Search Results (155)

Titanium, the second most abundant and one of the cheapest, non-toxic transition metals in the Earth’s crust, is highly favorable for catalytic applications due to its widespread availability, low cost, low toxicity, and well-documented biocompatibility. However, because of its high affinity for oxygen and inherent Lewis acidity, titanium complexes generally exhibit lower tolerance toward various functional groups compared with complexes of later transition metals. The incorporation of cyclopentadienyl ligands significantly enhances the structural tunability of these complexes in their 3D configuration. By modifying the ligand framework, it is possible to fine-tune the Lewis acidity of the central titanium atom as well as the lability and binding characteristics of the ligands. This strategy enables precise control over the catalytic performance of titanocene complexes. The main body of this review provides an overview of recent advances in titanocene catalysis within the field of chemical synthesis since 2019. It includes illustrative examples that demonstrate the substrate scope and practical applications of titanocene catalysts in the synthesis of complex organic molecules and natural products. Finally, the review outlines current research opportunities and strategic directions for future developments in titanocene-based catalysis. Full article

In this study, a novel magnetic nanocatalyst based on tin ferrite (SnFe₂O₄) was synthesized via a chemical co-precipitation method and thoroughly characterized using XRD, SEM, TGA-DTG, BET, FTIR, and FTIR-pyridine techniques. The catalyst exhibited high crystallinity, a mesoporous structure with a specific surface area of 79.7 m²/g, and well-defined Lewis and Brønsted acid sites. Its catalytic performance was assessed in the esterification of glycerol with acetic acid to produce monoacetin (MAG), diacetin (DAG), and triacetin (TAG). A Box–Behnken experimental design was employed to evaluate the influence of temperature, catalyst loading, and the acetic-acid-to-glycerol molar ratio on product distribution and glycerol conversion. Statistical analysis and regression modeling revealed excellent predictive accuracy (R² > 0.99), confirming the robustness of the model. Optimal reaction conditions (110 °C, 2 wt.% catalyst, and AA/GLY ratio of 3.6) yielded a maximum glycerol conversion of 93.2% and a combined DAG and TAG yield of ~59.1%. These results demonstrate the high efficiency and selectivity of the synthesized SnFe₂O₄ catalyst, making it a promising candidate for sustainable glycerol valorization. Full article

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

The efficient simultaneous removal of NO_x and CO from sintering flue gas under low-temperature conditions (110–180 °C) in iron and steel enterprises remains a significant challenge in the field of environmental catalysis. In this study, we present an innovative strategy to enhance the performance of CuSmTi catalysts through silver modification, yielding a bifunctional system capable of oxygen structure regulation and demonstrating superior activity for the combined NH₃-SCR and CO oxidation reactions under low-temperature, oxygen-rich conditions. The modified AgCuSmTi catalyst achieves complete NO conversion at 150 °C, representing a 50 °C reduction compared to the unmodified CuSmTi catalyst (T_100% = 200 °C). Moreover, the catalyst exhibits over 90% N₂ selectivity across a broad temperature range of 150–300 °C, while achieving full CO oxidation at 175 °C. A series of characterization techniques, including XRD, Raman spectroscopy, N₂ adsorption, XPS, and O₂-TPD, were employed to elucidate the Ag-Cu interaction. These modifications effectively optimize the surface physical structure, modulate the distribution of acid sites, increase the proportion of Lewis acid sites, and enhance the activity of lattice oxygen species. As a result, they effectively promote the adsorption and activation of reactants, as well as electron transfer between active species, thereby significantly enhancing the low-temperature performance of the catalyst. Furthermore, in situ DRIFTS investigations reveal the reaction mechanisms involved in NH₃-SCR and CO oxidation over the Ag-modified CuSmTi catalyst. The NH₃-SCR process predominantly follows the L-H mechanism, with partial contribution from the E-R mechanism, whereas CO oxidation proceeds via the MvK mechanism. This work demonstrates that Ag modification is an effective approach for enhancing the low-temperature performance of CuSmTi-based catalysts, offering a promising technical solution for the simultaneous control of NO_x and CO emissions in industrial flue gases. Full article

