Search Results (19)

The oxidation of glycerol offers a valuable route for producing high-value chemicals. This review provides an in-depth analysis of the current advancements and mechanistic insights into novel metal-based catalysts for glycerol oxidation. We discuss the catalytic roles of both precious metals (e.g., Pt, Pd, Au), noted for their high efficiency and selectivity, and cost-effective alternatives, such as Ni, Cu, and Fe. Bimetallic and metal oxide catalysts are highlighted, emphasizing synergistic effects that enhance catalytic performance. This review elucidates the key mechanism involving selective adsorption and oxidation, providing detailed insights from advanced spectroscopic and computational studies into the activation of glycerol and stabilization of key intermediates, including glyceraldehyde and dihydroxyacetone. Additionally, selective carbon–carbon bond cleavage to yield smaller, valuable molecules is addressed. Finally, we outline future research directions, emphasizing the development of innovative catalysts, deeper mechanistic understanding, and sustainable process scale-up, ultimately advancing efficient, selective, and environmentally friendly catalytic systems for glycerol valorization. Full article

The aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) plays a pivotal role in the synthesis of renewable, biodegradable plastics and sustainable chemicals. Although supported gold nanoclusters (NCs) exhibit significant potential in this process, they often suffer from low selectivity. To address this challenge, a series of gold-M (M means Ni, Fe, Cu, and Pd) bimetallic NCs catalysts were designed and synthesized to facilitate the selective oxidation of HMF to FDCA. Our findings indicate that the introduction of doped metals, particularly Ni and Pd, not only improves the reaction rates for HMF tandem oxidation but also promotes high yields of FDCA. Various characterizations techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), in situ diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption (CO-DRIFTS), and temperature-programmed desorption of oxygen (O₂-TPD), were employed to scrutinize the structural and electronic properties of the prepared catalysts. Notably, an electronic effect was observed across the Au-based bimetallic catalysts, facilitating the activation of reactant molecules and enhancing the catalytic performance. This study provides valuable insights into the alloy effects, aiding in the development of highly efficient Au-based bimetallic catalysts for biomass conversions. Full article

Bimetallic AuCu/SiO₂ nanosized catalysts were prepared using the wet chemical reduction technique. From among Au_0.1–1.5Cu₁₀/SiO₂ catalysts, the Au_0.5Cu₁₀/SiO₂ catalyst gave the highest yield of calcium lactate of 87% at a glycerol conversion of 96% when the reaction of glycerol with calcium hydroxide at a mole ratio of calcium hydroxide to glycerol of 0.8:1 was conducted under an anaerobic atmosphere at 200 °C for 2 h. The interactions between metallic Au⁰ and Cu⁰ nanoparticles facilitate calcium lactate formation. The simulation of glycerol consumption rate with an empirical power-function reaction kinetics equation yielded a reaction activation energy of 44.3 kJ∙mol⁻¹, revealing that the catalytic reaction of glycerol with calcium hydroxide to calcium lactate can be conducted by overcoming a mild energy barrier. The synthesis of calcium lactate through the catalytic reaction of glycerol with calcium hydroxide on a bimetallic AuCu/SiO₂ nanosized catalyst under a safe anaerobic atmosphere is an alternative to the conventional calcium lactate production technique through the reaction of expensive lactic acid with calcium hydroxide. Full article

This review extensively discusses current developments in bimetallic nanoparticle–GO and bimetallic nanoparticle–MOF nanocomposites as potential catalysts for HER, along with their different synthesis methodologies, structural characteristics, and catalytic mechanisms. The photoelectrocatalytic performance of these catalysts was also compared based on parameters such as Tafel slope, current density, onset potential, turnover frequency, hydrogen yield, activation energy, stability, and durability. The review shows that the commonly used metal alloys in the bimetallic nanoparticle–GO-based catalysts for HERs include Pt-based alloys (e.g., PtNi, PtCo, PtCu, PtAu, PtSn), Pd-based alloys (e.g., PdAu, PdAg, PdPt) or other combinations, such as AuNi, AuRu, etc., while the most used electrolyte sources are H₂SO₄ and KOH. For the bimetallic nanoparticle MOF-based catalysts, Pt-based alloys (e.g., PtNi, PtCu), Pd-based alloys (e.g., PdAg, PdCu, PdCr), and Ni-based alloys (e.g., NiMo, NiTi, NiAg, NiCo) took the lead, with KOH being the most frequently used electrolyte source. Lastly, the review addresses challenges and prospects, highlighting opportunities for further optimization and technological integration of the catalysts as promising alternative photo/electrocatalysts for future hydrogen production and storage. Full article

