- Controllable preparation of phosphonium-based polymeric ionic liquids as highly selective nanocatalysts for the chemical conversion of CO2 with epoxides
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A novel approach to overcoming the insulating properties of olivine 5 V electrode materials is realized in carbon-free LiCoPO4 thin films by tailoring its chemical composition via the incorporation of lithium cobalt triphosphate into the olivine phase, thereby forming a network of conductive channels. The cyclic voltammograms of the engineered material exhibited a redox potential of ≈4.8 V/4.9 V. The experimentally obtained energy diagram quantified the inductive effect which led to the increase of the redox energy by ≈1.0 eV in comparison to LiCoO2 layered oxide. Although the enhanced electronic conductivity and excellent electrochemical activity were obtained by using the thin film cathode material, the strategy of the design of olivine with triphosphate can be extended to more thick electrodes (>1 μm), giving a perspective for the development of 5 V all solid state batteries suitable for commercial application. The evident ability to exchange the charge of all Co2+ ions with lithiation/delithiation reaction and deliver high power in carbon free high voltage cathode material opens up new perspectives for the development of next generation of high energy density electrochemical storage devices.
- Liu, Ying,Cheng, Weiguo,Zhang, Yanqiang,Sun, Jian,Zhang, Suojiang
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Read Online
- Preparation method of cyclic carbonate
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The invention belongs to the technical field of materials, and particularly relates to a preparation method of a cyclic carbonate, which takes a double-center porous polymer as a catalyst and catalysis CO. 2 The conversion is cyclic carbonate, and the double-center porous polymer is a double-center heterogeneous porous catalyst of metalloporphyrin and quaternary phosphonium sites. The invention solves the problem of complicated recovery of the catalyst for synthesis of the existing cyclocarbonate, utilizes the double-center porous polymer containing the metalloporphyrin and the quaternary phosphonium site as a catalyst to realize the combination and synergistic combination of the two active centers on the molecular level, thereby efficiently converting carbon dioxide into cyclic carbonate.
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Paragraph 0029-0033
(2021/11/03)
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- Double-center porous polymer and preparation method thereof
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The invention belongs to the technical field of catalysts, and particularly relates to a double-center porous polymer, a preparation method thereof, a porphyrin and 4 - (diphenylphosphino) styrene monomer which are functionalized by vinyl, and are prepared by quaternary phosphonium and metal coordination. The invention solves the defect that an existing porous catalyst structure is not easy to regulate and control, utilizes metalloporphyrin and quaternary phosphonium sites as an active center and is fixed in a porous polymer to form a double-center heterogeneous porous catalyst.
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Paragraph 0025; 0028-0031
(2021/11/21)
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- Phosphine triply cross-linked by organic polymer, transition metal complex using said phosphine as a ligand, and catalyst
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Provided are: a polymer-supported phosphane compound exhibiting excellent catalytic reaction activity; a complex including the compound and a transition metal; and a catalyst including the complex. This polymer compound includes: units of threefold styrene cross-linked phosphane; and styrene units having substituent groups (R) in position 4 (provided that R represents hydrogen, a C1-6 lower alkyl group, a C1-6 lower alkoxy group, or a polar functional group). In the formula in which the polymer compound includes structure (1), PS represents a polystyrene unit chain including the styrene units having the substituent groups (R). The complex includes the polymer and a transition metal. The catalyst for an organic compound coupling reaction includes the complex.
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Page/Page column 12; 14
(2018/07/29)
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- Method for synthesizing novel fluoride-free organic phosphine ligand modified by carbonate ester
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The invention relates to the field of organic synthesis, and provides a method for synthesizing a novel fluoride-free organic phosphine ligand modified by carbonate ester. According the synthesis method, p-bromostyrene or derivatives of the p-bromostyrene are adopted as raw materials for preparing a Grignard reagent which reacts with a phosphorus source to produce a skeleton-structure molecule with triphenylphosphine, and after oxidation, epoxidation, cycloaddition, reduction are conducted, the target molecular structure can be obtained. The synthesis method has the advantages that by synthesizing the novel organic CO2-soluable phosphine ligand, the solubility of the phosphine ligand in supercritical CO2 is improved, so that the application of fluoride-free phosphine ligand- organo-metallic catalysts in the supercritical CO2 is realized; besides, due to the property that the organic carbonate ester compound is insoluble in weak or non-polar organic solvent, such as an alkane compound,the fluorine-free phosphine ligand modified by the carbonate group is provided with a function of phase separation in a reaction system so that the recovery and reuse of the catalysts can be achieved.
