We report a synthesis of amine-functionalized microporous organic nanotube frameworks supported Pt or Pd catalysts (Pt or Pd@NH2-MONFs) by a combination of hyper cross-linking tricomponent bottlebrush copolymers and subsequent gentle reduction. In this method, the intrabrush and interbrush cross-linking of polystyrene (PS) shell layer in the tricomponent bottlebrush copolymers led to the formation of micropores and large-sized nanopores (meso/macrospores) in NH2-MONFs, respectively, while selective removal of polylactide (PLA) core layer generated mesoporous tubular structure. Interestingly, the middle functional poly(Boc-aminoethyl acrylamide) (PBAEA) component could be deprotected to produce the free amine moieties in the channel of MONFs, which will play a key role to anchor Pt or Pd nanoparticles on the support by an in situ reduction with NaBH4. Owing to their high special surface area, robust organic framework, and hierarchically porous structure, the resultant Pt or Pd@NH2-MONFs show high heterogeneous catalytic activity and excellent reusability in the selective oxidation of alcohol and Heck reactions, respectively.

This work reports a triphenylphosphine-guided hyper-cross-linking self-assembly strategy to construct honeycomb-like bicontinuous P-doped porous polymers (HBPs) based on polylactide-b-polystyrene/4-diphenylphosphinostyrene (PLA-b-P(S/DPPS)) diblock copolymers. The triphenylphosphine (PPh3) groups derived from DPPS not only play as the cross-linkable monomer with S and DPPS but also serve as the strong P ligands for binding the metal species. Subsequently, Pd nanoparticles (NPs) can be effectly encapsulated into the synthesized HBPs by a simple impregnation-reduction method. The resultant Pd@HBPs show more excellent catalytic performance for selective hydrogenations than the corresponding homogeneous catalysts and synthesized heterogeneous analogues. The great performance could be attributed to the advantage of the three-dimensionally (3D) honeycomb-like interconnected mesoporous structure, which allows the accessible catalytically active sites to be efficiently exposed toward reactants. This strategy represents a new method for the preparation of porous organic polymers with special morphologies and various functionalizations for potential applications including energy storage, adsorption, separation, and catalysis.

•A synthesis of organic ligands incorporated hypercrosslinked microporous organic nanotube frameworks via Friedel-Crafts reaction of small aromatic organic ligands with core-shell bottlebrush copolymers was developed.•Hierarchical structure in O-HMONFs-based catalysts can accelerate mass transfer in efficient heterogeneous catalysis.•Such method could be a general approach to produce various functional microporous organic nanotube frameworks.Microporous organic polymers (MOP) usually have dominated micropores smaller than 2 nm, which may restrict their performance in the mass transfer processes. Adding mesopores into microporous materials to form hierarchical structure has been recognized as a promising route to eliminate their transport limitations and further improve their value in applications. Here we report a straightforward method for the synthesis of organic ligands incorporated hypercrosslinked microporous organic nanotube frameworks (O-HMONFs) via Friedel-Crafts hyper-crosslinking reaction of small aromatic organic ligands with core-shell bottlebrush copolymers as platforms for heterogeneous catalysts. In particular, because of the mesopores produced by the core degradation, O-HMONFs-based catalysts showed more comparable activities than the corresponding disordered MOP-based catalyst and homogeneous molecular catalyst under similar conditions. More importantly, this method might be suitable for various aromatic organic ligands and could be used as a general approach to produce a variety of functional microporous organic nanotube frameworks.A straightforward method for the synthesis of organic ligands incorporated hypercrosslinked microporous organic nanotube frameworks (O-HMONFs) via Friedel-Crafts hypercrosslinking reaction of small organic ligands with core-shell bottlebrush copolymers as platforms for heterogeneous catalysts is reported for the first time.Download high-res image (191KB)Download full-size image

Novel meso-tetraphenylporphyrin iron(III) chloride (Fe(TPP)Cl) functionalized microporous organic nanotube networks (Fe(TPP)Cl-MONNs) were successfully synthesized by an in situ hyper-crosslinking reaction between core–shell bottlebrush copolymers and Fe(TPP)Cl. The obtained Fe(TPP)Cl-MONN catalyst possesses a hierarchical porous structure, large surface area and good stability, which exhibits high catalytic activity and excellent reusability in the olefination of aldehydes and carbene insertion into N–H bonds with ethyl diazoacetate.

In this paper, we report a novel synthesis of amino-functionalized microporous organic nanotube networks (NH2-MONNs) by combination of hyper cross-linking and molecular templating of multicomponent bottlebrush copolymers. The amino-modified MONNs constructed from a unique trimodal micro, meso and macroporous architecture and flexible frameworks possess a specific surface area of 936 m2 g−1 and a pore volume of 1.67 cm3 g−1. Owing to the large surface area, good multi-porosity interconnectivity and excellent swelling properties in organic solvents, the resultant NH2-MONNs show highly efficient heterogeneous catalysis and excellent reusability in the Knoevenagel condensation and Henry reaction.

In this work, we present a novel synthesis of carboxyl-containing microporous organic nanotube networks (COOH-MONNs) by combination of hyper-cross-linking and molecular templating of core–shell bottlebrush copolymers. Highly dispersed palladium nanoparticles (Pd NPs) anchored on the COOH-MONNs (Pd@MONNs) have been prepared by in situ thermal decomposition of Pd(OAc)2. The Pd@MONNs composites were characterized by XRD, N2 adsorption, TEM, ICP-AES and XPS. The results show that bulk production of highly dispersed palladium nanoparticles can be achieved by a thermal decomposition method. Moreover, the obtained Pd@MONNs exhibit high activities for the Suzuki–Miyaura cross-coupling reaction and can be easily recovered and reused. This approach of using MONNs as a platform for catalysts is expected to open doors for new types of catalytic support for practical applications.

•A thiol-functionalized hierarchically porous material as Au catalyst support.•The catalyst shows unique framework structure and excellent stability.•Performance of the reduction reaction demonstrates its high catalytic activity.•Post-modification will develop its extensive application in numerous fields.In this work, we demonstrate a novel method that enables the fabrication of thiol-functionalized hierarchically porous materials (SH-HPMs) by combination of hyper-cross-linking and molecular templating of core-shell bottlebrush copolymers. Well-dispersed gold (Au) nanoparticles with an average size of 3.0 nm, synthesized by in situ reduction of HAuCl4, were then anchored into the SH-HPMs support, which showed remarkable catalytic performances on the reduction reaction of 4-nitrophenol.We demonstrate a novel fabrication of thiol-functionalized hierarchically porous materials (SH-HPMs) by combination of hyper-cross-linking and molecular templating of core-shell bottlebrush copolymers. Well-dispersed gold (Au) nanoparticles synthesized by in situ reduction of HAuCl4 were anchored into the SH-HPMs and showed remarkable catalytic performances in the reduction of 4-nitrophenol.

We demonstrate a novel method that enables the formation of core-confined bottlebrush copolymers (CCBCs) as catalyst supports. Significantly, owing to the site-isolated effect, these CCBC catalysts with the incompatible acidic para-toluenesulfonic acid (PTSA) and basic 4-(dimethylamino)pyridine (DMAP) groups can conduct a simple two-step sequential reaction in one vessel.

We demonstrate a novel method that enables the formation of core-confined bottlebrush copolymers (CCBCs) as catalyst supports. Significantly, owing to the site-isolated effect, these CCBC catalysts with the incompatible acidic para-toluenesulfonic acid (PTSA) and basic 4-(dimethylamino)pyridine (DMAP) groups can conduct a simple two-step sequential reaction in one vessel.