Marriage of Organic and Grubbs Catalysts for Tandem Synthesis of Bottlebrush Polyesters.

Bottlebrush polymers (BBPs) have gained wide attention for their special characters, such as rigid main/side chains, stemming from the exceedingly high graft density. This study aims to provide a simple synthetic approach to BBPs with polyester side chains by merging ring-opening alternating copolymerization (ROAP) and ring-opening metathesis polymerization (ROMP). A simple phosphazene base (tBuP1) is employed for the ROAP of phthalic anhydride and epoxide, after which Grubbs third-generation catalyst (G3) is added to in situ switch on ROMP of the macromonomer, i.e., norbornenyl-ended alternating polyester. The compatibility of tBuP1 with G3 and well-controlled ROMP is evidenced by DOSY-NMR of mixed catalysts, characterization of BBPs, and side-chain degradation. The method can also be extended to BBPs with one-step synthesized block copolyesters side chains. These results highlight the strength of the non-nucleophilic organobase catalyst for convenient construction of complex (degradable) polymers with compositional diversity.

ZnFe2O4-Ni5P4 Mott-Schottky Heterojunctions to Promote Kinetics for Advanced Li-S Batteries.

The practical progress of lithium-sulfur batteries is hindered by the serious shuttle effect and the slow oxidation-reduction kinetics of polysulfides. Herein, the ZnFe2O4-Ni5P4 Mott-Schottky heterojunction material is prepared to address these issues. Benefitting from a self-generated built-in electric field, ZnFe2O4-Ni5P4 as an efficient bidirectional catalysis regulates the charge distribution at the interface and accelerates electron transfer. Meanwhile, the synergy of the strong adsorption capacity derived from metal oxides and the outstanding catalytic performance that comes from metal phosphides strengthens the adsorption of polysulfides, reduces the energy barrier during the reaction, accelerates the conversion between sulfur species, and further accelerates the reaction kinetics. Hence, the cell with ZnFe2O4-Ni5P4/S harvests a high discharge capacity of 1132.4 mAh g-1 at 0.5C and displays a high Coulombic efficiency of 99.3% after 700 cycles. The ZnFe2O4-Ni5P4/S battery still maintains a capacity of 610.1 mAh g-1 with 84.4% capacity retention after 150 cycles at 0.1C under a high sulfur loading of 3.2 mg cm-2. This work provides a favorable reference and advanced guidance for developing Mott-Schottky heterojunctions in lithium-sulfur batteries.