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Paragraph 0029; 0030; 0040
(2018/03/09)
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- Frustrated Lewis Pair Polymers as Responsive Self-Healing Gels
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Steric bulk prevents the formation of strong bonds between Lewis acids and bases in frustrated Lewis pairs (FLPs), where latent reactivity makes these reagents transformative in small molecule activations and metal-free catalysis. However, their use as a platform for developing materials chemistry is unexplored. Here we report a fully macromolecular FLP, built from linear copolymers that containing either a sterically encumbered Lewis base or Lewis acid as a pendant functional group. The target functional copolymers were prepared by a controlled radical copolymerization of styrene with designer boron or phosphorus containing monomers. Mixtures of the B- and P-functionalized polystyrenes do not react, with the steric bulk of the functional monomers preventing the favorable Lewis acid base interaction. Addition of a small molecule (diethyl azodicarboxylate) promotes rapid network formation, cross-linking the reactive polymer chains. The resulting gel is dynamic, can self-heal, is heat responsive, and can be reshaped by postgelation processing.
- Wang, Meng,Nudelman, Fabio,Matthes, Rebecca R.,Shaver, Michael P.
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supporting information
p. 14232 - 14236
(2017/10/17)
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- Highly efficient aqueous phase chemoselective hydrogenation of α,β-unsaturated aldehydes catalysed by phosphine-decorated polymer immobilized IL-stabilized PdNPs
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Phosphino-decorated polymer immobilised ionic liquid phase stabilised palladium nanoparticles (PdNP@PPh2-PIILP) and their PEGylated counterparts (PdNP@PPh2-PEGPIILP) are remarkably active and exceptionally selective catalysts for the aqueous phase hydrogenation of α,β-unsaturated aldehydes, ketones, esters and nitriles with PdNP@PPh2-PEGPIILP giving complete conversion and 100% selectivity for reduction of the CC bond, under mild conditions. This is the most selective PdNP-based system to be reported for the aqueous phase hydrogenation of this class of substrates.
- Doherty,Knight,Backhouse,Abood,Alshaikh,Fairlamb,Bourne,Chamberlain,Stones
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supporting information
p. 1635 - 1641
(2017/06/05)
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- Flexibility Matters: Cooperative Active Sites in Covalent Organic Framework and Threaded Ionic Polymer
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The combination of two or more reactive centers working in concert on a substrate to facilitate the reaction is now considered state of the art in catalysis, yet there still remains a tremendous challenge. Few heterogeneous systems of this sort have been exploited, as the active sites spatially separated within the rigid framework are usually difficult to cooperate. It is now shown that this roadblock can be surpassed. The underlying principle of the strategy presented here is the integration of catalytic components with excellent flexibility and porous heterogeneous catalysts, as demonstrated by the placement of linear ionic polymers in close proximity to surface Lewis acid active sites anchored on the walls of a covalent organic framework (COF). Using the cycloaddition of the epoxides and CO2 as a model reaction, dramatic activity improvements have been achieved for the composite catalysts in relation to the individual catalytic component. Furthermore, they also clearly outperform the benchmark catalytic systems formed by the combination of the molecular organocatalysts and heterogeneous Lewis acid catalysts, while affording additional recyclability. The extraordinary flexibility and enriched concentration of the catalytically active moieties on linear polymers facilitate the concerted catalysis, thus leading to superior catalytic performance. This work therefore uncovers an entirely new strategy for designing bifunctional catalysts with double-activation behavior and opens a new avenue in the design of multicapable systems that mimic biocatalysis.
- Sun, Qi,Aguila, Briana,Perman, Jason,Nguyen, Nicholas,Ma, Shengqian
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supporting information
p. 15790 - 15796
(2016/12/16)
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- A Polymer-Bound Monodentate-P-Ligated Palladium Complex as a Recyclable Catalyst for the Suzuki-Miyaura Coupling Reaction of Aryl Chlorides
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A three-fold cross-linked polymer-bound phosphine (POL-Ph3P) with high phosphorus content has been prepared. The phosphorus-containing polymer forms a monodentate-P-ligated palladium complex, which shows excellent activity in Suzuki-Miyaura cross-coupling reactions of aryl chlorides. Importantly, the catalyst Pd/POL-Ph3P is highly stable and can be reused for at least 10 times without losing reactivity.
- Zhou, Yun-Bing,Li, Cun-Yao,Lin, Min,Ding, Yun-Jie,Zhan, Zhuang-Ping
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supporting information
p. 2503 - 2508
(2015/08/18)
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- Threefold cross-linked polystyrene-triphenylphosphane hybrids: Mono-P-ligating behavior and catalytic applications for aryl chloride cross-coupling and C(sp3)-H borylation
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Covalently bound polystyrene-phosphane hybrids were prepared by a method based on radical emulsion polymerization of styrenes in the presence of a tris(p-vinylphenyl)phosphane cross-linker. These hybrids favor mono-P-ligation to transition-metal complexes and are useful for challenging catalysis, such as Pd-catalyzed C-C/C-N couplings with unactivated chloroarenes and Ir- or Rh-catalyzed C(sp3)-H borylations. Copyright
- Iwai, Tomohiro,Harada, Tomoya,Hara, Kenji,Sawamura, Masaya
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supporting information
p. 12322 - 12326
(2013/12/04)
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- Highly chemoselective metal-free reduction of phosphine oxides to phosphines
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Unprecedented chemoselective reductions of phosphine oxides to phosphines proceed smoothly in the presence of catalytic amounts of specific Br?nsted acids. By utilizing inexpensive silanes, e.g., PMHS or (EtO)2MeSiH, other reducible functional groups such as ketones, aldehydes, olefins, nitriles, and esters are well-tolerated under optimized conditions.