Nitrogen oxides (NO_x), harmful pollutants primarily from fossil fuel combustion, pose significant environmental and health risks. Among mitigation technologies, NH₃-SCR is widely adopted due to its high efficiency and industrial viability. MnO₂-based catalysts, particularly α-MnO₂, have gained attention for low-temperature NH₃-SCR owing to their redox properties, low-temperature activity, and environmental compatibility. In this study, α-MnO₂ catalysts with tunable oxygen vacancy concentrations were synthesized by varying calcination atmospheres. Compared to α-MnO₂-Air, the oxygen vacancy-rich α-MnO₂-N₂ exhibited stronger acidity, enhanced redox properties, and superior NH₃/NO adsorption and activation, achieving 98% NO conversion at 125–250 °C. Oxygen vacancies promoted NH₃ adsorption on Lewis/Brønsted acid sites, facilitating -NH₂ intermediate formation, while enhancing NO oxidation to reactive nitrates. In situ DRIFTS revealed a dual E-R and L-H reaction pathway, with oxygen vacancies crucial for NO activation, intermediate formation, and N₂ generation. These findings underscore the importance of oxygen vacancy engineering in optimizing Mn-based SCR catalysts. Full article

The effective and deep removal of unreactive sulfides to achieve ultra-low-sulfur or sulfur-free oils has recently attracted extensive attention. In this work, a series of UiO-66 based catalysts have been prepared facilely for the effective removal of unreactive sulfides. Here, the incorporation of nitro functional groups into UiO-66, along with the construction of defects, results in remarkable sulfur removal for dibenzothiophene (DBT), achieving oil with sulfur content of less than 1 ppm. The successful construction of the designed catalysts was verified through a series of characterization studies. The exposed unsaturated metal sites help provide significantly more active reaction sites. In addition, the incorporated nitro group, with its electron-withdrawing property, would help increase the Lewis acidity of the catalytic metal sites. Thus, the catalytic oxidative capability of the designed UiO-66-based catalysts would be significantly increased. The enhanced catalytic oxidative performance helps ensure acceptable sulfur removal for oils with much higher sulfur concentrations. Additionally, the catalyst developed in this work can also be used to remove the derivatives of DBT with even lower reactivity. The relatively mild reaction conditions, combined with the exceptional sulfur removal, demonstrate the practicality of this reaction system. Full article

This study examines a catalyst based on graphitic carbon nitride (g-C₃N₄) for synthesizing glycerol carbonate through the coupling reaction of glycerol and CO₂. In this research, we focus on simultaneously improving CO₂ emission reduction and glycerol valorization by co-doping g-C₃N₄ with phosphorus (P), sulfur (S), magnesium (Mg), and lithium (Li) for a better catalytic performance. The catalysts were prepared through a one-step thermal condensation process and characterized using XRD, SEM, TGA, FTIR, and nitrogen adsorption–desorption techniques. The co-doping further enhanced the surface chemical properties, Lewis acidity, basicity, and thermal stability, evidenced by the lower crystallinity, wider pore, and better catalytic performance as assessed through glycerol carbonylation reaction, optimized using a Box–Behnken design. The MgPSCN catalyst exhibited the highest glycerol conversion (68.72%) and glycerol carbonate yield (44.90%) at 250 °C, using 50 mg catalyst and 10 bar pressure. The model accuracy was validated by ANOVA (R² > 0.99; p values < 0.0001). The results indicated that doping significantly enhanced the catalytic performance, most likely due to improved electron charge transfer and structural distortions within the g-C₃N₄ framework. Such a process highlights the potential of co-doped g-C₃N₄ catalysts for the sustainable glycerol utilization and valorization of CO₂ through a scalable pathway toward green chemical synthesis—an approach that comes in line with worldwide decarbonization goals. Full article

