Search Results (1,022)

The hydrodynamic and reaction characteristics of poly-alpha-olefin (PAO) polymerization in a continuous stirred tank reactor (CSTR) under Eulerian–Eulerian multiphase flow and a finite-rate chemical kinetics model were studied in this paper. A mathematical framework correlating 1-decene conversion with operational and structural parameters was established. Numerical simulations revealed an axial circulation flow pattern driven by combined impellers, with internal coils enhancing heat exchange and flow guidance. The gaseous catalyst, injected below the turbine impeller, achieved rapid dispersion and low gas holdup. The results demonstrated that 1-decene conversion exhibited insensitivity to impeller speed under fully turbulent mixing (mixing time <0.15% of space time), suggesting limited mass transfer benefits from further speed increases. Conversion positively correlated with temperature and space time, albeit with diminishing returns at prolonged durations. Series reactor configurations improved conversion efficiency, though incremental gains decreased with additional units. Optimal reactor design should balance conversion targets with economic factors, including energy consumption and capital investment. These findings provide critical insights into scaling PAO polymerization processes, emphasizing the interplay between reactor geometry, mixing dynamics, and reaction kinetics for industrial applications. Full article

A versatile, sustainable feedstock pathway to bio-based polymeric materials was developed utilizing lignin biomass and the ring-opening copolymerization (ROCOP) of cyclic anhydrides and epoxides to synthesize functional, lignin-derived, fully bio-based polyester polyols. The initial goal was to make the ROCOP reaction more applicable to bio-derived starting materials and more attractive to commercialization by conducting the polymerization under less constrained and industrially relevant conditions in air and without the extensive purification of reagents, catalysts, or solvents, typically used in the literature. A refined ROCOP system was applied as a powerful tool in lignin valorization by successfully synthesizing the lignin-derived copolyester prepolymers from lignin models and depolymerized native lignin sourced from the reductive catalytic fractionation of Pinus radiata wood biomass. After mechanistic studies based on NMR characterization, an alternative ROCOP-style mechanism was proposed. This was found to be (1) contributing to the acceleration of the observed reaction rates with added [PPNCl] organo-catalyst and (2) ‘self-initiation/self-promoted’ ROCOP without any added external [PPNCl] catalyst, likely due to the presence of inherent [OH] groups/ species in the lignin-derived glycidyl ether monomer promoting reactivity. As a final goal, the potential of these lignin-derived polyesters as intermediate polyols was demonstrated by applying them in the synthesis of polyurethane (PU) film materials with a high biomass content of 75–79%. A dramatic range of thermomechanical properties was observed for the resulting materials, demonstrating how the ROCOP reaction can be used to tailor the properties of the functional polyester and PU material based on the nature of the epoxide and anhydride substrates used. These findings help endeavors towards predicting the relationship between chemical structure and material thermomechanical properties and performance, relevant for industrial applications. Overall, this study demonstrated the proof of concept that PU materials can be prepared from lignocellulosic biomass utilizing industrially feasible ROCOP of bio-derived cyclic anhydrides and epoxides. Full article

In this contribution, two silsesquioxane–cyclopentadienyl titanium complexes featuring one or two chloride ancillary ligands, [Ti(η⁵-C₅H₄SiMeO₂Ph₇Si₇O₁₀-κO)Cl₂] (1) and [Ti(η⁵-C₅H₄SiMe₂OPh₇Si₇O₁₁-κ²O₂)Cl] (2), were synthesized and evaluated in the Ziegler–Natta polymerization of styrene and the ring-opening polymerization (ROP) of L-lactide, respectively. Complex 1, activated with methylaluminoxane (MAO), catalyzed the syndiotactic polymerization of styrene with turnover frequencies up to 28 h⁻¹, affording polymers with narrow dispersity, low number-average molecular weights (M_n = 5.2–8.2 kDa), and high stereoregularity, as confirmed by ¹³C NMR. Complex 2, in combination with benzyl alcohol, promoted the ring-opening polymerization of L-lactide in solution at 100 °C, achieving conversions up to 95% with good molecular weight control (M_n close to theoretical, Đ = 1.19–1.32). Under melt conditions at 175 °C, it converted up to 3000 equiv. of monomer within 1 h. Kinetic analysis revealed first-order dependence on monomer concentration. The results highlight the ability of these complexes to produce syndiotactic polystyrene with narrow molecular weight distributions and to catalyze controlled ROP of L-lactide under both solution and melt conditions. Computational studies provided insight into key structural and energetic features influencing reactivity, offering a framework for further catalyst optimization. This work broadens the application scope of silsesquioxane–cyclopentadienyl titanium complexes and supports their potential as sustainable and versatile catalysts for both commodity and biodegradable polymer synthesis. Full article

