Search Results (64)

A facile and versatile strategy to obtain NPs@ZnAlO nanocomposite materials, comprising controlled-size nanoparticles (NPs) within a ZnAlO matrix is reported. The mono-(Au, Ni) and bimetallic (Ni-Au) NPs serving as an active phase were prepared by the polyol-alkaline method, while the ZnAlO support was obtained via the thermal decomposition of its corresponding layered double hydroxide (LDH) precursors. X-ray diffraction (XRD) patterns confirmed the successful fabrication of the nanocomposites, including the synthesis of the metallic NPs, the formation of LDH-like structure, and the subsequent transformation to ZnO phase upon LDH calcination. The obtained nanostructures confirmed the nanoplate-like morphology inherited from the original LDH precursors, which tended to aggregate after the addition of gold NPs. According to the UV-Vis spectroscopy, loading NPs onto the ZnAlO support enhanced the light absorption and reduced the band gap energy. ATR-DRIFT spectroscopy, H₂-TPR measurements, and XPS analysis provided information about the functional groups, surface composition, and reducibility of the materials. The catalytic performance of the developed nanostructures was evaluated by the photodegradation of bisphenol A (BPA), under simulated solar irradiation. The conversion of BPA over the bimetallic Ni-Au@ZnAlO reached up to 95% after 180 min of irradiation, exceeding the monometallic Ni@ZnAlO and Au@ZnAlO catalysts. Its enhanced activity was correlated with good dispersion of the bimetals, narrower band gap, and efficient charge carrier separation of the photo-induced e⁻/h⁺ pairs. Full article

Cu-based layered double hydroxides (LDH) have been extensively employed as catalyst precursors. However, due to the Jahn–Teller effect of copper ions, it is a challenge to synthesize well-crystallized LDH with a high Cu content, which usually contains considerable CuO impurity. By adding competitive ligands during the coprecipitation process, such as glycine, a well-crystallized Cu-rich LDH with less CuO impurity was successfully synthesized. The Cu-Mg-Al mixed oxides derived from the well-crystallized Cu-rich LDH have relatively high S_BET, large pore volume, and well dispersion of Cu nanoparticles. The derived catalyst exhibited unexpectedly high catalytic activity in the water–gas shift (WGS) reaction, and the mass-specific reaction rate was reached as high as 33.5 μmol_CO${·\mathrm{g}}_{\mathrm{cat}}^{-1}$·s⁻¹ at 200 °C. The high catalytic activity of this catalyst may originate from the high S_BET and well dispersion of Cu particles and metal oxides. Moreover, the derived catalyst also displayed outstanding long-term stability in the WGS reaction, which should benefit from the enhanced metal–support interaction. Full article

Mixed oxides were obtained via calcination at 550 °C from layered double hydroxides (LDHs), which were synthesized in a previous study via co-precipitation and co-precipitation followed by hydrothermal treatment using aluminum residues as the source of this element. After characterization, these oxides (Mg-Al-_LDH-CP and Mg-Al-_LDH-H, named according to the synthesis methods of the precursor LDHs) were applied as heterogeneous catalysts in the methyl transesterification of ethyl acetate (EA). The formation of mixed oxides was confirmed by the absence of basal peaks associated with the layered LDH structure in the XRD analysis, due to calcination. Further characterization revealed that Mg-Al-_LDH-CP exhibited the highest number of acidic sites, while Mg-Al-_LDH-H had the highest number of basic sites. The transesterification activity was evaluated in the reaction between ethyl acetate (EA) and methanol (MeOH). The best result, obtained under a molar ratio of 1:5:0.005 (EA:MeOH:catalyst) at 120 °C, was a 63% conversion after 360 min of reaction for the Mg-Al-_LDH-CP catalyst, which had a higher number of acidic sites and fewer basic sites. Additionally, the catalysts demonstrated robustness, maintaining catalytic activity over four cycles without a significant decrease in performance. These results indicate the feasibility of using mixed oxides derived from LDH, synthesized from aluminum residues, as heterogeneous catalysts in transesterification reactions, highlighting their potential for advancing more sustainable catalyst development. Full article

