Search Results (46)

Metal carbonyl clusters, which can be seen as monodispersed and atomically defined nanoparticles stabilized by CO ligands, were used to prepare Ru-based catalysts with tuned basic properties to conduct the 5-hydroxymethylfurfural (HMF) aerobic oxidation to produce 2,5-furandicarboxylic acid (FDCA) in base-free conditions. The controlled decomposition of the carbonyl cluster [HRu₃(CO)₁₁]⁻, a methodology not yet applied to Ru catalysts for this reaction, on different supports focusing on controlling and tuning the basic properties of support allowed the formation of small Ru nanoparticles with a mean diameter of around 1 nm. The catalytic systems obtained resulted in more activity in the HMF oxidation than those prepared through a more common salt-impregnation technique, and the deposition of Ru nanoparticles on materials with basic functionalities has allowed avoiding the use of basic solutions in the reaction. The characterization by CO₂-TPD of Mg(Al)O catalysts obtained from decomposition of layered double hydroxide hydrotalcites with different composition and activation has allowed disclosure of an important correlation between the selectivity of FDCA and the fraction of weak basic sites, which is decreased by the calcination treatment at increased temperature. Full article

Understanding the microscopic structure and physical–chemical properties of materials with nanoconfined domains is essential for advancing technologies in catalysis, nanomaterial design, and pharmaceutical applications. Layered double hydroxides (LDHs) are promising candidates for such innovations due to their tunable interlayer environment, which can be precisely controlled by varying the type of intercalated anion and the amount of water present. However, optimizing LDH-based technologies requires detailed insights into the local structure within the interlayer region, where complex interactions occur among anions, water molecules, and the inorganic surfaces. In this work, we present a comprehensive computational study of LDHs intercalating small inorganic anions at varying hydration levels, using atomistic molecular dynamics simulations. Our findings show good agreement with existing experimental and simulation data. We observe that monoatomic ions form either a monolayered or double-layered structures, with water molecules lying flat at low hydration and adopting more disordered configurations near the surfaces at higher hydration. In contrast, polyatomic anions exhibit distinct structural behaviors: nitrates adopt tilted orientations and form double layers at high hydration, similar to perchlorates, while carbonates consistently remain flat. Additionally, water molecules strongly interact with both anions and the surface, whereas anion–surface interactions weaken slightly as hydration increases. These results offer valuable insights into the local structural dynamics of LDHs, paving the way for more efficient design and application of these versatile materials. Full article

In the search for technologies and materials to improve the safety and efficacy of active ingredients used in treating diseases, layered double hydroxides (LDHs) have been proposed as drug carriers since they can enhance the effects of active ingredients and even reduce toxicity. Doxorubicin (DOX) is one of the most widely used and studied antitumor drugs due to its broad spectrum; however, due to its low plasma bioavailability and slow systemic clearance, only a small fraction of the drug reaches and acts on the tumor, so LDHs have been proposed as vehicles to solve these disadvantages. The most used method to load the drug is incubating LDH particles in DOX solutions. In this work, two additional methods, co-precipitation, and mechanochemical reaction, were explored to evaluate the structural stability of the vehicle and the amount of DOX retained by LDHs structured by magnesium/aluminum and zinc/aluminum cations, which are the two most common compositions to design materials for biomedical applications. The zinc/aluminum LDH structure degraded in the loading process, whereas the magnesium/aluminum LDH particles were stable against the three loading processes. The mechanochemical procedure, a green and sustainable technology, loaded the highest content of DOX. Full article

The plant pathogenic fungus Botrytis cinerea causes significant losses in agricultural production and it is rather difficult to control due to its broad host range and environmental persistence. The management of gray mold disease is still mainly based on the use of chemicals, which could have harmful effects not only due to impacts on the environment and human health, but also because they favor the development of fungicide-resistant strains. In this scenario, the strategy of RNA interference (RNAi) is being widely considered, and Spray-Induced Gene Silencing (SIGS) is gaining interest as a versatile, sustainable, effective, and environmentally friendly alternative to the use of chemicals in the protection of crops. The SIGS approach was evaluated to control B. cinerea infection on lettuce plants. In vitro-synthesized dsRNA molecules (BcBmp1-, BcBmp3-, and BcPls1-dsRNAs) were used naked, or complexed to small layered double hydroxide (sLDH) clay nanosheets. Therefore, treatments were applied by pressure spraying whole lettuce plants lately inoculated with B. cinerea. All sprayed dsRNAs proved effective in reducing disease symptoms with a notable reduction compared to controls. The effectiveness of SIGS in reducing disease caused by B. cinerea was high overall and increased significantly with the use of sLDH clay nanosheets. The sLDH clay nanosheet–dsRNA complexes showed better plant protection over time compared to the use of naked dsRNA and this was particularly evident at 27 days post-inoculation. RNAi-based biocontrol could be an excellent alternative to chemical fungicides, and several RNAi-based products are expected to be approved soon, although they will face several challenges before reaching the market. Full article

