Search Results (22)

Polyolefins are widely used polymers, with an annual global production of hundreds of millions of tons. Because they are the simplest hydrocarbon polymers, their intrinsic non-polar properties limit further applications. Coordination–insertion copolymerization of an olefin with other monomers, mediated by transition metal catalysts, is the most efficient way to synthesize polar and multi-functionalized polyolefins with enhanced material performance. Previous reviews have primarily focused on the structural design of a specific catalyst or on binary copolymerization of an olefin with a particular comonomer. However, the transition-metal-catalyzed ternary coordination–insertion polymerization of olefin monomers remains scarce. In this contribution, early transition-metal catalysts, such as Ti, Zr, Hf, and V, are employed for the terpolymerization of all-hydrocarbon or non-polar monomers to access advanced polyolefin materials with high performance. By contrast, late transition metal catalysts based on Ni and Pd, as well as rare-earth metal catalysts ligated by Sc and Y, enable the terpolymerization of olefins with a variety of heteroatom-containing monomers. Their strong tolerance empowers the development of polyolefins with multiple functionalities, thereby distinguishing these systems. The catalyst structure, catalytic process, and mechanism studies are summarized, along with the microstructure and functionality of the polymerization products, by classifying the types of termonomers employed. Full article

Recent advances in designing multinuclear late transition metal catalysts for the oligo-/polymerization of olefins emphasize the great interest and promising approaches in the preparation and application of these catalytic systems. Accordingly, in this study, two dinuclear macrocyclic bis(iminopyridine) Fe- and Co-based complexes (FC and CC) were prepared at moderate yields through a one-pot template reaction. Upon activation by MMAO, not only did the catalysts show reasonable activities for the oligomerization of ethylene but also showed high selectivity for the production of tetramers (α-C₈). With respect to the catalyst structure, FC demonstrated higher catalyst activity (9.45 g mol⁻¹ Fe h⁻¹ × 10⁵ vs. 8.75 × 10⁵ g mol⁻¹ Co h⁻¹) along with higher selectivity for α-C₈ production compared to CC (96.6 vs. 96.1%). Both catalysts had thermal stability up to 70 °C, with FC being much more active and stable than CC under identical conditions. On the other hand, polymerization parameters had an influence on the catalyst performance and oligomer distribution. Moreover, molecular calculations were employed for geometry optimization and structural determination, which was consistent with the experimental results. Full article

Late transition metal olefin polymerization catalysts have received more attention in the field of catalytic olefin polymerization. Barrelene-based α-diimine nickel and palladium olefin polymerization catalysts are rising stars because of their backbone structure and catalytic properties. In this review, we present a comprehensive review of barrelene-derived α-diimine nickel and palladium olefin polymerization catalysts. α-Diimine nickel and palladium catalysts are introduced from two aspects: barrelene-derived backbone and aniline derivatives with different substituents. The relationship between catalyst structure and catalytic properties is also emphasized. This review attempts to provide an inspiration for the design of high-performance barrelene-based catalysts. Full article

As a kind of high-performance thermoplastic crystalline resin, poly(4-methyl-1-pentene) (PMP) is characterized by its low density, low dielectric constant, exceptional mechanical and chemical properties, high transparency, and gas permeability. PMP has recently received more attention since COVID-19, because it is used as a hollow-fiber membrane for extracorporeal membrane oxygenation (ECMO) based on its high permeability and excellent biocompatibility. This review summarizes the chemical structure, synthesis, properties, and application of PMP. The advancements in catalyst systems for the catalytic synthesis of PMP, including Ziegler–Natta, metallocene, post-metallocene, and late-transition metal catalysts are emphasized. Furthermore, the molecular chain structure, helical conformation, and crystallization morphology of PMP, as well as its properties and applications, are also introduced in detail. Additionally, PMP composites and functional PMP materials are also described as promising and high-performance materials. Full article

Late transition metal catalysts represent a significant class of olefin polymerization catalysts that have played an essential role in advancing the polyolefin industry owing to their highly tunable ligands and low oxophilicity. A key feature for the design of late transition metal catalysts lies in the steric bulk of the o-aryl substituents. Bulky 8-arylnaphthylamines have emerged as a promising aniline candidate for conducting high-performance catalysts by introducing axially steric hindrance around the metal center. This review focuses on late transition metal (Ni, Pd, Fe) catalysts derived from 8-arylnaphthylamines, surveying their synthesis, structural features, and catalytic applications in olefin (co)polymerizations. Additionally, the relationship between catalyst structure and catalytic performance is discussed, highlighting how these unique ligand systems influence polymerization activity, molecular weight, and polymer branching. Full article

