The Institute of Chemistry and The Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Jerusalem, 91904, Israel.
J Am Chem Soc. 2021 Jan 20;143(2):577-587. doi: 10.1021/jacs.0c10554. Epub 2020 Dec 22.
Semiconductor nanocrystals are promising photocatalysts for a wide range of applications, ranging from alternative fuel generation to biomedical and environmental applications. This stems from their diverse properties, including flexible spectral tunability, stability, and photocatalytic efficiencies. Their functionality depends on the complex influence of multiple parameters, including their composition, dimensions, architecture, surface coating, and environmental conditions. A particularly promising direction for rapid adoption of these nanoparticles as photocatalysts is their ability to act as photoinitiators (PIs) for radical polymerization. Previous studies served to demonstrate the proof of concept for the use of quantum confined semiconductor nanocrystals as photoinitiators, coining the term Quantum PIs, and provided insights for their photocatalytic mechanism of action. However, these early reports suffered from low efficiencies while requiring purging with inert gases, use of additives, and irradiation by high light intensities with very long excitation durations, which limited their potential for real-life applications. The progress in nanocrystal syntheses and surface engineering has opened the way to the introduction of the next generation of Quantum PIs. Herein, we introduce the research area of nanocrystal photocatalysts, review their studies as Quantum PIs for radical polymerization, from suspension polymerization to novel printing, as well as in a new family of polymerization techniques, of reversible deactivation radical polymerization, and provide a forward-looking view for the challenges and prospects of this field.
半导体纳米晶体是一类很有前途的光催化剂,可应用于各种领域,包括替代燃料的生成、生物医学和环境应用等。这是因为它们具有多种特性,包括灵活的光谱可调性、稳定性和光催化效率。它们的功能取决于多个参数的复杂影响,包括它们的组成、尺寸、结构、表面涂层和环境条件。这些纳米粒子作为光催化剂的一个特别有前途的应用方向是它们能够作为自由基聚合的光引发剂 (PI)。先前的研究证明了量子限制半导体纳米晶体作为光引发剂的概念验证,创造了“量子 PI”一词,并提供了其光催化作用机制的见解。然而,这些早期的报告效率低下,需要用惰性气体吹扫、使用添加剂,并需要高强度光长时间照射,这限制了它们在实际应用中的潜力。纳米晶体合成和表面工程的进展为引入下一代量子 PI 开辟了道路。在此,我们介绍了纳米晶体光催化剂的研究领域,综述了它们作为自由基聚合的量子 PI 的研究进展,包括悬浮聚合到新型印刷技术,以及在可逆失活自由基聚合这一新的聚合技术家族中的应用,并对该领域的挑战和前景进行了前瞻性展望。