The increasing challenges posed by plant viral diseases demand innovative and sustainable management strategies to minimize agricultural losses. Exogenous double-stranded RNA (dsRNA)-mediated RNA interference (RNAi) represents a transformative approach to combat plant viral pathogens without the need for genetic transformation. This review explores the mechanisms underlying dsRNA-induced RNAi, highlighting its ability to silence specific viral genes through small interfering RNAs (siRNAs). Key advancements in dsRNA production, including cost-effective microbial synthesis and in vitro methods, are examined alongside delivery techniques such as spray-induced gene silencing (SIGS) and nanocarrier-based systems. Strategies for enhancing dsRNA stability, including the use of nanomaterials like layered double hydroxide nanosheets and carbon dots, are discussed to address environmental degradation challenges. Practical applications of this technology against various plant viruses and its potential to ensure food security are emphasized. The review also delves into regulatory considerations, risk assessments, and the challenges associated with off-target effects and pathogen resistance. By evaluating both opportunities and limitations, this review underscores the role of exogenous dsRNA as a sustainable solution for achieving viral disease resistance in plants. Full article

Air pollutants are usually formed by easily spreading small molecules, representing a severe problem for human health, especially in urban centers. Despite the efforts to stem their diffusion, many diseases are still associated with exposure to these molecules. The present study focuses on modeling and designing two-dimensional systems called Layered Double Hydroxides (LDHs), which can potentially trap these molecules. For this purpose, a Density Functional Theory (DFT) approach has been used to study the role of the elemental composition of LDHs, the type of counterion, and the ability of these systems to intercalate NO₂ and SO₂ between the LDH layers. The results demonstrated how the counterion determines the different possible spacing between the layers, modulating the internalization capacity of pollutants and determining the stability degree of the system for a long-lasting effect. The variations in structural properties, the density of states (DOS), and the description of the charge transfer have been reported, thus allowing the investigation of aspects that are difficult to observe from an experimental point of view and, at the same time, providing essential details for the effective development of systems that can counteract the spread of air pollutants. Full article

Nanoclay, a processed clay, is utilized in numerous high-performance cement nanocomposites. This clay consists of minerals such as kaolinite, illite, chlorite, and smectite, which are the primary components of raw clay materials formed in the presence of water. In addition to silica, alumina, and water, it also contains various concentrations of inorganic ions like Mg²⁺, Na⁺, and Ca²⁺. These are categorized as hydrous phyllosilicates and can be located either in interlayer spaces or on the planetary surface. Clay minerals are distinguished by their two-dimensional sheets and tetrahedral (SiO₄) and octahedral (Al₂O₃) crystal structures. Different clay minerals are classified based on the presence of tetrahedral and octahedral layers in their structure. These include kaolinite, which has a 1:1 ratio of tetrahedral to octahedral layers, the smectite group of clay minerals and chlorite with a 2:1 ratio. Clay minerals are unique due to their small size, distinct crystal structure, and properties such as high cation exchange capacity, adsorption capacity, specific surface area, and swelling behavior. These characteristics are discussed in this review. The use of nanoclays as nanocarriers for fertilizers boasts a diverse array of materials available in both anionic and cationic variations. Layered double hydroxides (LDH) possess a distinctive capacity for exchanging anions, making them suitable for facilitating the transport of borate, phosphate, and nitrate ions. Liquid nanoclays are used extensively in agriculture, specifically as fertilizers, insecticides, herbicides, and nutrients. These novel nanomaterials have numerous benefits, including improved nutrient use, controlled nutrient release, targeted nutrient delivery, and increased agricultural productivity. Arid regions face distinct challenges like limited water availability, poor soil quality, and reduced productivity. The addition of liquid nanoclay to sandy soil offers a range of benefits that contribute to improved soil quality and environmental sustainability. Liquid nanoclay is being proposed for water management in arid regions, which will necessitate a detailed examination of soil, water availability, and hydrological conditions. Small-scale trial initiatives, engagement with local governments, and regular monitoring are required to fully comprehend its benefits and drawbacks. These developments would increase the practicality and effectiveness of using liquid nanoclay in desert agriculture. Full article