The α-diimine late transition metal catalyst represents a new strategy for the synthesis of atactic polypropylene elastomer. Taking into account the properties of the material, enhancing the molecular weight of polypropylene at an elevated temperature through modifying the catalyst structure, and further increasing the activity of α-diimine catalyst for propylene polymerization, are urgent problems to be solved. In this work, two α-diimine nickel(II) catalysts with multiple hydroxymethyl phenyl substituents were synthesized and used for propylene homopolymerization. The maximum catalytic activity was 5.40 × 10⁵ gPP/molNi·h, and the activity was still maintained above 10⁵ gPP/molNi·h at 50 °C. The large steric hindrance of catalysts inhibited the chain-walking and chain-transfer reactions, resulting in polypropylene with high molecular weights (407~1101 kg/mol) and low 1,3-enchainment content (3.57~16.96%) in toluene. The low tensile strength (0.3~1.0 MPa), high elongation at break (218~403%) and strain recovery properties (S.R. ~50%, 10 tension cycles) of the resulting polypropylenes, as well as the visible light transmittance of approximately 90%, indicate the characteristics of the transparent elastomer. Full article

Ultra-high molecular weight polyethylenes (UHMWPEs) are significant engineering plastics for their unique properties, such as high impact resistance, abrasion resistance, weatherability, lubricity, and chemical resistance. Consequently, developing a suitable catalyst is vital in facilitating the preparation of UHMWPE. The late transition metal catalysts have emerged as effective catalysts in producing UHMWPE due to their availability, enhanced tolerance to heteroatom groups, active polymerization characteristics, and good copolymerization ability with polar monomers. In this review, we mainly focus on the late transition metal catalysts, summarizing advancements in their application over the past decade. Four key metals (Ni, Pd, Fe, Co) for generating linear or branched UHMWPE will be primarily explored in this manuscript. Full article

With the intensification of global resource shortages and the environmental crisis, hydrogen energy has garnered significant attention as a renewable and clean energy source. Water splitting is considered the most promising method of hydrogen production due to its non-polluting nature and high hydrogen concentration. However, the slow kinetics of the two key reactions, the Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER), have greatly limited the development of related technologies. Meanwhile, the scarcity and high cost of precious metal catalysts represented by Pt and Ir/RuO₂ limit their large-scale commercial application. Thus, it is essential to develop catalysts based on Earth’s transition metals that have abundant reserves. Vanadium (V) is an early transition metal with a distinct electronic structure from late transition metals such as Fe, Co, and Ni, which has been emphasized and studied by researchers. Numerous vanadium-based electrocatalysts have been developed for the HER and OER. In this review, the mechanisms of the HER and OER are described. Then, the compositions, properties, and modification strategies of various vanadium-based electrocatalysts are summarized, which include vanadium-based oxides, hydroxides, dichalcogenides, phosphides, nitrides, carbides, and vanadate. Finally, potential challenges and future perspectives are presented based on the current status of V-based electrocatalysts for water splitting. Full article

The introduction of polar functional groups into polyolefin chain structures creates opportunities to enhance specific properties, such as adhesion, dyeability, printability, compatibility, thermal stability, and electrical conductivity, which widen the range of potential applications for these modified materials. Transition metal catalysts, especially late transition metals, have proven to be highly effective in copolymerization processes due to their reduced Lewis acidity and electrophilicity. However, when compared to the significant progress and summary of synthetic methods, there is a distinct lack of a comprehensive summary of mechanistic studies pertaining to the catalytic systems involved in ethylene copolymerization catalyzed by palladium and nickel catalysts. In this review, we have provided a comprehensive summary of the latest developments in mechanistic studies of ethylene copolymerization with polar monomers catalyzed by late-transition-metal complexes. Experimental and computational methods were employed to conduct a detailed investigation of these organic and organometallic systems. It is mainly focused on ligand substitution, changes in binding modes, ethylene/polar monomer insertion, chelate opening, and β-H elimination. Factors that control the catalytic activity, molecular weight, comonomer incorporation ratios, and branch content are analyzed, these include steric repulsions between ligands and monomers, electronic effects arising from both ligands and monomers, and so on. Full article

As a powerful protocol for the preparation of common polymers, such as polyolefins, polyesters, and polycarbonates, late-transition-metal-catalyzed polymerization can be carried out by controlling the reaction conditions or developing dynamic catalytic systems that use external stimuli to influence the performance of the active sites, resulting in well-defined polymeric materials. In particularly, under the latter conditions, ‘one catalyst’ can provide more than one kind of polymer with a controlled sequence from the monomer mixture, making full use of the prepared catalyst. In this review, tunable modes, including reaction conditions, redox, light or electrochemical properties, Lewis acids, and alkali metal cations, of late-transition-metal-complex (especially iron, cobalt, and nickel)-catalyzed polymerization were collected and thoroughly discussed. Full article

3,4-Enhanced polymerization of isoprene catalyzed by late transition metal with high activity remains one of the great challenges in synthetic rubber chemistry. Herein, a library of [N, N, X] tridentate iminopyridine iron chloride pre-catalysts (Fe 1–4) with the side arm were synthesized and confirmed by the element analysis and HRMS. All the iron compounds served as highly efficient pre-catalysts for 3,4-enhanced (up to 62%) isoprene polymerization when 500 equivalent MAOs were utilized as co-catalysts, delivering the corresponding high-performance polyisoprenes. Furthermore, optimization via single factor and response surface method, it was observed that the highest activity was obtained by complex Fe 2 with 4.0889 × 10⁷ g·mol(Fe)⁻¹·h⁻¹ under the following conditions: Al/Fe = 683; IP/Fe = 7095; t = 0.52 min. Full article