The incorporation of the metal phase into cellulose hydrogels, resulting in the formation of metallogels, greatly expands their application potential by introducing new functionalities and improving their performance in various fields. The unique antiviral, antibacterial, antifungal, and anticancer properties of metal and metal oxide nanoparticles (Ag, Au, Cu, Cu_xO_y, ZnO, Al₂O₃, TiO₂, etc.), coupled with the biocompatibility of cellulose, allow the development of composite hydrogels with multifunctional therapeutic potential. These materials can serve as efficient carriers for controlled drug delivery, targeting specific cells or pathogens, as well as for the design of artificial tissues or wound and burn dressings. Cellulose-based metallogels can be used in the food packaging industry to provide biodegradable and biocidal materials to extend the shelf life of the goods. Metal and bimetallic nanoparticles (Au, Cu, Ni, AuAg, and AuPt) can catalyze chemical reactions, enabling composite cellulose hydrogels to be used as efficient catalysts in organic synthesis. In addition, metal-loaded hydrogels (with ZnO, TiO₂, Ag, and Fe₃O₄ nanoparticles) can exhibit enhanced adsorption capacities for pollutants, such as dyes, heavy metal ions, and pharmaceuticals, making them valuable materials for water purification and environmental remediation. Magnetic properties imparted to metallogels by iron oxides (Fe₂O₃ and Fe₃O₄) simplify the wastewater treatment process, making it more cost-effective and environmentally friendly. The conductivity of metallogels due to Ag, TiO₂, ZnO, and Al₂O₃ is useful for the design of various sensors. The integration of metal nanoparticles also allows the development of responsive materials, where changes in metal properties can be exploited for stimuli-responsive applications, such as controlled release systems. Overall, the introduction of metal phases augments the functionality of cellulose hydrogels, expanding their versatility for diverse applications across a broad spectrum of industries not envisaged during the initial research stages. Full article

Plasmonic gold (Au) and Au-based nanocatalysts have received significant attention over the past few decades due to their unique visible light (VL) photocatalytic features for a wide variety of chemical reactions in the fields of environmental protection. However, improving their VL photocatalytic activity via a rational design is prevalently regarded as a grand challenge. Herein we boosted the VL photocatalysis of the TiO₂-supported Au-Cu nanocatalyst by applying O₂ plasma to treat this bimetallic plasmonic nanocatalyst. We found that O₂ plasma treatment led to a strong interaction between the Au and Cu species compared with conventional calcination treatment. This interaction controlled the size of plasmonic metallic nanoparticles and also contributed to the construction of AuCu-TiO₂ interfacial sites by forming AuCu alloy nanoparticles, which, thus, enabled the plasmonic Au-Cu nanocatalyst to reduce the Schottky barrier height and create numbers of highly active interfacial sites. The catalyst’s characterizations and density functional theory (DFT) calculations demonstrated that boosted VL photocatalytic activity over O₂ plasma treated Au-Cu/TiO₂ nanocatalyst arose from the favorable transfer of hot electrons and a low barrier for the reaction between CO and O with the construction of large numbers of AuCu-TiO₂ interfacial sites. This work provides an efficient approach for the rational design and development of highly active plasmonic Au and Au-based nanocatalysts and deepens our understanding of their role in VL photocatalytic reactions. Full article

The role of ion-exchange resins (IERs) as catalysts or catalysts supports, in hydrogenation reactions is revised and their potential application is presented. Both gel-type and macroreticular, basic or acid, IERs have been used for manifold metal-catalyzed hydrogenation processes in gas and liquid phase, including hydrogenation of alkenes, alkynes, carbonyls, arenes, nitroaromatics, and more. When available, qualitative relationships between the morphology and structure of resins and their performance as solid supports for metal catalysts are observed. Noble metals, such as Pt, Au, and Pd, and non-noble metals, such as Fe and Cu, have been introduced into IERs polymeric backbones by simple ion-exchange of a metal salt precursor with the resin, or by a combination of ion-exchange and other protocols, to obtain mono- and bimetallic catalysts supported on IERs. High yields towards target product, as well as the recyclability of metal-doped IERs, have been reported in the literature, with low metal leaching, which makes them highly interesting solid catalysts for a wide array of industrial applications. Multistep reaction processes, involving hydrogenation and hydration/cyclization/aldol condensation/etc., constitute promising applications due to the one-pot synthesis approach and relatively low temperatures required, which adds environmental interest in terms of process integration and optimization. Full article

