Tetrameric self-assembling of water-lean solvents enables carbamate anhydride-based CO2 capture chemistry.

Carbon capture, utilization and storage is a key yet cost-intensive technology for the fight against climate change. Single-component water-lean solvents have emerged as promising materials for post-combustion CO2 capture, but little is known regarding their mechanism of action. Here we present a combined experimental and modelling study of single-component water-lean solvents, and we find that CO2 capture is accompanied by the self-assembly of reverse-micelle-like tetrameric clusters in solution. This spontaneous aggregation leads to stepwise cooperative capture phenomena with highly contrasting mechanistic and thermodynamic features. The emergence of well-defined supramolecular architectures displaying a hydrogen-bonded internal core, reminiscent of enzymatic active sites, enables the formation of CO2-containing molecular species such as carbamic acid, carbamic anhydride and alkoxy carbamic anhydrides. This system extends the scope of adducts and mechanisms observed during carbon capture. It opens the way to materials with a higher CO2 storage capacity and provides a means for carbamates to potentially act as initiators for future oligomerization or polymerization of CO2.

Non-thermal plasma-assisted rapid hydrogenolysis of polystyrene to high yield ethylene.

The evergrowing plastic production and the caused concerns of plastic waste accumulation have stimulated the need for waste plastic chemical recycling/valorization. Current methods suffer from harsh reaction conditions and long reaction time. Herein we demonstrate a non-thermal plasma-assisted method for rapid hydrogenolysis of polystyrene (PS) at ambient temperature and atmospheric pressure, generating high yield (>40 wt%) of C1-C3 hydrocarbons and ethylene being the dominant gas product (Selectivity of ethylene, SC2H4 > 70%) within ~10 min. The fast reaction kinetics is attributed to highly active hydrogen plasma, which can effectively break bonds in polymer and initiate hydrogenolysis under mild condition. Efficient hydrogenolysis of post-consumer PS materials using this method is also demonstrated, suggesting a promising approach for fast retrieval of small molecular hydrocarbon modules from plastic materials as well as a good capability to process waste plastics in complicated conditions.

Improved Polydopamine Deposition in Amine-Functionalized Silica Aerogels for Enhanced UV Absorption.

Silica aerogels are interesting porous materials with extremely low density and high surface area, making them advantageous for a number of aerospace and catalysis applications. Here, we report the preparation of polydopamine (PDA)-functionalized silica aerogels using an in situ coating method, wherein the dopamine monomer was allowed to diffuse through the underlying structure of the gels in the absence of any external base and polymerize on the surface of the gel. The use of a siloxane precursor with an amine functionality decorates the silica backbone, allowing for a superior PDA coating, as evident in the darker color of PDA-coated amine-functionalized silica gels than PDA-coated silica-only gels and the X-ray photoelectron spectroscopy results. Furthermore, by varying the coating time, a series of aerogels with increasing optical absorption are prepared. Analyses using Brunauer-Emmett-Teller, scanning electron microscopy, and pycnometry show that the in situ PDA coating does not affect the inherent properties of the silica aerogels as opposed to PDA coatings deposited using an external base. Aerogels coated for 12 h and 24 h offer a surface area of 614 ± 35 and 658 ± 15 m2/g along with a porosity of 92.6 ± 0.9 and 92.4 ± 0.7%, respectively, properties similar to the native silica aerogels. PDA-coated aerogels have the potential to serve as UV ray mitigating materials due to the tortuosity of the underlying structure and the unique chemical properties of the PDA coating.