γ-Valerolactone (GVL) is a promising bio-based platform molecule with significant potential for energy applications. The production of GVL via biomass-based levulinic acid (LA) is an important reaction. To enhance the conversion and selectivity of non-precious-metal catalysts in the LA-to-GVL process and to better understand the key factors influencing this conversion, we conducted a series of experiments. In this study, supported Cu-Ni bimetallic catalysts (Cu-Ni₂/Al₂O₃) were prepared using layered double hydroxides (LDHs) as a precursor. Compared with Cu-Ni catalysts synthesized via the conventional impregnation method, the Cu-Ni₂/Al₂O₃ catalysts exhibit higher catalytic activity and stability. The results demonstrated that efficient conversion was achieved with isopropanol as the hydrogen donor solvent, a reaction temperature of 180 °C, and a reaction time of 1 h. The yield of GVL reached nearly 90%, with a decrease of approximately only 6% after six consecutive cycles. The Cu-Ni₂/Al₂O₃ catalyst proved to be effective for converting biomass-derived LA to GVL, offering a route that not only reduces production costs and environmental impact but also enables efficient biomass-to-energy conversion. Full article

Novel catalytic silicon carbide membrane filters (SCMFs) are synthesized with Co/Al–layered double hydroxide (Co/Al-LDH)-coated silicon carbide powder. After capsuled in a self-designed membrane shell, the SCMFs are utilized in activating persulphate for aniline degradation. Thermal analysis conducted via TG/DTG/DSC examination shows that the heating treatment is beneficial in elevating the activating ability of SCMFs, and the derived Co₃O₄ displays superior catalytical efficiency than Co/Al-LDHs precursor. The XRD patterns and SEM images indicate the sheet-like Co/Al-LDHs are uniformly coprecipitated throughout the surface of SCMFs. Within 20 min, around 95% of aniline is eliminated under 0.7 m of flow velocity and 8:1 of persulphate to aniline ratio. Three-dimensional fluorescence and GC chromatography reveal that distinct by-products exist in the early stage of the aniline degradation process between the sintered and non-sintered Co/Al-LDH-coated SCMFs. The integration strategy of Co/Al-LDH coatings and heating treatment endows traditional SCMFs with robust catalytic properties for engineering-oriented applications in wastewater treatment. Full article

Converting CO₂ and green hydrogen into products such as methane and methanol not only has a negative carbon effect, but also stores renewable energy into energy chemicals. This represents a promising route for hydrogen energy storage technologies. The hydrogenation of CO₂ to methane and methanol, which represent strongly exothermic reactions, are thermodynamically favored at low temperatures. However, the inherent inertness of CO₂ makes it difficult to activate CO₂ at low temperatures. Both reactions face the challenge of activating CO₂ at low temperature, so catalysts exhibiting high activity under such conditions are a critical need. Layered double hydroxides (LDHs) have attracted considerable interest owing to their regular layered structure and uniform dispersion of multiple metallic components. However, there are few studies on the same effects of promoters over LDHs-derived catalysts. Here, we investigated the same effects of promoters on two LDHs-derived catalysts in different CO₂ hydrogenation reactions to illustrate the effects of promoters on facilitating low-temperature CO₂ activation in LDHs-derived catalysts. By adding promoters Fe and Mn to the catalysts NiAl-Fe and CuZnAl-Mn, the crystal lattices were expanded, surface areas were increased 38% and 25%, and the reduction temperatures were decreased to 97 °C and 10 °C, respectively. These promoters significantly enhanced the CO₂ adsorption and activation of the catalysts NiAl-Fe and CuZnAl-Mn. The methanation catalyst NiAl-Fe achieved a CO₂ conversion of 80.8% at 200 °C and 2 MPa, while the methanol synthesis catalyst CuZnAl-Mn exhibited a CO₂ conversion of 21.3% and a methanol selectivity of 61.8% under the conditions of 250 °C and 3 MPa. The influence of the LDHs precursors’ structure and the addition of promoters Fe and Mn on the catalytic performance were studied by XRD, N₂ adsorption–desorption, H₂-TPR, H₂-TPD, and CO₂-TPD. Full article