Developing high-performance and cost-competitive electrocatalysts have great significance for the massive commercial production of water-splitting hydrogen. Ni-based electrocatalysts display tremendous potential for electrocatalytic water splitting. Herein, we synthesize a novel NiFe-layered double hydroxide (LDH) electrocatalyst in nanosheets array on high-purity Ni foam. By adjusting the Ni/Fe ratio, the microstructure, and even the behavior of the electrocatalyst in the oxygen evolution reaction (OER), changes significantly. The as-obtained material shows a small overpotential of 223 mV at 10 mAcm⁻² as well as a low Tafel slope of 48.9 mV·dec⁻¹ in the 1 M KOH electrolyte. In addition, it can deliver good stability for at least 24 h of continuous working at 10 mAcm⁻². This work proposes a strategy for engineering catalysts and provides a method for the development of other Ni-based catalysts with excellent performance. Full article

Layered double hydroxides (LDHs) are fascinating clay-like materials that display versatile properties, making them an extremely fertile playground for diverse applications, ranging from bio-compatible materials to the pharmaceutical industry to catalysis and photocatalysis. When intercalating organic and bio-organic species between the inorganic layers, such materials are named hybrid LDHs. The structure–property relation in these systems is particularly relevant, since most of the properties of the materials may be fine-tuned if a comprehensive understanding of the microscopic structure in the interlamellar space is achieved, especially with respect to the reorganization under water uptake (swelling). In this work, we combined experiments and simulations to rationalize the behavior of LDHs intercalating three carboxylates, the general structure of which can be given as $\left[{\mathrm{Mg}}_4{\mathrm{Al}}_2{\left(\mathrm{OH}\right)}_{12}\right]{\mathrm{A}}^{2-}$·${\mathrm{XH}}_2$O (with ${\mathrm{A}}^{2-}$ = succinate, aspartate, or glutamate and X representing increasing water content). Following this strategy, we were able to provide an interpretation of the different shapes observed for the experimental water adsorption isotherms and for the evolution of the infrared carboxylate band of the anions. Apart from small differences, due to the different reorganization of the conformational space under confinement, the behavior of the two amino acids is very similar. However, such behavior is quite different in the case of succinate. We were able to describe the different response of the anions, which has a significant impact on the isotherm and on the size of the interlamellar region, in terms of a different interaction mechanism with the inorganic layer. Full article

Graphene materials, used as electrocatalyst support in green hydrogen production, contribute to increasing the efficiency and robustness of various systems. However, the preparation of a hybrid catalyst containing graphene materials from industrial wastes is still a challenge due to the heterogeneity of the waste. We report the synthesis of 3D electrodes using graphene oxides (GOs) from industrial waste (IW) prepared by immersion onto Toray carbon paper as a 3D support onto GO suspensions and electrodepositing NiFe layered double hydroxides (LDHs). Standard graphite was also used as the reference. The morphology of the two hybrid electrodes was determined by SEM, HRTEM, XPS. Although very similar in both, the sample containing graphene from IW (higher Csp³ hybridization in the graphene layer) has a NiFe phase with less crystallinity and larger presence of Fe²⁺ ions. These electrodes exhibited similar activity and stability as electrocatalysts of the oxygen evolution reaction (OER), demonstrating the proactive effect of the graphene into the 3D electrode even when this is prepared from heterogeneous industrial waste. Moreover, the defective graphenic structure of the waste GO enhances the reaction kinetics and improves the electron transfer rate, possibly due to the small differences in the electrodeposited NiFe LDH structure. Full article

The oxygen evolution reaction (OER) is a slow step in electrocatalytic water splitting. NiFe layered double hydroxides (LDH) have shown promise as affordable OER electrocatalysts, but their performance is hindered by poor charge transfer and sluggish kinetics. To address this, we doped NiFe LDH with sulfur (S) using an in situ electrodeposition method. By growing S-doped NiFe LDH on Cu nanoarrays, we created core–shell structures that improved both the thermodynamics and kinetics of OER. The resulting S-NiFe LDH@Cu core–shell nanoarrays exhibited enhanced activity in water oxidation, with a low potential of 236 mV (at 50 mA cm⁻²) and a small Tafel slope of 50.64 mV dec⁻¹. Moreover, our alkaline electrolyzer, based on these materials, demonstrated remarkable activity, with a low voltage of 1.56 V at 100 mA cm⁻² and excellent durability. The core–shell nanoarray structures provided a larger electroactive surface area, facilitated fast electron transport, and allowed for effective gas release. These findings highlight the potential of S-NiFe LDH@Cu core–shell nanoarrays as efficient OER electrocatalysts. Full article

