Palladium complex embedded crosslinked polystyrene nanofibers as a green and efficient heterogeneous catalyst for coupling reactions

A simple and green chemical modification coupled with electrospinning technique has been developed to incorporate tetrakis(triphenylphosphine)palladium [Pd(PPh₃)₄] inside crosslinked polystyrene nanofibers (Pd@CPS) as an efficient and stable heterogeneous palladium catalyst. The catalytic activities and recyclabilities of the prepared Pd@CPS catalyst have been evaluated by using Suzuki and Heck reactions of various aromatic halides separately with phenylboronic acid and alkenes. The Pd@CPS exhibited high-catalytic activities for the Suzuki and Heck reactions of aromatic iodides to afford the products in excellent yields (coupling yields >88%). The catalytic activities and the nanofiber structure remained essentially unchanged even after recycling for five times. The high activities and stabilities of the prepared Pd@CPS catalyst can be attributed to the ultrafine fiber and embedment of palladium active species inside the nanofibers.     

Palladium nanoparticles embedded chitosan/poly(vinyl alcohol) composite nanofibers as an efficient and stable heterogeneous catalyst for Heck reaction

In this study, palladium nanoparticles were successfully embedded into modified chitosan/poly(vinyl alcohol) composite nanofibers (Pd-CS/PVA nanofibers) by electrospinning. Then, the Pd-CS/PVA nanofibers were treated at evaluated temperature to improve its solvent resistance and in situ reduce Pd²⁺ cations into Pd⁰ active species. The incorporated palladium nanoparticles with ultra small mean diameter of 3.73 ± 1.04 nm are evenly distributed inside the Pd-CS/PVA nanofiber. The resulting Pd-CS/PVA nanofiber mat exhibits high catalytic activity for Heck reaction of aromatic iodides with alkenes and can be recycled for 18 times without loss of initial activity. The high catalytic activity and stability of Pd-CS/PVA nanofiber mat can be attributed to the ultra small diameter nanofibers, strong chelating ability of chitosan, and fine embedment of palladium species inside the nanofiber. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48026.     

Novel zein‐based electrospun fibers with the water stability and strength necessary for various applications

BACKGROUND: Some of the problems with electrospun zein fiber are that it has very low tenacities in the dry and wet states and that mats of the fiber become films when immersed in water. The fibers are therefore unusable for various applications despite their good biocompatibility and biodegradability. This research was conducted to overcome these problems by electrospinning novel fibers containing various concentrations of zein, citric acid (CA) and sodium hypophosphite monohydrate (SHP) and by crosslinking the zein with CA and with SHP serving as a catalyst. RESULTS: The CA‐crosslinked electrospun zein fiber has as much as 10‐fold greater wet tenacity and 15‐fold greater dry tenacity than regular electrospun zein fiber. The average diameter of these fibers is 451 nm, which is the smallest diameter ever reported for zein‐based electrospun fiber. A mat of this fiber retains its fibrous structure when immersed in water, and the fiber retains about 70% of its tenacity after 16 days at 50 °C and 90% relative humidity. CONCLUSION: The high dry and wet tenacities, good water stability and small diameter of the novel CA‐crosslinked electrospun zein fiber make it attractive for biomedical and other applications that expose zein to water or that require high surface area. Copyright © 2008 Society of Chemical Industry     

Highly active and selective catalytic transfer hydrogenolysis of α-methylbenzyl alcohol catalyzed by supported Pd catalyst

A novel supported Pd catalyst was synthesized by using plant tannin grafted collagen fiber as the supporting matrix. The as-prepared Pd catalyst was subsequently used for the catalytic transfer hydrogenolysis of α-methylbenzyl alcohol. Due to the fibrous morphology of collagen fiber and the well dispersed Pd nanoparticles anchored by tannins, the as-prepared Pd catalyst showed superior activity for the catalytic transfer hydrogenolysis of α-methylbenzyl alcohol when compared with the Pd catalyst supported on inorganic oxides. Moreover, the as-prepared Pd catalyst can be reused at least 6 times without significant loss of activity and selectivity, suggesting a satisfied reusability.     