Designing and fabricating a highly sensitive non-enzymatic glucose sensor is crucial for the early detection and management of diabetes. Meanwhile, the development of innovative electrode substrates has become a key focus for addressing the growing demand for constructing flexible sensors. Here, a simple one-step laser engraving method is applied for preparing laser-induced graphene (LIG) on polyimide (PI) film, which serves as the sensor substrate. NiCo-layered double hydroxides (NiCo-LDH) are synthesized on LIG as a precursor, utilizing the zeolitic imidazolate framework (ZIF-67), and then reacted with Ni(NO₃)₂ via solvent-thermal methods. The sensitivity of the non-enzymatic electrochemical glucose sensor is significantly improved by employing NiCo-LDH/LIG as the sensing material. The porous and interconnected structure of NiCo-LDH, derived from ZIF-67, enhances the accessibility of electrochemically active sites, while the incorporation of LIG ensures exceptional conductivity. The combination of NiCo-LDH with LIG enables efficient electron transport, leading to an increased electrochemically active surface area and enhanced catalytic efficiency. The fabricated electrode achieves a low glucose detection limit of 0.437 μM and demonstrates a high sensitivity of 1141.2 and 631.1 μA mM⁻² cm⁻² within the linear ranges of 0–770 μM and 770–1970 μM, respectively. Furthermore, the NiCo-LDH/LIG glucose sensor demonstrates superior reliability and little impact from other substances. A flexible integrated LIG-based non-enzymatic glucose sensor has been developed, demonstrating high sensitivity and suggesting a promising application for LIG-based chemical sensors. Full article

A series of M(x)CoCeMgAlO mixed oxides with different transition metals (M = Cu, Fe, Mn, and Ni) with an M content x = 3 at. %, and another series of Fe(x)CoCeMgAlO mixed oxides with Fe contents x ranging from 1 to 9 at. % with respect to cations, while keeping constant in both cases 40 at. % Co, 10 at. % Ce and Mg/Al atomic ratio of 3 were prepared via thermal decomposition at 750 °C in air of their corresponding layered double hydroxide (LDH) precursors obtained by coprecipitation. They were tested in a fixed bed reactor for complete methane oxidation with a gas feed of 1 vol.% methane in air to evaluate their catalytic performance. The physico-structural properties of the mixed oxide samples were investigated with several techniques, such as powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), elemental mappings, inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction under hydrogen (H₂-TPR) and nitrogen adsorption–desorption at −196 °C. XRD analysis revealed in all the samples the presence of Co₃O₄ crystallites together with periclase-like and CeO₂ phases, with no separate M-based oxide phase. All the cations were distributed homogeneously, as suggested by EDX measurements and elemental mappings of the samples. The metal contents, determined by EDX and ICP-OES, were in accordance with the theoretical values set for the catalysts’ preparation. The redox properties studied by H₂-TPR, along with the surface composition determined by XPS, provided information to elucidate the catalytic combustion properties of the studied mixed oxide materials. The methane combustion tests showed that all the M-promoted CoCeMgAlO mixed oxides were more active than the M-free counterpart, the highest promoting effect being observed for Fe as the doping transition metal. The Fe(x)CoCeMgAlO mixed oxide sample, with x = 3 at. % Fe displayed the highest catalytic activity for methane combustion with a temperature corresponding to 50% methane conversion, T₅₀, of 489 °C, which is ca. 40 °C lower than that of the unpromoted catalyst. This was attributed to its superior redox properties and lowest activation energy among the studied catalysts, likely due to a Fe–Co–Ce synergistic interaction. In addition, long-term tests of Fe(3)CoCeMgAlO mixed oxide were performed, showing good stability over 60 h on-stream. On the other hand, the addition of water vapors in the feed led to textural and structural changes in the Fe(3)CoCeMgAlO system, affecting its catalytic performance in methane complete oxidation. At the same time, the catalyst showed relatively good recovery of its catalytic activity as soon as the water vapors were removed from the feed. Full article

