Linker Independent Regioselective Protonation Triggered Detoxification of Sulfur Mustards with Smart Porous Organic Photopolymer.

The development of efficient metal-free photocatalysts for the generation of reactive oxygen species (ROS) for sulfur mustard (HD) decontamination can play a vital role against the stockpiling of chemical warfare agents (CWAs). Herein, one novel concept is conceived by smartly choosing a specific ionic monomer and a donor tritopic aldehyde, which can trigger linker-independent regioselective protonation/deprotonation in the polymeric backbone. In this context, the newly developed vinylene-linked ionic polymers (TPA/TPD-Ionic) are further explored for visible-light-assisted detoxification of HD simulants. Time-resolved-photoluminescence (TRPL) study reveals the protonation effect in the polymeric backbone by significantly enhancing the life span of photoexcited electrons. In terms of catalytic performance, TPA-Ionic outperformed TPD-Ionic because of its enhanced excitons formation and charge carrier abilities caused by the donor-acceptor (D-A) backbone and protonation effects. Moreover, the formation of singlet oxygen (1 O2 ) species is confirmed via in-situ Electron Spin Resonance (ESR) spectroscopy and density functional theory (DFT) analysis, which explained the crucial role of solvents in the reaction medium to regulate the (1 O2 ) formation. This study creates a new avenue for developing novel porous photocatalysts and highlights the crucial roles of sacrificial electron donors and solvents in the reaction medium to establish the structure-activity relationship.

Putting forward a Ni-metallosalphen-based porous organic polymer for detoxification of sulfur mustard gas simulant.

We have introduced a Friedel-Crafts alkylation strategy of a Ni-salphen complex as derived from 2-hydroxy-5-methoxybenzaldehyde, an isomer of biomass derived vanillin, to construct a Ni-salphen based porous organic polymer (Ni@T-POP). The X-ray absorption spectroscopy (XAS) analysis revealed the existence of Ni-N2O2 core sites in the Ni@T-POP framework, which demonstrates unprecedented catalytic efficiency towards oxidative decontamination of sulfur mustards (HD's) compared to its complex precursor.

Selective photocatalytic CO2 reduction to CH4 over metal-free porous polyimide in the solid-gas mode.

Using a catalyst-free one-pot polycondensation approach, a new donor-acceptor (D-A) based porous polyimide (PeTt-POP) photocatalyst was developed. PeTt-POP produced CH4 (125.63 ppm g-1 in 6 h) from CO2 under visible light irradiation in the gas-solid mode without the use of co-catalysts or sacrificial agents. The progress of the reaction and the corresponding intermediate species involved in the CO2 reduction were identified by operando DRIFTS experiments, from which a plausible reaction mechanism was proposed.