The synthesis of polar functionalized cyclic olefin copolymers (COCs) from the coordination copolymerization of norbornene (NB) and polar monomers catalyzed by late transition metal catalysts has been a recent research hotspot. However, few catalysts have achieved efficient copolymerization with commercial vinyl-type polar monomers, such as methyl acrylate (MA). In this contribution, nickel complexes bearing 2-(diarylphosphino)-N-phenylbenzenamine ligands were synthesized and applied as pre-catalysts to catalyze the (co)polymerization of norbornene. Upon the activation of methylaluminoxane (MAO), these nickel catalysts were active for norbornene polymerization with the highest activity achieved being 3.6 × 10⁶ g mol⁻¹ h⁻¹ and the highest number average molecular weight (M_n) of polynorbornene (PNB) reaching 27.4 × 10⁵ g mol⁻¹. Moreover, these nickel catalysts also promoted the copolymerization of norbornene and MA to furnish high-molecular-weight NB/MA copolymers (M_n up to 6.20 × 10⁴ g mol⁻¹) with reasonable MA contents (3.07−5.90 mol%). The molecular weight of PNB and NB/MA copolymers obtained by the present nickel catalysts are remarkably higher than those of the (co)polymers from our previous reported dimethyl substituted phosphinobenzenamine nickel catalyst, suggesting significant progress in this field. Full article

Ethylene cross-bridged tetraazamacrocycles are known to produce kinetically stable transition metal complexes that can act as robust oxidation catalysts under harsh aqueous conditions. We have synthesized ligand analogs with single acetate pendant arms that act as pentadentate ligands to Mn, Fe, Co, Ni, Cu, and Zn. These complexes have been synthesized and characterized, including the structural characterization of four Co and Cu complexes. Cyclic voltammetry demonstrates that multiple oxidation states are stabilized by these rigid, bicyclic ligands. Yet, redox potentials of the metal complexes are modified compared to the “parent” ligands due to the pendant acetate arm. Similarly, gains in kinetic stability under harsh acidic conditions, compared to parent complexes without the pendant acetate arm, were demonstrated by a half-life seven times longer for the cyclam copper complex. Due to the reversible, high oxidation states available for the Mn and Fe complexes, the Mn and Fe complexes were examined as catalysts for the bleaching of three commonly used pollutant model dyes (methylene blue, methyl orange, and Rhodamine B) in water with hydrogen peroxide as oxidant. The efficient bleaching of these dyes was observed. Full article

Polyolefins are the most consumed polymeric materials extensively used in our daily life and are usually generated by coordination polymerization in the polyolefin industry. Olefin polymerization catalysts containing transition metal–organic compound combinations are undoubtedly crucial for the development of the polyolefin industry. The nitrogen donor atom has attracted considerable interest and is widely used in combination with the transition metal for the fine-tuning of the chemical environment around the metal center. In addition to widely reported olefin polymerization catalysts with imine and amide donors (sp² hybrid N), late transition metal catalysts with chelating amine donors (sp³ hybrid N) for olefin polymerization have never been reviewed. In this review paper, we focus on late transition metal (Ni, Pd, Fe, and Co) catalysts with chelating amines for olefin polymerization. A variety of late transition metal catalysts bearing different neutral amine donors are surveyed for olefin polymerization, including amine–imine, amine–pyridine, α-diamine, and [N, N, N] tridentate ligands with amine donors. The relationship between catalyst structure and catalytic performance is also encompassed. This review aims to promote the design of late transition metal catalysts with unique chelating amine donors for the development of high-performance polyolefin materials. Full article

Recently, electrocatalysts for oxygen reduction reaction (ORR) as well as oxygen evolution reaction (OER) hinged on electrospun nanofiber composites have attracted wide research attention. Transition metal elements and heteroatomic doping are important methods used to enhance their catalytic performances. Lately, the construction of electrocatalysts based on metal-organic framework (MOF) electrospun nanofibers has become a research hotspot. In this work, nickel-cobalt zeolitic imidazolate frameworks with different molar ratios (Ni_xCo_y-ZIFs) were synthesized in an aqueous solution, followed by Ni_xCo_y-ZIFs/polyacrylonitrile (PAN) electrospun nanofiber precursors, which were prepared by a simple electrospinning method. Bimetal (Ni-Co) porous carbon nanofiber catalysts doped with nitrogen, oxygen, and sulfur elements were obtained at high-temperature carbonization treatment in different atmospheres (argon (Ar), Air, and hydrogen sulfide (H₂S)), respectively. The morphological properties, structures, and composition were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Moreover, the specific surface area of materials and their pore size distribution was characterized by Brunauer-Emmett-Teller (BET). Linear sweep voltammetry curves investigated catalyst performances towards oxygen reduction and evolution reactions. Importantly, Ni₁Co₂-ZIFs/PAN-Ar yielded the best ORR activity, whereas Ni₁Co₁-ZIFs/PAN-Air exhibited the best OER performance. This work provides significant guidance for the preparation and characterization of multi-doped porous carbon nanofibers carbonized in different atmospheres. Full article