Buyin Shi

Synthesis of triphenylphosphine-based microporous organic nanotube framework supported Pd catalysts with excellent catalytic activity

This work reports an efficient strategy to prepare a type of triphenylphosphine-based microporous organic nanotube framework (MONFs-PPh3) as a platform for Pd catalyst (MONFs-PPh3@Pd) via hyper-crosslinking core–shell multicomponent bottlebrush copolymers. The triphenylphosphine ligands not only act as functional groups, but as a supporting part of the nanotube walls. This novel material possesses great adjustability for the mesopore sizes of nanotubes and the concentration of triphenylphosphine ligands within the frameworks, which can be tuned during bottlebrush copolymer synthesis at the molecular level. Moreover, MONFs-PPh3@Pd exhibits excellent catalytic activity in the Suzuki–Miyaura reaction of aryl chlorides in aqueous media, which is much higher than that of the corresponding disordered microporous organic polymer-based Pd catalyst and homogeneous molecular catalysts under similar conditions.

“Click Chemistry” Mediated Functional Microporous Organic Nanotube Networks for Heterogeneous Catalysis

The synthesis of azide functional microporous organic nanotube networks (N3-MONNs) via a Friedel-Crafts hyper-cross-linking reaction is reported. Subsequently, a general method for obtaining heterogeneous catalysts through a Cu-catalyzed alkyne-azide reaction is presented. The small-molecule catalysts such as 2,2,6,6,-tetramethylpiperidine-1-oyl and 4-(N,N-dimethylamino)pyridine can be anchored into the MONNs. Owing to the hierarchically porous structure and high surface area, these catalysts show high activity in selective oxidation of alcohols and acylation reaction, respectively.

Preparation of multifunctional hollow microporous organic nanospheres via a one-pot hyper-cross-linking mediated self-assembly strategy

Herein we report a universal method for the preparation of multifunctional hollow microporous organic nanospheres (H-MONs) using functional aromatic monomers (such as benzylamine, 2,2-bipyridine, triphenylamine or carbazole) and the polylactide-b-polystyrene (PLA-b-PS) diblock copolymer as precursors based on a one-pot hyper-cross-linking mediated self-assembly strategy. In this method, co-hyper-cross-linking among the PS block and various aromatic monomers forms the functional microporous organic shell frameworks, while the degradable PLA block produces the hollow core structure. By introducing functional organic ligands, various metal-loaded or heteroatom-doped H-MONs can be successfully synthesized. Owing to their high special surface area, robust organic framework, and hierarchically porous structure, these multifunctional H-MONs exhibited excellent catalytic activity or high adsorption capacity for radioactive iodine. The proposed one-pot strategy may provide a general approach to produce a variety of functional H-MONs for various applications in the future.

A Polymerization-Cutting Strategy: Self-Protection Synthesis of Thiol-Based Nanoporous Adsorbents for Efficient Mercury Removal

Highly toxic heavy metal ions such as mercury ions (Hg2+ ) are a great threat to human life and the environment. Developing new strategies and materials to remove the toxic heavy metal ions has attracted more and more attentions. Herein a facile self-protection synthesis of thiol-based nanoporous adsorbents for efficient mercury removal via a polymerization-cutting strategy is reported. The direct free-radical polymerization of divinyl disulfide derivative and subsequently cutting off the disulfide linkage, without post-synthesis or modification, can give rise to an exceptionally high density of thiol chelating sites. Moreover, the resultant thiol-based nanoporous adsorbents (NAs-SH) exhibit a high saturation uptake capacity (1240u2005mgu2009g-1 ) and reused ability for mercury removal from water solution. The proposed polymerization-cutting strategy may provide an alternative and cost-effective method for the design and synthesis of various efficient nanoporous adsorbents at large scale in the future.