CO-selective methanation (CO-SMET) is an efficient hydrogen-rich (H₂-rich) gas purification technology for proton exchange membrane fuel cells. It is vital to develop suitable catalysts with good low-temperature activity for CO-SMET reactions. In this study, RuNi/TiZr_x-mixed metal oxide (RuNi/TiZr_x-MMO) catalysts with different molar ratios of Zr/Ti, derived from a Zr-promoted NiTi-layered double hydroxide (NiTi-LDH) precursor were successfully prepared using the co-precipitation and wet impregnation methods. The RuNi/TiZr_0.2-MMO catalyst possesses higher catalytic performance in a lower temperature window of 180–280 °C, which can reduce the CO concentration to be below 10 ppm. The characterization results obtained from XRD, BET, SEM, TEM, XPS, TPR, and TPD suggest that the addition of ZrO₂ increases the surface area of the catalyst, improves the dispersion of metallic nanoparticles, increases the reducibility of Ni species on the RuNi/TiZr_0.2-MMO catalyst’s surface, and enhances the adsorption and activation ability of CO, resulting in remarkable catalytic performance at lower reaction temperatures. Moreover, the RuNi/TiZr_0.2-MMO catalyst demonstrated long-term catalytic stability and carbon resistance. Full article

Acid–base M²⁺MgAlO and M²⁺AlO mixed oxides (where M²⁺ = Mg, Cu, Co, Zn, and Ni) were obtained by thermal decomposition of the corresponding layered double hydroxide (LDH) precursors and used as catalysts for cyclohexanol and benzaldehyde condensation under solvent-free conditions. The catalysts were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), and temperature-programmed desorption of CO₂ (TPD-CO₂). Gas chromatography–mass spectroscopy (GC/MS) was used for the identification and quantification of the product mixtures. In the reaction of cyclohexanol and benzaldehyde on M²⁺MgAlO and MgAlO catalysts, a 2,6-dibenzylidene-cyclohexanone was obtained as the main product as a result of consecutive one-pot dehydrogenation of cyclohexanol to cyclohexanone and subsequent Claisen–Schmidt condensation. In the reaction mixture obtained in the presence of NiAlO, CoAlO, and ZnAlO catalysts, a cyclohexyl ester of 6-hydroxyhexanoic acid was detected together with the main product. This is most likely a by-product obtained after the oxidation, ring opening, and subsequent esterification of the cyclohexanol. Full article

It is well-established that the structural, morphological and performance characteristics of nanoscale materials critically depend upon the dispersion state of the nanofillers that is, in turn, largely determined by the preparation protocol. In this report, we review synthetic strategies that capitalise on the in situ generation of nanoparticles on and within polymeric materials, an approach that relies on the chemical transformation of suitable precursors to functional nanoparticles synchronous with the build-up of the nanohybrid systems. This approach is distinctively different compared to standard preparation methods that exploit the dispersion of preformed nanoparticles within the macromolecular host and presents advantages in terms of time and cost effectiveness, environmental friendliness and the uniformity of the resulting composites. Notably, the in situ-generated nanoparticles tend to nucleate and grow on the active sites of the macromolecular chains, showing strong adhesion on the polymeric host. So far, this strategy has been explored in fabrics and membranes comprising metallic nanoparticles (silver, gold, platinum, copper, etc.) in relation to their antimicrobial and antifouling applications, while proof-of-concept demonstrations for carbon- and silica-based nanoparticles as well as titanium oxide-, layered double hydroxide-, hectorite-, lignin- and hydroxyapatite-based nanocomposites have been reported. The nanocomposites thus prepared are ideal candidates for a broad spectrum of applications such as water purification, environmental remediation, antimicrobial treatment, mechanical reinforcement, optical devices, etc. Full article

Catalytic total oxidation is an effective technique for the treatment of industrial VOCs principally resulting from industrial processes using solvents and usually containing mono-aromatics (BTEX) and oxygenated compounds (acetone, ethanol, butanone). The aim of this work is to deposit gold nanoparticles on CoAl mixed oxide issued from layered double hydroxide (LDH) precursor by using the deposition precipitation (DP) method, which is applied with two modifications, labeled method (A) and method (B), in order to enhance the interaction of the HAuCl₄ precursor with the support. Method (A) involves the hydrolysis of the HAuCl₄ precursor after addition of the support, while in method (B), the gold precursor is hydrolyzed before adding the support. The two methods were applied using as support the CoAl mixed oxide and the LDH precursor. Samples were characterized by several physical chemical techniques and evaluated for ethanol total oxidation. Method (B) allowed the ethanol oxidation activity to be enhanced for the resulting Au/CoAlOx catalysts thanks to the high surface concentration of Co²⁺ and improved reducibility at low temperature. The presence of gold permits to minimize the formation of by-products, notably, methanol, allowed for a total oxidation of ethanol at lower temperature than the corresponding support. Full article

