The synthesis of hierarchically mesoporous polymers with multiple functionalities is challenging. Herein we reported a template-free strategy for synthesis of phenolic azo-polymers with hierarchical porous structures based on diazo-coupling reaction in aqueous solution under mild conditions. The resultant polymers have surface areas up to 593 m(2)  g(-1) with the mesopore ratio of >80 %, and a good ability to complex with metal ions, such as Cu(2+) , Zn(2+) ,Ni(2+) , achieving a metal loading up to 26.24 wt %. Moreover, the polymers complexed with Zn showed excellent performance for catalyzing the reaction of CO2 with epoxide, affording a TOF of 2570 h(-1) in the presence of tetrabutyl ammonium bromide (7.2 mol %). The polymer complexed with Cu could catalyze the oxidation of alcohol with high efficiency.

COMMUNICATIONThis journal is B(C 6 F 5 ) 3 was proved to be an efficient metal-free catalyst for the methylation of amines using CO 2 as a C1 building block in the presence of hydrosilanes under easy-handling conditions. A broad scope of N-alkylanilines, dialkylamines and primary anilines all proceeded well under the catalytic conditions.

Core/shell structured NiCo2O4@NiMn LDH hybrids were fabricated as efficient electrocatalysts for rechargeable Zn–air batteries.

Azo-functionalized MOPs (Azo-MOPs) were synthesized via oxidative polymerization of aromatic amines catalyzed by t-BuOCl/NaI (25 °C, 1 h, yield: >95%), which displayed an excellent coordinating ability with a Ru complex. The resulting Ru-coordinated Azo-MOPs displayed high CO2 capacity and high performances for catalyzing the methylation of amines with CO2 under low pressure (0.5 MPa).

Mesoporous poly­(triphenylphosphine) with azo functionality (poly­(PPh 3 )-azo) is reported, which was synthesized via oxidative polymerization of P­(m-NH2Ph)3 at ambient conditions. This kind of polymer could strongly coordinate with metal ions (e.g., Ru3+) and could reduce Ag+ in situ to metallic form. The resultant metalated poly­(PPh 3 )-azo (e.g., poly­(PPh 3 )-azo-Ag or -Ru) were discovered to be highly efficient catalysts for CO2 transformation. Poly­(PPh 3 )-azo-Ag showed more than 400 times higher site-time-yield (STY) for the carboxylative cyclization of propargylic alcohols with CO2 at room temperature compared with the best heterogeneous catalyst reported. Poly­(PPh 3 )-azo-Ru also exhibited good activity for the methylation of amines with CO2. It was demonstrated that the high performances of the catalysts originated from the cooperative effects between the polymer and the metal species. In addition, both catalysts showed good stability and easy recyclability, thus demonstrating promising potential for practical utilization for the conversion of CO2 into value-added chemicals.

Mesoporous nitrogen-doped carbons with high nitrogen content and ultrahigh surface areas were prepared, which showed high efficiency for oxidation of alkanes in aqueous phase.

Fluorinated microporous organic polymers (F-MOPs) were designed, showing twice higher CO2 adsorption capacity than corresponding non-fluorous MOPs. The incorporation of phenanthroline moieties into F-MOPs afforded them the ability to coordinate with Ag(I), and the resultant F-MOP-Ag(I) displayed high efficiency for the reaction of CO2 with propargyl alcohols to form α-alkylidene cyclic carbonates at 25 °C.

A Tröger's base-derived microporous organic polymer (TB-MOP) was designed, which could adsorb CO2 and coordinate with a Ru(III) complex. The resultant TB-MOP-Ru showed good CO2 and H2 adsorbing performances, and high efficiency for catalysing hydrogenation of CO2 to HCOOH with a turnover number up to 2254 at 40 °C.