Guojian Chen

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway.

Phase-transfer hydroxylation of benzene with H2O2 catalyzed by a nitrile-functionalized pyridinium phosphovanadomolybdate†

A new nitrile-tethered pyridinium polyoxometalate (POM) was prepared by anion-exchange of the ionic liquid precursor [N-butyronitrile pyridine]Cl ([C3CNpy]Cl) with the Keggin phosphovanadomolybdic acid H5PMo10V2O40 (PMoV2), and the obtained organic POM salt [C3CNpy]4HPMoV2 was characterized by XRD, SEM, TG, 1H NMR, 13C NMR, ESI-MS, CHN elemental analysis, nitrogen sorption experiment, and melting point measure. When used as a catalyst, [C3CNpy]4HPMoV2 causes the first example of reaction-controlled phase-transfer hydroxylation of benzene with H2O2, showing high activity and stable reusability. Based on spectral characterizations and comparisons of reaction results, plus the reversible color change between fresh and recovered catalyst, a unique reaction mechanism is proposed for understanding the highly efficient [C3CNpy]4HPMoV2-catalyzed phase-transfer catalysis. The formation of dissolvable active species [VO(O2)]+ is responsible for the phase-transfer behavior, while the intramolecular charge transfer and the protonated nitrile in cations accelerate the reaction and favor a better catalyst recovery rate.

Construction of porous cationic frameworks by crosslinking polyhedral oligomeric silsesquioxane units with N-heterocyclic linkers

In fields of materials science and chemistry, ionic-type porous materials attract increasing attention due to significant ion-exchanging capacity for accessing diversified applications. Facing the fact that porous cationic materials with robust and stable frameworks are very rare, novel tactics that can create new type members are highly desired. Here we report the first family of polyhedral oligomeric silsesquioxane (POSS) based porous cationic frameworks (PCIF-n) with enriched poly(ionic liquid)-like cationic structures, tunable mesoporosities, high surface areas (up to 1,025 m2 g−1) and large pore volumes (up to 0.90 cm3 g−1). Our strategy is designing the new rigid POSS unit of octakis(chloromethyl)silsesquioxane and reacting it with the rigid N-heterocyclic cross-linkers (typically 4,4′-bipyridine) for preparing the desired porous cationic frameworks. The PCIF-n materials possess large surface area, hydrophobic and special anion-exchanging property, and thus are used as the supports for loading guest species PMo10V2O405−; the resultant hybrid behaves as an efficient heterogeneous catalyst for aerobic oxidation of benzene and H2O2-mediated oxidation of cyclohexane.

Hydrophobic Mesoporous Poly(ionic liquid)s towards Highly Efficient and Contamination‐Resistant Solid‐Base Catalysts

Mesoporous poly(ionic liquid)s were synthesized by radical copolymerization of the ionic liquid 1‐aminoethyl‐3‐vinylimidazolium bromide with divinylbenzene plus the ion exchange of bromide anions with hydroxyls. Characterizations revealed the high ionic liquid content, large surface area, and hydrophobicity for the sample prepared with equimolar amounts of ionic liquid and divinylbenzene, with good accessibility to organic compounds and resistance to CO2/H2O contamination. The mesoporous copolymer behaved as a superior and recyclable solid‐base catalyst for solvent‐free Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate, giving the much higher turnover frequency of 304 h−1 (yield 99 %, 0.5 h) than those of the nonporous analogues, commercial strong basic resins, and even homogeneous NaOH. The high activity was confirmed by Knoevenagel condensation with various substrates and Claisen–Schmidt condensation. A possible synergistic Lewis–Brønsted dual‐base‐center mechanism is proposed for understanding the catalytic behavior.

Schiff Base Structured Acid-Base Cooperative Dual Sites in an Ionic Solid Catalyst Lead to Efficient Heterogeneous Knoevenagel Condensations

An acid-base bifunctional ionic solid catalyst [PySaIm](3)PW was synthesized by the anion exchange of the ionic-liquid (IL) precursor 1-(2-salicylaldimine)pyridinium bromide ([PySaIm]Br) with the Keggin-structured sodium phosphotungstate (Na(3) PW). The catalyst was characterized by FTIR, UV/Vis, XRD, SEM, Brunauer-Emmett-Teller (BET) theory, thermogravimetric analysis, (1)H NMR spectroscopy, ESI-MS, elemental analysis, and melting points. Together with various counterparts, [PySaIm](3)PW was evaluated in Knoevenagel condensation under solvent and solvent-free conditions. The Schiff base structure attached to the IL cation of [PySaIm](3)PW involves acidic salicyl hydroxyl and basic imine, and provides a controlled nearby position for the acid-base dual sites. The high melting and insoluble properties of [PySaIm](3)PW are relative to the large volume and high valence of PW anions, as well as the intermolecular hydrogen-bonding networks among inorganic anions and IL cations. The ionic solid catalyst [PySaIm](3)PW leads to heterogeneous Knoevenagel condensations. In solvent-free condensation of benzaldehyde with ethyl cyanoacetate, it exhibits a conversion of 95.8 % and a selectivity of 100 %; the conversion is even much higher than that (78.2 %) with ethanol as a solvent. The solid catalyst has a convenient recoverability with only a slight decrease in conversion following subsequent recyclings. Furthermore, the new catalyst is highly applicable to many substrates of aromatic aldehydes with activated methylene compounds. On the basis of the characterization and reaction results, a unique acid-base cooperative mechanism within a Schiff base structure is proposed and discussed, which thoroughly explains not only the highly efficient catalytic performance of [PySaIm](3)PW, but also the lower activities of various control catalysts.

A dicationic ionic liquid-modified phosphotungstate hybrid catalyst for the heterogeneous oxidation of alcohols with H 2 O 2

An ionic hybrid catalyst 1,1′-(butane-1,4-diyl)-bis(3-methylimidazolium) phosphotungstate (abbreviated [Dmim]1.5PW) has been prepared by anion-exchange of the divalent ionic liquid (IL) 1,1′-(butane-1,4-diyl)-bis(3-methylimidazolium) di(bromide) with the Keggin phosphotungstic acid H3PW12O40, and characterized by IR, 1H NMR, 13C NMR, ESI-MS, TG, SEM, XRD, BET surface area measurements, elemental analysis, and melting point. The hybrid material was evaluated as a catalyst for the oxidation of alcohols with aqueous hydrogen peroxide under various conditions. The catalytic performance of [Dmim]1.5PW was also compared with related catalysts bearing other cations or anions. The new hybrid [Dmim]1.5PW proved to be an efficient liquid-solid heterogeneous catalyst for H2O2-based oxidation of alcohols, with the advantages of high conversion and selectivity, easy recovery, and quite good reusability.