This study reports a binder-free, catalyst-free method for fabricating vertically aligned carbon nanotubes (VACNTs) directly on copper (Cu) foil using plasma-enhanced chemical vapor deposition (PECVD) for electrochemical double-layer capacitor (EDLC) applications. This approach eliminates the need for catalyst layers, polymeric binders, or substrate pre-treatments, simplifying electrode design and enhancing electrical integration. The resulting VACNTs form a dense, uniform, and porous array with strong adhesion to the Cu substrate, minimizing contact resistance and improving conductivity. Electrochemical analysis shows gravimetric specific capacitance (C_grav) and areal specific capacitance (C_areal) of 8 F g⁻¹ and 3.5 mF cm⁻² at a scan rate of 5 mV/s, with low equivalent series resistance (3.70 Ω) and charge transfer resistance (0.48 Ω), enabling efficient electron transport and rapid ion diffusion. The electrode demonstrates excellent rate capability and retains 92% of its initial specific capacitance after 3000 charge–discharge cycles, indicating strong cycling stability. These results demonstrate the potential of directly grown VACNT-based electrodes for high-performance EDLCs, particularly in applications requiring rapid charge–discharge cycles and sustained energy delivery. Full article

Although transition metal catalysts have been used extensively for the polymerization of hydrocarbon monomers, several cationic aluminum catalysts have been also known to promote polymerization of ethylene and 1,3-butadiene. Transition-metal catalyzed polymerization generally proceeds via coordination and insertion of the monomer on one metal center. In contrast, in ethylene polymerization using aluminum catalysts, a bimolecular chain growth mechanism, including the reaction between neutral aluminum species and the monomer activated by cationic aluminum species, is proposed. Although previously reported aluminum catalysts are based on a monoaluminum complex, a dialuminum complex is expected to catalyze the polymerization more efficiently, considering the proposed mechanism. In this work, we found that a combination of diphosphines and MAO promotes polymerization of ethylene and 1,3-butadiene. The 1,4-bis(diphenylphosphino)butane (DPPB)/methylaluminoxane (MAO) system showed a much higher activity toward ethylene polymerization than other monophosphine or diphosphine/MAO systems. NMR analysis of a mixture of diphosphine and MAO indicates the formation of cationic dialuminum species in the presence of DPPB, whereas the formation of cationic monoaluminum species occurs in the presence of other diphosphines. The 2,2′-bis(diphenylphosphino)-1,1′-biphenyl (BIPHEP)/MAO system promoted 1,3-butadiene polymerization to give polybutadiene having a cis-1,4 selectivity of up to 93.8%. Full article

The increasing demand for sustainable materials has propelled the development of bio-based elastomers derived from renewable terpenes. This study presents the synthesis of high-cis poly(butadiene-co-terpene) copolymers using coordination chain transfer polymerization with neodymium-based catalysts, enabling precise control of molecular weight and microstructure. Two terpene monomers, β-myrcene and trans-β-farnesene, were incorporated up to 45 wt% without compromising the elastomeric 1,4-cis polybutadiene segments. The copolymers were evaluated as impact modifiers in acrylonitrile–butadiene–styrene (ABS) and as vulcanizable rubber formulations. ABS containing bio-based copolymers exhibited distinct rubber morphologies, including elongated and rod-like particles with average particle diameters greater than 1042 nm and rubber phase volume fraction values ≥ 0.49, resulting in improved impact resistance exceeding 580 J/m and elongation at break higher than 12%. Vulcanized rubbers incorporating terpene segments displayed tunable curing kinetics, mechanical properties, and dynamic mechanical behavior, with notable increases in elongation (up to ~520%) and elasticity attributed to lower crosslink density (<1.20 × 10⁻⁴ mol/mL). Additionally, its energy dissipation capacity has been enhanced compared to the high-cis polybutadiene. These findings highlight the potential of terpene-derived bioelastomers as sustainable alternatives to fossil-based rubbers, offering comparable or enhanced performance for engineering polymer applications. The study underscores important structure–property relationships, providing a foundation for further optimization toward industrial adoption. Full article

The oxidative dehydrogenation of propane (ODHP) catalyzed by oxygen offers several advantages, including resistance to carbon deposition and low energy consumption. However, achieving high propylene selectivity at industrially relevant conversions remains challenging, as existing catalysts typically require temperatures exceeding 500 °C, promoting over-oxidation to CO_x. In this study, we developed a NiO nanoparticle-decorated graphitic carbon nitride catalyst (NiO@CN-600) via thermal polymerization–oxidation for photo-thermal synergistic ODHP. At 430 °C, thermal catalysis achieved a propane conversion of 14%. Remarkably, introducing light irradiation boosted conversion to 24%, a 10% increase. Further experimental results reveal that the photo-thermal synergistic catalysis can be described by the following mechanism: initial thermal energy provides sufficient activation energy, enabling the reaction to overcome the energy barrier and proceed smoothly. Simultaneously, the introduction of light energy enhances the activity of lattice oxygen, making it more likely to detach from the lattice and form oxygen vacancies, which in turn boosts the efficiency of the oxidation reaction on the catalyst surface. Full article

