehensive overview of recent advances in biomass-derived porous carbon materials for CO₂ capture, emphasizing the fundamental adsorption mechanisms, including physisorption, chemisorption, and their synergistic effects. Key synthesis pathways, such as pyrolysis and hydrothermal carbonization, are discussed in relation to the development of biomass-derived porous carbon materials. Furthermore, performance-enhancing strategies, such as activation treatments, heteroatom doping, and templating methods, are critically evaluated for their ability to tailor surface properties and improve CO₂ uptake capacity. Recent progress in typical biomass-derived porous carbon materials, including active carbon, hierarchical porous carbon, and other innovative carbon materials, is also highlighted. In addition to summarizing recent advances in porous carbon synthesis, this review introduces a unified techno-economic framework that integrates cost, sustainability, and performance-driven benefits. Overall, this review aims to provide systematic insights into the performance of biomass-derived porous carbon materials and to guide the rational design of efficient, sustainable adsorbents for real-world carbon capture applications. Full article

The widespread corrosion of mild steel in acidic environments presents a persistent and economically significant challenge across multiple industries. Compounding this issue, many conventional corrosion inhibitors carry substantial environmental and toxicological hazards, underscoring the critical need for developing high-performance, environmentally benign alternatives. This study investigates a corrosion inhibitor composite comprising collagen and 1-butyl-3-methylimidazolium bromide (BMIM·Br) for mild steel in 1.5 M HCl. Gravimetric analysis demonstrated exceptional inhibition efficiency (>95%) across a temperature range of 30–60 °C, with remarkable thermal stability evidenced by less than a 1% decrease at elevated temperatures. The adsorption process was found to be spontaneous and followed the Langmuir isotherm, with thermodynamic parameters (ΔG°_ads ≈ −17 to −19 kJ/mol) indicating a mixed physisorption–chemisorption mechanism. FTIR and XRD analyses confirmed molecular-level interactions and the formation of a more amorphous composite structure. A multi-modal adsorption mechanism, supported by Density Functional Theory (DFT) insights, is proposed, elucidating the synergy through ionic bridging and the formation of a co-accreted polymeric film. These findings establish the collagen–BMIM·Br composite as a highly effective, stable, and sustainable corrosion inhibitor for demanding industrial applications in aggressive acidic environments. Full article

The development of highly sensitive gas sensors for toxic industrial gases (TIGs) is paramount for environmental monitoring and public safety. Here, the first-principles calculations were employed to systematically investigate the potential of Pt- and Rh-decorated InS (Pt-InS and Rh-InS) monolayers as advanced gas sensing materials for the five TIGs (SO₂, NH₃, NO, CO, and NO₂). The results reveal that Pt and Rh atoms can be stably anchored at the InS monolayer, inducing significant modulation of its electronic properties. The Pt-InS system exhibits strong chemisorption of NH₃ and CO, while the other TIGs interact via physisorption. In contrast, the Rh-InS monolayer demonstrates strong chemisorption and distinct electronic responses to all five gases, driven by robust hybridization between the Rh-d and TIG-p orbitals. Based on comprehensive analyses of sensitivity and recovery time, Rh-InS is identified as a theoretically promising candidate for a reusable SO₂ sensor at room temperature, boasting a calculated rapid theoretical recovery time of 2.20 s. The Pt-InS system, conversely, shows potential for high-temperature NH₃ sensing. Our findings highlight the exceptional and tunable gas sensing capabilities of Pt- and Rh-decorated InS monolayers, offering a theoretical foundation for designing InS-based sensing devices. Full article

Silica aerogels are highly attractive due to their outstanding properties, including their low density, ultralow thermal conductivity, large porosity, high optical transparency, and strong sorption activity. However, their inherent brittleness has limited widespread applications. Constructing a robust, highly porous three-dimensional network is critical to achieving the desired mechanical properties in aerogels. In this study, we introduce a novel synthesis route for fabricating lightweight and mechanically strong aerogels by incorporating poly(ethylene-co-vinyl alcohol) (EVOH) through thermally induced phase separation (TIPS). EVOH exhibits upper critical solution temperature (UCST) behavior in a mixture of isopropanol (IPA) and water, which can be utilized to reinforce the silica skeletal structure. Robust aerogels were prepared via the sol–gel process and TIPS method, followed by supercritical CO₂ drying, yielding samples with bulk densities ranging from 0.136 to 0.200 g/cm³. N₂ physisorption analysis revealed a mesoporous structure, with the specific surface area decreasing from 874 to 401 m²/g as EVOH content increased from 0 to 80 mg/mL. The introduced EVOH significantly enhanced mechanical performance, raising the flexural strength and compressive strength to 0.545 MPa and 18.37 MPa, respectively—far exceeding those of pure silica aerogel (0.098 MPa and 0.74 MPa). This work demonstrates the effectiveness of the TIPS strategy for developing high-strength, low-density silica aerogels with well-preserved porosity. Full article

