Well-shaped poly(dimethylsiloxane)-based copolymer nanowires from spherical micelles via kinetic shape evolution.

The formation of self-assembled arrays or superstructures from copolymers has attracted intense research interest. Herein, we propose a kinetic approach to form self-assembled nanowires using a PDMS-based block copolymer consisting of poly(dimethylsiloxane)-b-poly[2-(cinnamoyloxy)ethyl methacrylate] (PDMS-b-PCEMA). The copolymer was synthesized by using the macroinitiator PDMS-Br to initiate 2-(trimethylsiloxy)ethyl methacrylate (HEMA-TMS) via ATRP, followed by hydrolysis of the TMS group and gradual esterification with cinnamoyl chloride. PDMS-b-PCEMA presented core-shell spherical micelles in tetrahydrofuran, which transformed into nanowires within 5 days self-assembly via a typical kinetic shape evolution. The diameter of the assembled nanowires with a PCEMA inner core and PDMS shell was about 25-35 nm. The formation of these nanowires reflected a balance between the PDMS and PCEMA components: the PDMS segment was soluble enough to form a corona block, which was beneficial for the transformation of the micellar shape. Meanwhile, the PCEMA segment was able to control the diameter of the nanowire micelles but had no decisive effect on their formation. The effect of solvents on the self-assembled micelles indicated that nanowires were formed in tetrahydrofuran and dichloromethane, while core-shell micelles were formed in acetone. This was due to the different permittivities of these solvents. The nanowires were fixed by cross-linking the PCEMA group under UV irradiation, which enhanced their stability. We believe that this work provides a new strategy for the formation of nanowires and offers a guide for the diversified self-assembly of nanostructures from copolymers.

CsPbBr3 Perovskite Nanocrystal Grown on MXene Nanosheets for Enhanced Photoelectric Detection and Photocatalytic CO2 Reduction.

All-inorganic CsPbX3 (X = Cl, Br or I) perovskite nanocrystals have attracted extensive interest recently due to their exceptional optoelectronic properties. In an effort to improve the charge separation and transfer following efficient exciton generation in such nanocrystals, novel functional nanocomposites were synthesized by the in situ growth of CsPbBr3 perovskite nanocrystals on two-dimensional MXene nanosheets. Efficient excited state charge transfer occurs between CsPbBr3 NCs and MXene nanosheets, as indicated by significant photoluminescence (PL) quenching and much shorter PL decay lifetimes compared with pure CsPbBr3 NCs. The as-obtained CsPbBr3/MXene nanocomposites demonstrated increased photocurrent generation in response to visible light and X-ray illumination, attesting to the potential application of these heterostructure nanocomposites for photoelectric detection. The efficient charge transfer also renders the CsPbBr3/MXene nanocomposite an active photocatalyst for the reduction of CO2 to CO and CH4. This work provides a guide for exploration of perovskite materials in next-generation optoelectronics, such as photoelectric detectors or photocatalyst.