The coordination chemistry of benzimidazole ligands combines σ donation and π backbonding. Owing to this electronic flexibility, benzimidazole ligands stabilize both electron deficient and electron-rich transition states in the catalytic cycle of Ziegler-Natta polymerizations. In this study, Fe(III) and Ni(II) complexes of 2-substituted-benzimidazoles were tested as catalysts for ethylene and 1-butene oligomerization. The tests realized in toluene yielded mainly butenes and minor amounts of hexenes. When dichloromethane was used as solvent, a tandem reaction took place and 1-butene produced by ethylene dimerization was further oligomerized, yielding octenes and dodecenes as main products. All tested catalysts exhibited moderate selectivity for 1-octene, indicating 1-ω enchainment in 1-butene dimerization. Beyond catalytic tests, a theoretical study of the ligand 2,2′-(furan-2,5-diyl)bis(1H-benzimidazole) confirmed the planar structure of this compound as evidenced by NMR spectroscopy. Full article

This study reports the synthesis of high cis-1,4 polybutadiene with a narrow molecular weight distribution (Đ < 2.0) by coordinative chain transfer polymerization (CCTP) using a homogeneous ternary NdV₃/diisobutyl aluminum hydride (DIBAH)/dimethyldichlorosilane (Me₂SiCl₂) Ziegler–Natta catalyst system. The polymerization parameters, notably the monomer-to-initiator ratio ([M]/[Nd]) and the halogen-to-initiator ratio ([Cl]/[Nd]), were systematically varied to define the CCTP operational window. It was found that CCTP conditions are achieved only at low [M]/[Nd] ratios (<2500) and intermediate [Cl]/[Nd] ratios between 1.0 and 2.0, facilitating the production of polymers with molecular weights below 32 kDa and narrow dispersity. Increasing these ratios beyond these thresholds potentially induces the formation of insoluble, hyper-halogenated catalytic species and increases medium viscosity, which significantly broadens the molecular weight distribution (Đ > 4.0) and impairs CCTP control. These findings challenge previous assumptions that higher halogen concentrations are necessary for CCTP, thereby providing important mechanistic insights for tuning active species and achieving improved polymer architecture. The work demonstrates a viable pathway to control polymer microstructure and molecular weight in neodymium-based CCTP, which is critical for design of high-performance elastomeric materials. Full article

Zeolites are widely used as solid acid catalysts and also as supports in complex multifunctional heterogeneous systems. In recent years, there has been an increase in the development of zeolite-based catalysts with hierarchical porosity combined with metal dopants (modifiers or catalysts). These modifications can significantly improve the catalytic characteristics of such materials. In this review, we discuss the application of hierarchically porous zeolites, including metal-doped ones, in catalytic reactions employed in the production and upgrading of liquid fuels, i.e., pyrolysis of biomass and polymeric wastes; conversion of alcohols to fuel hydrocarbons, aromatics and olefins; cracking and hydrocracking of polymeric wastes and hydrocarbons; and hydroisomerization. It is revealed that, in many cases, higher activity, selectivity and stability can be achieved for metal-doped hierarchical zeolites in comparison with parent ones due to control over the diffusion, surface acidity and coke deposition processes. Full article

A series of polyether and poly(ether carbonate) polyols have been synthesized via Zn(II)-Co(III) double metal cyanide (DMC)-catalyzed ring-opening (co)polymerization of various epoxides, such as propylene oxide, 1,2-epoxybutane, epichlorohydrin, styrene oxide, and glycidol, with and without CO₂. The resulting polyether polyols exhibit linear and branched architectures (degrees of branching, DB = 0.27), high catalytic activities with turnover frequencies up to 461 min⁻¹, narrow dispersities (1.15–1.25), and low levels of unsaturation (0.004 meq g⁻¹). The DMC catalysts also enable the efficient synthesis of poly(propylene carbonate) polyol with carbonate contents up to 40% and yields reaching 63%. Additionally, branched poly(ether carbonate) polyols with tunable DB values (0.14–0.21), yields up to 70%, and carbonate contents up to 33% are synthesized via CO₂ fixation to glycidol. The synthesized polyols hold strong potential for industrial applications in polyurethanes and other advanced materials, offering versatile performance for use in coatings, adhesives, sealants, and elastomers. Overall, this study highlights the effectiveness of DMC catalysts in producing high-performance polyols, contributing to the development of sustainable materials with precise architectural control. Full article