The challenge of improving the activity of TiO₂ by modifying it with metals and using it for targeted applications in microreactor environments is an active area of research. Recently, microreactors have emerged as successful candidates for many photocatalytic reactions, especially for the selective oxidation process. The current work introduces ultrasound-assisted catalyst deposition on the inner walls of a perfluoro-alkoxy alkane (PFA) microtube under mild conditions. We report Cu-Au/TiO₂ and Fe-Au/TiO₂ nanoparticles synthesized using the sol–gel method. The obtained photocatalysts were thoroughly characterized by UV–Vis diffuse-reflectance spectroscopy (DRS), high-resolution scanning electron microscopy (HR-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and N₂ physisorption. The photocatalytic activity under UV (375 nm) and visible light (515 nm) was estimated by the oxidation of lignin-based model aromatic alcohols in batch and fluoropolymer-based flow systems. The bimetallic catalyst exhibited improved photocatalytic selective oxidation. Herein, four aromatic alcohols were individually investigated and compared. In our experiments, the alcohols containing hydroxy and methoxy groups (coniferyl and vanillin alcohol) showed high conversion (93% and 52%, respectively) with 8% and 17% selectivity towards their respective aldehydes, with the formation of other side products. The results offer an insight into ligand-to-metal charge transfer (LMCT) complex formation, which was found to be the main reason for the activity of synthesized catalysts under visible light. Full article

With a focus on catalysts prepared by an excess-chloride wet impregnation procedure and supported on the zeolite ZSM-5(30), the introduction of low concentrations of tertiary base metals, in particular Cu, into supported AuPd nanoparticles can be observed to enhance catalytic activity towards the direct synthesis of H₂O₂. Indeed the optimal catalyst formulation (1%AuPd_(0.975)Cu_(0.025)/ZSM-5) is able to achieve rates of H₂O₂ synthesis (115 mol_H2O2kg_cat⁻¹h⁻¹) approximately 1.7 times that of the bi-metallic analogue (69 mol_H2O2kg_cat⁻¹h⁻¹) and rival that previously reported over comparable materials which use Pt as a dopant. Notably, the introduction of Cu at higher loadings results in an inhibition of performance. Detailed analysis by CO-DRFITS and XPS reveals that the improved performance observed over the optimal catalyst can be attributed to the electronic modification of the Pd species and the formation of domains of a mixed Pd²⁺/Pd⁰ oxidation state as well as structural changed within the nanoalloy. Full article

This work addresses the Suzuki cross-coupling between 4-bromoanisole (BrAn) and phenylboronic acid (PBA) in an environmentally benign ethanol–water solvent catalysed by mono- (Pd) and bimetallic (PdAu, PdCu, PdZn) nanoparticles (NPs) stabilised within hyper-cross-linked polystyrene (HPS) bearing tertiary amino groups. Small Pd NPs of about 2 nm in diameters were formed and stabilized by HPS independently in the presence of other metals. High catalytic activity and complete conversion of BrAn was attained at low Pd loading. Introduction of Zn to the catalyst composition resulted in the formation of Pd/Zn/ZnO NPs, which demonstrated nearly double activity as compared to Pd/HPS. Bimetallic core-shell PdAu/HPS samples were 3-fold more active as compared to Pd/HPS. Both Pd/HPS and PdAu/HPS samples revealed promising stability confirmed by catalyst recycling in repeated reaction runs. Full article

Three bimetallic catalysts of the type M–Cu with M = Ag, Au and Ni supports were successfully prepared by a two-step synthesized method using Cu/Al₂O₃-CeO₂ as the base monometallic catalyst. The nanocatalysts were characterized using X-ray diffraction (XRD), temperature-programmed reduction of H₂ (H₂-TPR), N₂ adsorption-desorption, scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and ultraviolet–visible spectroscopy with diffuse reflectance (DR-UV-Vis) techniques. This synthesized methodology allowed a close interaction between two metals on the support surface; therefore, it could have synthesized an efficient transition–noble mixture bimetallic nanostructure. Alloy formation through bimetallic nanoparticles (BNPs) of AgCuAlCe and AuCuAlCe was demonstrated by DR–UV–Vis, EDS, TEM and H₂-TPR. Furthermore, in the case of AgCuAlCe and AuCuAlCe, improvements were observed in their reducibility, in contrast to NiCuAlCe. The addition of a noble metal over the monometallic copper-based catalyst drastically improved the phenol mineralization. The higher activity and selectivity to CO₂ of the bimetallic gold–copper- and silver–copper-supported catalysts can be attributed to the alloy compound formation and the synergetic effect of the M–Cu interaction. Petroleum Refinery Wastewater (PRW) had a complex composition that affected the applied single CWAO treatment, rendering it inefficient. Full article