- Li, Yuehui,Lu, Liang-Qiu,Das, Shoubhik,Pisiewicz, Sabine,Junge, Kathrin,Beller, Matthias
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p. 18325 - 18329
(2013/01/15)
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- Novel polymer incarcerated palladium with phosphinated polymers: Active catalyst for Suzuki-Miyaura coupling without external phosphines
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(Chemical Equation Presented) Immobilization of a palladium catalyst with use of new phosphinated polymers was carried out utilizing the polymer incarcerated (PI) method. This phosphinated PI Pd catalyst showed excellent activity in Suzuki-Miyaura couplin
- Nishio, Ryo,Sugiura, Masaharu,Kobayashi, Shu
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p. 4831 - 4834
(2007/10/03)
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- Direct Radical Polymerization of 4-Styryldiphenylphosphine: Preparation of Cross-Linked and Non-Cross-Linked Triphenylphosphine-Containing Polystyrene Polymers
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We report herein a simple synthesis of 4-styryldiphenylphosphine and the radical copolymerization of it with styrene, both with and without a cross-linker, to directly form cross-linked and non-cross-linked polystyrene supported triphenylphosphine in which the level of phosphine incorporation can be easily and accurately controlled. The utility of these polymers is demonstrated by their use in Mitsunobu and alcohol bromination reactions.
- Choi, Matthew Kwok Wai,He, Helen Song,Toy, Patrick H.
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p. 9831 - 9834
(2007/10/03)
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- Acetonyltriphenylphosphonium bromide and its polymer-supported analogues as catalysts in protection and deprotection of alcohols as alkyl vinyl ethers
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Both acetonyltriphenylphosphonium bromide (ATPB, 1) and poly-p-styryldiphenylacetonylphosphonium bromide (A) were effective catalysts in the protection of alcohols as THP, THF, and EE ethers as well as the cleavage of THP, THF, and EE ethers to the corresponding alcohols. They could be applied to 1°, 2° and 3° alcohols, phenol and acid-labile alcohols. Both ATPB and catalyst A are excellent catalysts in the present study. It needed only 1×10-2-1.25×10-2 mol equiv. of the polymer-supported catalyst A in the reactions.
- Hon, Yung-Son,Lee, Chia-Fu,Chen, Rong-Jiunn,Szu, Ping-Hui
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p. 5991 - 6001
(2007/10/03)
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- Manganese(II) complexes containing polystyryl Diphenylphosphine oxide as ligand and their reactivity with sulfur dioxide
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The ligand polystyryl diphenylphosphine oxide (L) and several manganese(II) complexes with empirical formulae MnLmX2·nH2O and MnLmSO4·3H2O (m = 2, 3; n=1-4; X=Cl, Br, I, NCS, NO3) have been synthesised and characterised. The absorption of sulfur dioxide by these complexes has been examined in the solid state, at room temperature and in the 230-30 °C temperature range, and also in SO2-saturated toluene suspensions. After the interaction between sulfur dioxide and metallic complexes some air-stable SO2 adducts of accurate formulae could be isolated. Nitrate complexes appear to exhibit distinct behaviour due to an additional reaction with SO2; viz. nitrate ions appear to be replaced by sulfate ions in the SO2 adducts. Sulfur dioxide desorption was studied for SO2 adducts by heating at 16O °C under reduced pressure for 1 h or at 300 °C for about 15 min at atmospheric pressure. Acta Chemica Scandinavica 1997.
- Sanmartin, Jesus,Bermejo, Manuel R.,Sousa, Antonio,Fondo, Matilde,Gomez-Forneas, Esther,McAuliffe, Charles A.
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- POLYMER-IMMOBILIZED COMPLEXES OF PLATINUM(II): THEIR PRECURSORS AND PREPARATION STUDIED BY HIGH-RESOLUTION SOLID-STATE 31P NMR USING MAGIC-ANGLE SPINNING TECHNIQUES.
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Solid-state **3**1P NMR employing high-power proton decoupling, cross-polarization, and magic-angle spinning has been used to characterize various polymer-immobilized phosphine ligands and their platinum complexes. The reduction of polymer (polystyrene cr
- Fyfe,Clark,Davies,Hayes,Wasylishen
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p. 6577 - 6584
(2007/10/02)
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