Hydrogen (H₂) has become a more important alternative source in the current energy transition process. Beyond its role in clean energy production, it also serves as a key reactant in a wide range of industrial chemical transformations, such as hydrogenation and hydroprocessing. A fundamental step in many of these processes is the dissociation of hydrogen on catalyst surfaces. This short review provides an overview of the fundamental mechanisms involved in hydrogen dissociation over catalysts, with a specific emphasis on heterolytic pathways. Meanwhile, the influence of surface coordination environments on hydrogen activation is discussed, focusing on key factors—Lewis acid–base pairs, lattice oxygen and oxygen vacancies, and metal–support interfaces. With recognizing the significance of understanding the reaction mechanisms, we provide a critical review of experimental techniques, including spectroscopy, temperature-programmed methods, and kinetic analysis, that have been successfully applied or appear promising for probing active sites, reaction dynamics, chemisorbed intermediates, and elementary steps. Our goal is to highlight how these techniques contribute to a mechanistic understanding and to outline future directions, making this review a valuable resource for both new and experienced researchers. Full article

Nickel phosphides (Ni_xP_y) are recognized as promising alternatives to noble-metal catalysts for the oxygen evolution reaction (OER). NiP, consisting of the equal stoichiometric ratio of Ni and P, could help quantify the catalytic effect of P and Ni. In this work, density functional theory (DFT) is employed to investigate the OER mechanism on NiP surfaces. We found that P atoms help stabilize O* at the adsorption sites. The rich electron donation from the Ni atom can alter the local charge distribution and enhance the interaction between O* and P atoms. Both oxygen intermediate adsorption energy and OER overpotential exhibit linear correlations with the charge of adsorption sites. Electron loss at the site induces the overall system to exhibit Lewis acidic characteristics, facilitating the OER and leading to a substantial overpotential reduction of up to 0.61 V compared to Lewis basic structures. Leveraging electronic structure theory and Lewis acid–base theory, we offer a new insight into the OER mechanism on the NiP surface, demonstrating that the catalytic activity of bulk metallic surface materials like NiP can be optimized by tailoring the local surface chemical environment. Full article

The ozonation of norfloxacin (NOF), a widely used fluoroquinolone antibiotic, in the presence of Na⁺, Fe²⁺, Cu²⁺, Ni²⁺, and Co²⁺ cations and their montmorillonite-supported counterparts was investigated. The NOF degradation and the toxicity of the ozonized mixtures towards an aquatic organism (Lemna minor) were evaluated in terms of changes in its frond number, chlorophyll content, photosynthesis efficacy, and production of reactive oxygen species (ROS). The evolution over time of the NOF degradation grade and the toxicity were discussed in terms of i. the observed changes in the interactions of the cation and clay catalyst with NOF molecules; ii. the pH decay, during ozonation. Ion-exchange and Lewis acid–base interactions appear to govern NOF adsorption and clay catalyst dispersion in correlation with the progressive formation of acidic species in the aqueous media. These findings reveal promising prospects for tailoring optimum oxidative water treatments with minimum toxicity and for predicting their environmental impacts on aquatic media. Full article

A sustainable and efficient approach for converting carbohydrates into 5-hydroxymethylfurfural (HMF) via heterogeneous catalysis is crucial for effectively utilizing biomass. In this study, we synthesized a series of CrX-polyphenol-formaldehyde resin (PTF) catalysts, which are composites of Cr-doped phenolic-resin-based hydrothermal carbon, using a chelation-assisted multicomponent co-assembly strategy. The performance of the synthesized catalysts was assessed through various analytical techniques, including scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, pyrolysis–Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller analysis. Cr incorporation into the catalysts enhanced the total and Lewis acidities. Notably, the optimized catalyst, designated as Cr0.6-PTF, achieved an effective glucose conversion into HMF, yielding a maximum of 69.5% at 180 °C for 180 min in a saturated NaCl solution (NaClaq)/dimethyl sulfoxide (2: 18) solvent system. Furthermore, Cr0.6-PTF maintained excellent catalytic activity and a stable chemical structure after nine cyclic reactions, resulting in a 63.8% HMF yield from glucose. This study revealed an innovative approach for utilizing metal-doped phenolic resin hydrothermal carbon to transform glucose into platform chemicals. Full article