Conobea scoparioides (Plantaginaceae) is an herbaceous plant known as “pataqueira” that grows wild in seasonally wet areas of the Amazon region. It is used for aromatic baths and anti-protozoan remedies by the Brazilian Amazon native people. The main volatile compounds identified in the essential oil of “Pataqueira” were the phenolic monoterpenes thymol and thymol methyl ether and their precursors, the monoterpene hydrocarbons α-phellandrene and p-cymene. A hydrotalcite synthesized from blast-furnace slag exhibited a 3:2 (Mg/Al) molar ratio, and this layered double hydroxide (LDH) was evaluated as a catalyst in converting the main monoterpenes of the “Pataqueira” oil. This action significantly increased the thymol content, from 41% to 95%, associated with the percentual reduction in other main components, such as thymol methyl ether, α-phellandrene, and p-cymene. The LDH reaction showed a strong tendency towards producing hydroxylated derivatives, and its behavior was similar to the hypothetical plant biosynthetic pathway, which leads to the production of the monoterpenes of “Pataqueira” oil. Thymol and its derivatives are potent antiseptics applied in pharmaceutical and hygienic products as antibacterial, antifungal, and antioxidant properties, among others. The present work reports a natural source with a high thymol content in aromatic plants from the Amazon, with evident economic value. Full article

The highly crystalline ZnAl layered double hydroxides (ZnAl-NO₃-LDHs) are utilized for the potential transformation into mixed metal oxides (MMOs) through thermal decomposition and used further for the photodegradation of phenol to assess the influence of calcination on ZnAl-LDHs with enhanced photoactivity. The structure, composition, and morphological evolution of ZnAl-LDHs to ZnO-based MMO nanocomposites, which are composed of ZnO and ZnAl₂O₄, after calcination at different temperatures (400–600 °C), are all thoroughly examined in this work. The final ZnO and ZnAl₂O₄-based nanocomposites showed enhanced photocatalytic activity. The findings demonstrated that calcining ZnAl-LDHs from 400 to 600 °C increased the specific surface area and also enhanced the interlayer spacing of d₀₀₃ while the transformation of LDHs into ZnO/ZnAl₂O₄ nanocomposites through calcining the ZnAl-LDH precursor at 600 °C showed significant photocatalytic properties, leading to complete mineralization of phenol under UV irradiation. Full article

Activated carbon (AC) compounds derived from biomass precursors have garnered significant attention as electrode materials in electric double-layer capacitors (EDLCs) due to their ready availability, cost-effectiveness, and potential for mass production. However, the accessibility of their active sites in electrochemistry has not been investigated in detail. In this study, we synthesized two novel macro/micro-porous carbon structures prepared from a chitosan precursor using an acid/potassium hydroxide activation process and then examined the relationship between their textural characteristics and capacitance as EDLCs. The material characterizations showed that the ACs, prepared through different activation processes, differed in porosity, with distinctive variations in particle shape. The sample activated at 800 °C (Act-chitosan) was characterized by plate-shaped particles, a specific surface area of 4128 m²/g, and a pore volume of 1.87 cm³/g. Assessment of the electrochemical characteristics of Act-chitosan showed its remarkable capacitance of 183.5 F/g at a scan rate of 5 mV/s, and it maintained exceptional cyclic stability even after 10,000 cycles. The improved electrochemical performance of both chitosan-derived carbon structures could thus be attributed to their large, well-developed active sites within pores < 2 nm, despite the fact that interconnected macro-porous particles can enhance ion accessibility on electrodes. Our findings provide a basis for the fabrication of biomass-based materials with promising applications in electrochemical energy storage systems. Full article