Suzuki‐ and Heck‐Type Cross‐Coupling with Palladium Nanoparticles Immobilized on Spherical Polyelectrolyte Brushes

We report on a systematic study of the use of palladium nanoparticles immobilized on spherical polyelectrolyte brushes – Pd@SPB – for Heck‐ and Suzuki‐type coupling reactions. The spherical polyelectrolyte brush particles serving as carriers for the palladium nanoparticles consist of a solid polystyrene core with a radius of 46 nm onto which long chains of cationic polyelectrolytes are grafted. The palladium nanoparticles have directly been generated within this brush layer and the stabilization of the nanoparticles is effected by the colloidal carriers, no further surface stabilization is necessary. We demonstrate that these composite particles present robust catalysts for the Heck‐ and Suzuki‐type coupling reactions. This was shown by carrying out the Suzuki‐ and Heck‐type coupling reactions at relatively low temperatures (Suzuki reaction: 50 °C, Heck reaction: 70 °C). We demonstrate that the catalytic composite particles are not changed by these reaction conditions and retain their full activity for at least four runs. The yields obtained for both reactions are good to excellent. The mild operation conditions of the palladium nanoparticles are traced back to the absence of surface stabilization. Further mechanistic implications are discussed.     

Polypyrrole–Palladium Nanocomposite-Coated Latex Particles as a Heterogeneous Catalyst in Water

Abstract  

Polypyrrole–palladium nanocomposite-coated cross-linked polystyrene latex particles (PS/PPy–Pd) showed an excellent catalytic activity for Suzuki and Heck reactions in aqueous media. The PS/PPy–Pd can be recovered easily and quantitatively through the repeated uses with simple filtration and they maintain their high catalytic activities.     

In situ Formation of Palladium Nanoparticles Inside the Pore Channels of Ordered Mesoporous Silica

Palladium-containing SBA-15 (SBA-15-Pd) was synthesized via an in situ approach. In this procedure, molecular assembly template was employed as a hydrophobic carrier to provide the compatible environment for the hydrophobic compounds. The hydrophobic solvent (CHCl₃) was used as a transport medium to inject the Pd precursor (Pd(acetylacetonate)₂) directly into the inner core of the surfactant micelles. A 1.46 wt% Pd loading was achieved without the loss of pore ordering. Highly dispersed and uniform palladium nanoparticles could be detected using transmission electron microscopy confirming also the absence of large particles outside the mesopore silica. The catalytic activities of the SBA-15-Pd nanocomposites were investigated in Heck coupling reactions with activated and non-activated aryl substrates. The SBA-15-Pd nanocomposites exhibit excellent catalytic activities and reuse ability in air for the Heck carbon–carbon coupling reactions.     

A highly efficient polymer‐anchored palladium(II) complex catalyst for hydrogenation,Heck cross‐coupling and cyanation reactions

BACKGROUND: Precise architectures of steric and electronic properties of palladium species play a crucial role in designing highly functionalized catalyst systems responsible for target organic transformations. Pd catalysts supported on polymer materials have been employed extensively as catalysts not only for hydrogenation but also for coupling reactions in the production of fine chemicals. RESULTS: A new polymer‐anchored Pd(II) complex has been synthesized and characterized. The catalyst shows high catalytic activity in the hydrogenation of styrene oxide, Heck cross‐coupling and cyanation reactions of aryl halides. The effect of various reaction parameters were investigated to optimize reaction conditions. The catalytic system shows good activity in the hydrogenation of styrene oxide (conversion 98%) with a selectivity to 2‐phenylethanol (93%) which is higher than its homogeneous analogues. The catalyst also exhibits excellent catalytic activity for the Heck cross‐coupling and cyanation reactions of various substituted and non‐substituted aryl halides. CONCLUSIONS: Results demonstrate that the catalyst is robust and stable and can be recovered quantitatively by simple filtration and reused several times without loss of activity. Copyright © 2010 Society of Chemical Industry     