The catalytic properties of nanoparticles depend on their size, shape and surface/defect structure, with the entire catalyst performance being governed by the corresponding distributions. Herein, we present two routes of mono- and bimetallic nanoparticle synthesis that enable control of the structural parameters, i.e., wet-chemical synthesis and laser ablation in liquid-phase. The latter is particularly suited to create defect-rich nanoparticles. Impregnation routes were applied to prepare Ni and NiCu nanoparticles, whereas nano- and femtosecond laser ablation in liquid-phase were employed to prepare Ni and NiAu nanoparticles. The effects of the Ni:Cu ratio in impregnation and of laser fluence and liquid-medium on laser ablation are discussed. The atomic structure and (surface) composition of the nanoparticles were characterized by electron microscopic (BF-TEM, DF-TEM, HRTEM) and spectroscopic/diffraction techniques (EDX, SAED, XPS, IR), complemented by theory (DFT). The chemically synthesized bimetallic NiCu nanoparticles initially had Cu-rich surfaces, which changed to Ni-rich upon reaction. For laser ablation, depending on conditions (fluence, type of liquid), highly defective, ordered, or core/shell-like nanoparticles were produced. The case studies highlight the specific benefits of each preparation method for catalyst synthesis and discuss the potential of nanoparticles produced by pulsed laser ablation for catalytic applications. Full article

The selective oxidation of veratryl alcohol as lignin-derived compound was studied under mild conditions, using Au-Cu catalysts synthesized from pre-formed nanoparticles with different Au:Cu molar ratios. Bimetallic catalysts show higher activity compared to monometallic counterparts, highlighting a clear synergistic effect. By comparing the physico-chemical surface properties of catalysts supported on carbon and Al₂O₃, we were able to establish a strong support effect, with alumina-based catalysts being more active than carbon-supported ones. Moreover, TEM and X-ray photoelectron spectroscopy (XPS) analyses showed a different composition of nanoparticles (NPs) and metal exposure, and we established that Au is the active phase of the reaction. The co-presence of Au and Cu species, and their different interaction with the support, enabled obtaining more than 70% conversion of veratryl alcohol to veratryl aldehyde as a unique product. Moreover, the Au₁Cu₁ supported on alumina catalyst was recovered by filtration and reused without significant loss of activity and selectivity up to four times. Full article

Dimethyl disulfide (DMDS, CH₃SSCH₃) is an odorous and harmful air pollutant (volatile organic compound (VOC)) causing nuisance in urban areas. The abatement of DMDS emissions from industrial sources can be realized through catalytic oxidation. However, the development of active and selective catalysts having good resistance toward sulfur poisoning is required. This paper describes an investigation related to improving the performance of Pt and Cu catalysts through the addition of Au to monometallic “parent” catalysts via surface redox reactions. The catalysts were characterized using ICP-OES, N₂ physisorption, XRD, XPS, HR-TEM, H₂-TPR, NH₃-TPD, CO₂-TPD, and temperature-programmed ¹⁸O₂ isotopic exchange. The performance of the catalysts was evaluated in DMDS total oxidation. In addition, the stability of a Pt–Au/Ce–Al catalyst was investigated through 40 h time onstream. Cu–Au catalysts were observed to be more active than corresponding Pt–Au catalysts based on DMDS light-off experiments. However, the reaction led to a higher amount of oxygen-containing byproduct formation, and thus the Pt–Au catalysts were more selective. H₂-TPR showed that the higher redox capacity of the Cu-containing catalysts may have been the reason for better DMDS conversion and lower selectivity. The lower amount of reactive oxygen on the surface of Pt-containing catalysts was beneficial for total oxidation. The improved selectivity of ceria-containing catalysts after the Au addition may have resulted from the lowered amount of reactive oxygen as well. The Au addition improved the activity of Al₂O₃-supported Cu and Pt. The Au addition also had a positive effect on SO₂ production in a higher temperature region. A stability test of 40 h showed that the Pt–Au/Ce–Al catalyst, while otherwise promising, was not stable enough, and further development is still needed. Full article

Development of a sustainable process for designing and synthesising an active and stable catalyst for hydrochlorination of acetylene is challenging, yet crucial, for industrial vinyl chloride monomer (VCM) production. Herein, direct synthesis of bimetallic AuCu catalysts using organic aqua regia (OAR) preparation methods was investigated. In comparison with conventional aqua regia (AR), bimetallic AuCu catalysts synthesised from OAR exhibit enhanced activity and stability. After careful characterisation of the catalyst samples using X-ray diffraction patterns (XRD), Scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), and Temperature-programmed desorption (TPD), this observation was justified for the following reasons: 1) the existence of sulphur and nitrogen atoms stabilised the cationic Au active sites, and 2) OAR helped to sustain the function of the Cu promotor by stabilising it. Advanced understanding on the importance of promoter stability has unveiled new perspectives for this research area. Full article