Calcium (Ca²⁺ ions) is one of the dominant elements that contribute to water hardness, scaling in pipes, bathroom faucets, and kitchen utensils. Herein, we report on the development of poly(vinylidene fluoride-co-hexafluoropropylene) cellulose acetate (PVDF-HFP/CA) films for the treatment of Ca²⁺ ions as one of the constituents that causes water hardness. CA and PVDF-HFP polymers, and their blend consisting of 3 wt.% PVDF-HFP/CA, were effectively synthesised through the phase inversion technique. Analysis using thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) confirmed the effective incorporation of 3 wt.% PVDF-HFP into the cellulose acetate film. Parameters such as temperature, initial concentration, pH, adsorbent dosage and contact time were investigated in batch studies during the removal of Ca²⁺ ions in synthetic water samples. Under optimal conditions (pH 7, adsorbent dosage of 0.5 mg/L, and concentration of 120 mg/L), the 3 wt.% PVDF-HFP/CA film achieved a 99% adsorption efficiency for Ca²⁺ ions in 90 min. The adsorption process adhered to pseudo-second-order and Freundlich isotherm models, which suggest that the adsorption of Ca²⁺ ions is heterogeneous. The maximum adsorption efficiency achieved was 56 mg/g, indicating an endothermic physisorption process. The 3 wt.% PVDF-HFP/CA film maintained higher adsorption in the presence of counter ions and in a binary system, and it could be recycled at least three times. Thus, the findings demonstrated that the 3 wt.% PVDF-HFP/CA film could be a valuable material for Ca²⁺ ions removal to acceptable drinking water levels. Full article

This work examines the effect of gadolinium (Gd) promotion on nickel-based SBA-16 catalysts for the dry reforming of methane (DRM), with the goal of improving syngas production by optimizing catalyst composition and operating conditions. Catalysts with varying Gd loadings (0.5–3 wt.%) were synthesised using co-impregnation. XRD, N₂ physisorption, FTIR, XPS, and H₂-TPR–CO₂-TPD–H₂-TPR were used to examine the structural features, textural properties, surface composition, and redox behaviour of the catalysts. XPS indicated formation of enhanced metal–support interactions, while initial and post-treatment H₂–TPR analyses showed that moderate Gd loadings (1–2 wt.%) maintained a balanced distribution of reducible Ni species. The catalysts were tested for DRM performance at 800 °C and a gas hourly space velocity (GHSV) of 42,000 mL g⁻¹ h⁻¹. 1–2 wt.% Gd-promoted catalysts achieved the highest H₂ (~67%) and CO yield (~76%). Response surface methodology (RSM) was used to identify optimal reaction conditions for maximum H₂ yield. RSM predicted 848.9 °C temperature, 31,283 mL g⁻¹ h⁻¹ GHSV, and a CH₄/CO₂ ratio of 0.61 as optimal, predicting a H₂ yield of 96.64%, which closely matched the experimental value of H₂ yield (96.66%). The 5Ni–2Gd/SBA-16 catalyst exhibited minimal coke deposition, primarily of a graphitic character, as evidenced by TGA–DSC and Raman analyses. These results demonstrate the synergy between catalyst design and process optimization in maximizing DRM efficiency. Full article

An increase in the production of cationic dyes is expected over the next decade, which will have an impact on health and the environment. This work reports an adsorbent hydrogel composed of poly(acrylic acid) [poly(AA)] and Fe₃O₄ particles, prepared by radical polymerization and in situ co-precipitation of Fe³⁺ and Fe²⁺. This Fe₃O₄/poly(AA) composite hydrogel was used to evaluate its potential for removing the cationic dyes methylene blue (MB) and crystal violet (CV) from aqueous solutions. Instrumental characterization of the hydrogel was performed by FTIR, XRD, TGA, VSM, and physicochemical analysis (swelling and response to changes in pH). The results show that the incorporation of Fe₃O₄ particles improves the adsorption capacity of MB and CV dyes to a maximum adsorption of 571 and 321 mg/g, respectively, under the best conditions (pH 6.8, dose 1 g/L, time 24 h). The adsorption data best fit the pseudo-first order (PFO) kinetic model and the Freundlich isothermal model, indicating mass transfer via internal and/or external diffusion and active sites with different adsorption potentials. Moreover, the thermodynamic analysis confirmed that the adsorption process was spontaneous and exothermic, with physisorption as the dominant mechanism. In addition, the Fe₃O₄/poly(AA) hydrogel is capable of removing 95% of the dyes after ten consecutive adsorption–desorption cycles, demonstrating the potential of hydrogels loaded with Fe₃O₄ particles for the treatment of wastewater contaminated with dyes. Full article

p-toluenesulfonic acid (pTSA) was used for the synthesis of porous silica xerogels while applying different synthesis conditions. Key parameters included acid concentration, drying temperature and the method of acid removal. The resulting organic–inorganic composites were investigated by nitrogen physisorption, X-ray powder diffraction (XRD), solid-state NMR and thermal analysis. The results demonstrated that both the drying temperature and quantity of the pTSA significantly influenced the pore structure of the xerogels. The utilization of such strong acids like pTSA yielded high surface area and pore volume, as well as narrow pore size distribution. Environmentally friendly template removal by solvent extraction produced materials with superior textural properties compared to traditional calcination, enabling the recovery and reuse of pTSA with over 95% efficiency. A selected mesoporous silica xerogel was modified by a simple two-step post-synthesis procedure with 1-(2-Hydroxyethyl) piperazine (HEP). High CO₂ adsorption capacity was determined for the HEP-modified material in dynamic conditions. The isosteric heat of adsorption revealed the stronger interaction between functional groups and CO₂ molecules. Total CO₂ desorption could be achieved at 60 °C. Leaching of the silica functional groups could not be detected even after four consecutive adsorption cycles. These findings provide valuable insights into the sustainable synthesis of tunable piperazine-modified mesoporous silica xerogels with potential applications in CO₂ capture. Full article