交联腐植酸负载钯催化剂对Heck反应催化性能研究

通过简单的方法制得了环氧氯丙烷交联腐植酸负载钯配合物催化剂,并通过IR、TG进行表征。该催化剂能够成功地催化芳基卤和不同取代芳基卤与丙烯酸、苯乙烯和丙烯酰胺的Heck反应。进一步研究显示:环氧氯丙烷交联腐植酸负载钯催化剂还能够催化溴苯与丙烯酸、苯乙烯和丙烯酰胺的反应,产率都达到95%以上;在62℃及催化剂钯含量为0.038%的条件下也能很好地催化碘苯与丙烯酸的反应。催化剂经过简单的分离处理重复使用7次仍然可以得到75.6%的产率。     

Palladium‐Iminodiacetic Acid Immobilized on pH‐Responsive Polymeric Microspheres: Efficient Quasi‐Homogeneous Catalyst for Suzuki and Heck Reactions in Aqueous Solution

The pH‐responsive core‐shell microspheres of poly(styrene‐co‐methylacrylic acid) (PS‐co‐PMAA) containing a polystyrene (PS) core and a poly(methylacrylic acid) (PMAA) shell are synthesized by one‐stage soap‐free copolymerization and the catalyst system palladium‐iminodiacetic acid (IDA‐Pd) is immobilized on the outer shell‐layer of the core‐shell microspheres to form the quasi‐homogeneous and easily accessible catalyst PS‐co‐PMAA‐IDA‐Pd. This quasi‐homogeneous PS‐co‐PMAA‐IDA‐Pd catalyst is highly dispersed in the reaction medium just like a homogeneous one and can be separated like a heterogeneous catalyst by adjusting the pH of the reaction medium. Suzuki reactions employing the quasi‐homogeneous PS‐co‐PMAA‐IDA‐Pd catalyst are efficiently performed in water as the sole solvent under mild conditions such as room temperature. The PS‐co‐PMAA‐IDA‐Pd catalyst is also used in Heck reactions of a wide range of aryl halides with styrene and proves to be efficient in aqueous solution. The PS‐co‐PMAA‐IDA‐Pd catalyst has a low leaching loss and can be reused at least 4 times without loss of activity.     

Carboncarbon bond forming reactions: Application of covalently anchored 2,4,6-triallyloxy-1,3,5-triazine (TAT) Pd(II) complex over modified surface of SBA-15 to Heck,Suzuki, Sonogashira and Hiyama cross coupling reactions

A highly active SBA-15-TAT-Pd(II) catalyst was synthesized from organofunctionalized SBA-15 and 2,4,6-triallyloxy-1,3,5-triazine. The catalyst was employed in carrying out Heck, “copper-free” Sonogashira, Suzuki and Hiyama cross coupling reactions. Under the optimized conditions the catalyst displays excellent catalytic activity in delivering the desired products in good to excellent yields. The catalytic system exhibited superior activity regarding the time taken for the completion of reaction, isolation, Pd loading (0.62 mmol%) and yields of products as compared to the earlier reported heterogeneous SBA-15 anchored Pd catalysts. The catalyst could be recycled and reused for five times without any appreciable loss of catalytic activity.     

Structure and catalytic properties of Pd encapsulated in mesoporous silica SBA-15 fabricated by two-solvent strategy

The two-solvent method was employed to prepare Pd encapsulated in mesoporous silica (Pd/SBA-15). A 3.01 wt% Pd loading was achieved without the loss of pore ordering. Highly dispersed and uniform palladium nanoparticles could be detected using transmission electron microscopy confirming also the absence of large particles outside the mesopore silica. The catalytic activities of the Pd/SBA-15 nanocomposites were investigated in Heck coupling reactions with activated and non-activated aryl substrates. The Pd/SBA-15 nanocomposite exhibits excellent catalytic activities and reuse ability in air for the Heck carbon–carbon coupling reactions.     