The oxygen evolution reaction (OER) is a key half-reaction in electrocatalytic water splitting. Large-scale water electrolysis is hampered by commercial noble-metal-based OER electrocatalysts owing to their high cost. To address these issues, we present a facile, one-pot, room-temperature co-precipitation approach to quickly synthesize carbon-nanotube-interconnected amorphous NiFe-layered double hydroxides (NiFe-LDH@CNT) as cost-effective, efficient, and stable OER electrocatalysts. The hybrid catalyst NiFe-LDH@CNT delivered outstanding OER activity with a low onset overpotential of 255 mV and a small Tafel slope of 51.36 mV dec⁻¹, as well as outstanding long-term stability. The high catalytic capability of NiFe-LDH@CNT is associated with the synergistic effects of its room-temperature synthesized amorphous structure, bi-metallic modulation, and conductive CNT skeleton. The room-temperature synthesis can not only offer economic feasibility, but can also allow amorphous NiFe-LDH to be obtained without crystalline boundaries, facilitating long-term stability during the OER process. The bi-metallic nature of NiFe-LDH guarantees a modified electronic structure, providing additional catalytic sites. Simultaneously, the highly conductive CNT network fosters a nanoporous structure, facilitating electron transfer and O₂ release and enriching catalytic sites. This study introduces an innovative approach to purposefully design nanoarchitecture and easily synthesize amorphous transition-metal-based OER catalysts, ensuring their cost effectiveness, production efficiency, and long-term stability. Full article

Layered double hydroxides (LDHs) present exciting possibilities across various industries, ranging from catalytic applications to water remediation. By immobilizing nanoparticles, LDHs’ characteristics and functionality can be enhanced, allowing for synergetic interactions that further expand their potential uses. A simple chemical method was developed to produce well-dispersed Pd-Cu NPs on a Co-Cr LDH support using a combination of in situ coprecipitation/hydrothermal and sol-immobilization techniques. The Pd-Cu@Co-Cr LDH catalysts was obtained, showing its catalytic activity in promoting the aerobic oxidation of alcohols and enabling the reduction of nitro-compounds through NaBH₄ mediation. The physicochemical properties of the prepared catalyst were comprehensively investigated utilizing a range of analytical techniques, comprising FTIR, XRD, XPS, TGA, nitrogen adsorption isotherm, FESEM, and HRTEM-EDX. The findings showed the significance of immobilizing the bimetallic Pd-Cu nanoparticles on the Co-Cr LDH via an exceptional performance in the aerobic oxidation of benzyl alcohol (16% conversion, 99.9% selectivity to benzaldehyde) and the reduction of nitrobenzene (98.2% conversion, rate constant of 0.0921 min⁻¹). The improved catalytic efficacy in benzyl alcohol oxidation and nitrobenzene reduction on the Pd-Cu@Co-Cr LDH catalyst is attributed to the uniform distribution and small size of the Pd-Cu NPs as active sites on the Co-Cr LDH surface. The prepared catalyst demonstrated exceptional stability during repeated runs. This study paves the way for multiple opportunities in tailoring, producing, and precisely controlling catalysts for various organic transformation reactions. Full article

The design of high-performance and low-cost oxygen evolution reaction (OER) electrocatalysts is crucial for environment friendly hydrogen production. Some transition metals have been proven to be good substitutes for noble metals due to their unique electronic structural characteristics and good electrocatalytic performances, with examples including nickel and cobalt, which are usually used to prepare OER electrocatalysts. In this work, we synthesized three-dimensional Ni-Co-Fe ternary layered double hydroxide nanosheet array electrocatalysts via hydrothermal process. Iron element was introduced into the Ni-Co based hydroxide. The ternary layered double hydroxide has a nanoarrays microstructure. Theoretical analysis confirms that by adjusting the ratio of Ni/Co/Fe, the microstructure of the catalyst changes significantly. Attributed to the special nanostructure, the catalysts show superior catalytic activities in oxygen evolution reaction (OER). The results show that a small overpotential of 222 mV at the current density of 20 mA·cm⁻² for the OER in 1.0 M KOH is acquired. A small Tafel slope of 61.22 mVdec⁻¹ and a maximum specific capacitance of 239 Fg⁻¹ are also obtained. Full article

In the present study, Mg-Al layered double hydroxide (Mg-Al/LDH) was synthesized on the surface of AZ31 Mg alloy substrate via in-situ hydrothermal treatment. Synthesis parameters were changed to determine their effect on the lateral size of LDH. For this purpose, etching in nitric acid and anodizing in sodium hydroxide solution were performed as surface pretreatments. Moreover, the influence of LDH solution pH (10 and 11) on the lateral size of LDH coating was investigated. Morphology, chemical composition, and crystalline structure were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD). The corrosion resistance of the coatings was investigated by H₂ measurements, salt spray, and electrochemical impedance spectroscopy (EIS). Moreover, the epoxy coating was applied on the best anti-corrosive LDH sample for assessing the compatibility and effectiveness of LDH on the corrosion properties of the substrate with the epoxy layer. At pH = 11, the lateral size of LDH was smaller than samples at pH = 10. In addition, small-sized LDH, as well as LDH/epoxy coating, revealed enhanced corrosion protection. Full article