Over the past three decades, β-lactones have emerged as valuable intermediates for producing diverse industrial chemicals and biodegradable polymers. The ring-expansion carbonylation (REC) of epoxides has become an atom-economical and direct approach to β-lactone production, leveraging readily available carbon monoxide and epoxides. While homogeneous catalysts, particularly bimetallic [Lewis acid]⁺[Lewis base]⁻-type systems, have demonstrated exceptional activity and selectivity, issues like recycling and separation limit the industrial scalability. Heterogenized catalysts offer advantages such as ease of separation and reusability but suffer from reduced efficiency. Recent advancements in porous polymer-based heterogeneous systems, including immobilized cobaltate anions, address these challenges by combining high surface areas with enhanced catalytic performance. Herein, we explore the evolution of homogeneous to heterogeneous REC catalysts, highlighting emerging porous materials and their potential for scalable β-lactone synthesis. Future directions emphasize overcoming the remaining barriers to establish robust, efficient, and sustainable catalytic processes. Full article

Mn-based oxides are promising catalysts for the selective catalytic reduction (SCR) of NO_x by NH₃ at low temperatures. However, fundamental NH₃-SCR mechanisms and resistance mechanisms against SO_x remain controversial. This study employed density functional theory (DFT) calculations to explore the intrinsic mechanisms of NH₃-SCR and SO_x poisoning on Mn₃O₄(001). Both NH₃ and NO adsorb atop the surface Mn site (the Lewis acid site). In contrast to the traditional Langmuir–Hinshelwood (L-H) mechanism in which gaseous NO is first oxidized to form adsorbed nitrites or nitrates and then react with adsorbed NH_x species to produce H₂O and N₂, a new potential L-H pathway is proposed that involves gaseous NO first adsorbing and then reacting with NH* to generate the key intermediate NHNO*, followed by the formation of H₂O and N₂. This L-H pathway is more efficient as it bypasses the NO oxidation step and is more selective for N₂ formation by avoiding N₂O production. In addition, the L-H mechanism is more favorable than the Eley–Rideal (E-R) mechanism because of the lower free energy profile. SO₂ exhibits limited poisoning effects, whereas SO₃ strongly poisons the Mn₃O₄(001) surface by occupying adsorption sites, hindering intermediate formation and producing ammonium bisulfate. Full article

Metal species and carbonate are often found as minerals in extraterrestrial rocky bodies. Based on this, the mechanochemical-induced degradation of canonical purine and pyrimidine ribonucleosides into their corresponding nucleobases mediated by some of the main constituents of those materials (iron, nickel, or aluminum) was accomplished. In some cases, the previous heating of the samples intensified mechanochemical degradation. Additionally, carbonate acts as an activator for ribonucleoside degradation with a catalyst (a Lewis acid ion); however, it has almost no effect on ribonucleoside degradation in the absence of a catalyst. These results can contribute to the hypothesis that organic matter in extraterrestrial samples could have undergone mechanochemical reactions (i.e., shock/impact events), from its formation until its journey to Earth. Mechanochemical energy could occur in planetesimal accretion, asteroid formation (i.e., through planetesimal disintegration), and meteoroid atmospheric entry. Additionally, this hypothesis can clarify and relate some identified biosignatures with pathways of prebiological evolution. Full article

Ruthenium-based catalysts were prepared through a deposition–precipitation approach, taking beta zeolites with Si/Al ratios of 12.5, 18.5, and 150, respectively, as supports, and 1–3 wt% loadings of metal. Their activation was performed in the presence of either H₂ or NaBH₄. The dispersion of the Ru species and the acid–base properties were influenced by both the preparation method and the activation protocol. The catalysts reduced under H₂ flow presented well-dispersed Ru(0) and RuO_x nanoparticles, while the reduction with NaBH₄ led to larger RuO_x crystallites and highly dispersed Ru(0). These characteristics exerted an important role in the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). The H₂ dissociation occurred via a heterolytic mechanism involving Lewis acid–base pairs associated with RuO_x and the framework oxygen (Si-O-Al) located near the zeolite pore edge. The Ru(0) nanoparticles activated the –C=O bond of the LA substrate, while the presence of the carrier zeolite Brønsted acid sites promoted the ring-closure esterification of the 4-hydroxyvaleric acid (4-HVA) intermediate to GVL. An optimal combination of these features was achieved for the catalyst with 3 wt% Ru and a Si/Al ratio of 150, which selectively converted LA (X_LA = 96.5%) to GVL (S_GVL = 97.8%) at 130 °C and 10 bars of H₂. Full article