Facile method to prepare Pd/Polystyrene composite microspheres and investigation on their catalytic properties

Nano-sized Pd/polystyrene composite nanoparticles were prepared via surfactant-free emulsion polymerization. The as-prepared composite particles were used as a catalyst for Suzuki reaction, and they showed excellent catalytic properties in the conversion and recyclability. First, polystyrene (PS) latex particles bearing carboxyl groups on the surfaces were synthesized via one-stage surfactant-free emulsion polymerization employing acrylic acid as the functional monomer. Thus, made the PS particles negatively charged and could attract positively charged Pd²⁺ ions. By adding PdCl₂ solution to this functional polystyrene emulsion, Pd²⁺ ions were attached to the surfaces and reduced to zero valent particles by the reducing agent, NaBH₄. Nano-sized Pd/PS composite particles could be synthesized via this facile method. The amount of the functional monomers, the Pd²⁺ content and the amount of the initiator played important roles to the final morphologies of the composite particles. The resulting composite microspheres were observed by TEM. Furthermore, catalytic properties of the as-prepared Pd/PS composite particles were studied via Suzuki reaction, and the results were characterized by FTIR and ¹H-NMR. The Pd/PS composite particles showed excellent conversion and could be recycled easily for reuse. After each round of Suzuki reaction, the Pd/PS composite particles could be separated just by filtration, the conversion still remained as high as 70.2?%, even when used 5 times.     

Oxidative Heck Coupling Using Pd(II) Supported on Organosilane-Functionalized Silica Mesocellular Foam

Oxidative Heck couplings of arylboronic acids and olefins are carried out under air to facilitate reoxidation of palladium without the need for an added co-oxidant using Pd(II) supported on silica surface-tethered bipyridyl, iminopyridine, or 3-aminopropyl ligands. Use of silica-supported iminopyridine or bipyridine ligands gives active catalysts, with the bipyridine-based catalyst being most efficient. The Heck products are formed with high yields and selectivities over the 1,4-addition product, and the silica supported bipyridine-based catalyst is easily recovered via simple filtration. Unlike similar supported catalysts in traditional Heck reactions involving aryl halides and olefins, the catalysts presented here can be used for multiple catalytic cycles without activity or selectivity loss.     

Highly active recyclable SBA-15-EDTA-Pd catalyst for Mizoroki-Heck,Stille and Kumada C–C coupling reactions

Highly efficient SBA-15-EDTA-Pd(11) heterogeneous catalyst was synthesized by covalent anchoring Pd-EDTA complex over organo-modified surface of SBA-15. SBA-15-EDTA-Pd(11) catalyst was found to exhibit excellent catalytic activity in appreciable yield for Heck, Stille and Kumada cross-coupling reactions. Catalytic system exhibited excellent activity for completion of reaction, isolation, Pd loading (0.87 mmol%) and yields of products as compared to earlier reported heterogeneous supported Pd catalysts. Covalently anchored heterogeneous SBA-15-EDTA-Pd(11) catalyst can be recycled for more than five times without noticeable loss in activity and selectivity.     

Polymer electrolyte membranes composed of an electrospun poly(vinylidene fluoride) fibrous mat in a poly(4‐vinylpyridine) matrix

Newly proposed polymer electrolyte membranes (PEMs) composed of an electrospun poly(vinylidene fluoride) (PVDF) fibrous mat embedded in a poly(4‐vinylpyridine) (P4VP) matrix were successfully fabricated in order to improve the mechanical and dimensional stabilities and ionic conductivity of membranes in lithium rechargeable batteries. Fourier transform infrared spectroscopic analysis showed that as a result of the use of a high voltage during electrospinning the crystalline structure of PVDF changed partially from α‐phase to β‐phase. Energy‐dispersive X‐ray spectroscopy confirmed the existence of crosslinked P4VP in the PVDF fibrous mat. The electrolyte uptakes of PVDF and PVDF/P4VP composite mats were higher than that of PVDF cast film. The tensile properties of PVDF/P4VP composite mat were considerably improved compared to those of the pristine PVDF fibrous mat under both dry and wet (soaked with electrolyte) conditions. In addition, the mechanical and dimensional stabilities of the PVDF/P4VP composite PEM were further enhanced due to crosslinking between the P4VP chains. Furthermore, the PVDF/P4VP composite PEM exhibited an ionic conductivity that was an order of magnitude higher than that of traditional PVDF film. © 2012 Society of Chemical Industry     