Herein, we report a combined computational and experimental investigation into the recently reported universal pyrazole-based reversible addition-fragmentation chain transfer (RAFT) agents (Z−C(=S)−S−R, where Z is 3,5-dimethyl-1H-pyrazol-1-yl), which can mediate controlled radical polymerization of a broad scope of monomers without the need for an additional initiator or catalyst. The results reveal that the high molar absorption coefficient and efficient photolysis kinetics of pyrazole-based chain transfer agents (CTAs) under blue light (${\lambda }_{\max }$ = 465 nm) enable rapid radical generation, underpinning ultrafast polymerization of acrylates, acrylamides, methacrylates, and N-vinylpyrrolidone (NVP). While the efficient light absorption is attributed to structural dissimilarity between the Z group and the S–R group (which breaks the local symmetry of the C=S group), the fast photolysis originates from favorable $\pi$ electron donation from the Z group to the C=S group. Meanwhile, the $\pi$ electron donation is still weaker than in xanthates, which explains the excellent control of a wide range of monomers, except methacrylates. This work establishes design principles for next-generation CTAs for ultrafast and monomer-universal photoiniferter RAFT polymerization. Full article

This paper shows that low concentrations of either a low-molecular-weight or a recyclable polymeric cosolvent can be used to design recyclable, tunable alkane polymeric solvent systems. We have shown that dyes experience a microheterogeneous environment that is ca. 40–50% like that of a polar solvent with as little as 0.1 M added cosolvent. Dyes like Nile red or a polyisobutylene (PIB)-bound dansyl fluorophore both detected microheterogeneity in macrohomogeneous mixtures of heptane or a poly(α-olefin) (PAO) with 0.1–2.0 M added polar solvents. H-Bonding cosolvents have greater effects than cosolvents that only interact with dyes by dipole–dipole interactions. Microheterogeneity was also seen when a PIB-bound version of a low-molecular-weight solvent is used as the added polar cosolvent. These microheterogeneous environments can advantageously be used in synthetic and catalytic reactions. This was demonstrated in transesterification and S_N2 chemistry. Reactions in PAO solutions polarized by 2 M added THF or by 0.5 M of a PIB-bound HMPA analog both had enhanced reactivity versus reactions in a PAO solution without added cosolvent. In the latter case, the catalyst, the PAO solvent, and the PIB-bound cosolvent were all fully recyclable. Full article

Reactive oxygen species (ROS) are increasingly recognized as decisive actors in photocatalytic redox chemistry, dictating both the selectivity and efficiency of target reactions, while most photocatalytic systems generate a mixture of ROS under illumination. Recent studies have revealed that tailoring the generation of specific ROS, rather than maximizing the overall ROS yield, holds the key to unlocking high-performance and application-specific catalysis. In this context, the selective production of specific ROS has emerged as a critical requirement for achieving target-oriented and sustainable photocatalytic transformations. Among the various photocatalytic materials, polymeric carbon nitride (PCN) has garnered considerable attention due to its metal-free composition, visible-light response, tunable structure, and chemical robustness. More importantly, the tunable band structure, surface chemistry, and interfacial environment of PCN collectively make it an excellent scaffold for the controlled generation of specific ROS. In recent years, numerous strategies including molecular doping, defect engineering, heterojunction construction, and co-catalyst integration have been developed to precisely tailor the ROS profile derived from PCN-based systems. This review provides a comprehensive overview of ROS regulation in PCN-based photocatalysis, with a focus on type-specific strategies. By classifying the discussion according to the major ROS types, we highlight the mechanisms of their formation and the design principles that govern their selective generation. In addition, we discuss representative applications in which particular ROS play dominant roles and emphasize the potential of PCN systems in achieving tunable and efficient photocatalytic performance. Finally, we outline key challenges and future directions for developing next-generation ROS-regulated PCN photocatalysts, particularly in the context of reaction selectivity, dynamic behavior, and practical implementation. Full article

The management of solid waste and the supply of energy are two of the most important environmental problems of our time. Projections indicate that by 2050, the global demand for electrical energy is expected to increase by 35% and the amount of solid waste generated to increase by 45%. In this context, polymeric waste materials such as biomass and plastics can be valorised through thermochemical processes for the generation of energy. Gasification, which converts carbonaceous materials into syngas, tar, and char, is one of the most promising recycling technologies. The composition and relative quantities of the products are influenced by the process configuration, operating parameters, and the type of fuel used. Tar removal is facilitated by adding specific catalysts to the process. The co-processing of biomass and plastics in the gasification process, called co-gasification, improves the gas yield and reduces solid residues. This review evaluates catalytic and non-catalytic co-gasification of biomass waste and non-biodegradable plastics, with a focus on syngas production and its energy potential. Full article