Gold‐nanoparticle‐decorated thermoplastic polyurethane electrospun fibers prepared through a chitosan linkage for catalytic applications

Thermoplastic polyurethane (TPU)‐electrospun‐fiber‐mat‐supported gold catalysts were prepared by the adsorption of gold nanoparticles (AuNPs) onto a TPU electrospun fiber mat after functionalization with chitosan (CS) by a dip‐coating method. The mechanism for the adsorption of AuNPs was electrostatic interaction between the positive charge of CS (? N ) and the negative charge of the AuNP surface (? COO^?) and coordination between the amine groups of CS and gold. The mat was crosslinked with glutaraldehyde vapor to strengthen the adhesion between the CS coating and TPU fibers after the adsorption of AuNPs. The catalytic activity of the supported gold catalyst was evaluated with the reduction of 4‐nitrophenol by NaBH₄ to demonstrate the excellent catalytic performance and its reusability for at least 10 cycles without a loss in activity. The rate constant increased with both an increase in the amount of supported catalyst and an increase in the ratio of the mat surface area to AuNP within the investigated scope. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133 , 44336.     

Dppc~+PF_6~-Pd(dba)_2催化的水相中的Heck偶联反应

研究了二茂钴阳离子双膦配体Dppc+PF6-催化的纯水中Heck反应的活性。结果表明Dppc+PF6-与Pd(dba)2形成的催化剂,以三乙胺为碱,在120℃反应2个或4个小时能够有效地催化不同碘代芳烃与不同烯烃的Heck偶联反应。该催化体系操作和后处理简单,通过乙醚萃取就可以很容易实现催化剂与底物的分离。     

Preparation of an Immobilized Lipase‐Palladium Artificial Metalloenzyme as Catalyst in the Heck Reaction: Role of the Solid Phase

A p‐nitrophenylphosphonate palladium pincer was synthesized and selectively inserted by irreversible attachment on the catalytic serine of different commercial lipases with good to excellent yields in most cases. Among all, lipase from Candida antarctica B (CAL‐B) was the best modified enzyme. The artificial metalloenzyme CAL‐B‐palladium (Pd) catalyst was subsequently immobilized on different supports and by different orienting strategies. The catalytic properties of the immobilized hybrid catalysts were then evaluated in two sets of Heck cross‐coupling reactions under different conditions. In the first reaction between iodobenzene and ethyl acrylate, the covalent immobilized CAL‐B‐Pd catalyst resulted to be the best one exhibiting quantitative production of the Heck product at 70 °C in dimethylformamide (DMF) with 25% water and particularly in pure DMF, where the soluble Pd pincer was completely inactive. A post‐immobilization engineering of catalyst surface by its hydrophobization enhanced the activity. The selectivity properties of the best hybrid catalyst were then assessed in the asymmetric Heck cross‐coupling reaction between iodobenzene and 2,3‐dihydrofuran retrieving excellent results in terms of stereo‐ and enantioselectivity.

     

Hydrophilic polystyrene/maleic anhydride ultrafine fibrous membranes

Polystyrene/maleic anhydride (PSMA) was synthesized to reach a viscosity‐average molecular weight of 700 kDa and fabricated into ultrafine fibrous membranes consisting of fibers with an average diameter of 300 nm. These ultrafine PSMA fibers were rendered insoluble in organic solvents by reactions with hydrazine and ethylenediamine (ED). The highly efficient incorporation of diamines into the fibrous membranes was easily achieved by brief immersions in either dilute (0.5 wt %) hydrazine for 1 min or ED ether solution for 2 min. Heating at 150°C for 5 min produced crosslinked PSMA with very little or no solubility in acetone with the retention of the fibrous membrane structure. The ED‐crosslinked membranes were particularly stable to both bases and acids as well as hydrophilic solvents, had a 46° water contact angle, and absorbed 22 times the amount of water as the as‐spun fibrous membrane. This post‐fiber‐formation crosslinking approach was robust, highly efficient, and fast and required very little crosslinking reagent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010