Wang Boyang, Waterhouse Geoffrey I N, Yang Bai, Lu Siyu
College of Chemistry, Pingyuan Laboratory, Zhengzhou University, Zhengzhou 450000, China.
School of Chemical Sciences, The University of Auckland, Auckland 1142, New Zealand.
Acc Chem Res. 2024 Oct 1;57(19):2928-2939. doi: 10.1021/acs.accounts.4c00516. Epub 2024 Sep 19.
ConspectusCarbon dots (CDs), as a novel type of fluorescent nanocarbon material, attract widespread attention in nanomedicine, optoelectronic devices, and energy conversion/storage due to their excellent optical properties, low toxicity, and high stability. They can be classified as graphene quantum dots, carbon quantum dots, and carbonized polymer dots (CPDs). Among these, CPDs exhibit tunable structures and components that allow fine-tuning of their optoelectronic properties, making them one of the most popular types of CDs in recent years. However, the structural complexity of CPDs stimulates deep exploration of the relationship between their unique structure and luminescent performance. As an organic-inorganic hybrid system, the diversity of self-limited quantum state carbon cores and polymer-hybrid shell layers makes understanding the underlying mechanisms and structure-property relationships in CPDs a very challenging task. In this context, elucidating the structural composition of CPDs and the factors that affect their optical properties is vital if the enormous potential of CPDs is to be realized. Achieving controllable structures with predefined optical properties via the adoption of specific functionalization strategies is the prized goal of current researchers in the field.In this Account, we describe the efforts made by our group in the synthesis, mechanism analysis, structural regulation, and functional applications of CPDs, with particular emphasis on the design of CPDs core-shell structures with tailored optoelectronic properties for applications in the fields of optoelectronics and energy. Specifically, through the rational selection of precursors, optimization of reaction conditions, and postmodification strategies for CPDs, we have demonstrated that it is possible to regulate both the carbon core and polymer shell layers, thereby achieving full-spectrum emission, high quantum yield, persistent luminescence, thermally activated delayed fluorescence, and laser action in CPDs. Furthermore, we have established structure-performance relationship in CPDs and proposed a universal strategy for synergistic interactions between hybrid carbon-based cores and surface micronanostructures. In addition, we unveiled a novel luminescence mechanism in cross-linked CPDs, specifically "cross-linking synergistically inducing quantum-state luminescence", which addresses the challenge of efficient circularly polarized luminescence in the liquid and solid phases of CPDs. Subsequently, strong cross-linking, dual-rigidity, and ordering preparation methods were introduced, thereby pioneering tunable laser emission from blue to near-infrared wavelengths. Additionally, we developed a new strategy of "confined composite nanocrystals of CPDs", leading to various high-performance hydrogen evolution catalysts for water electrolysis. The CPDs developed by this strategy not only possessed excellent optical properties but also enabled high efficiencies in field of energy conversion, thus maximizing the utilization of CPDs. Finally, we discuss important new trends in CPD research and development. Overall, this Account summarizes the latest advancements in CPDs in recent years, providing case-studies that enable deep understanding of structure-property-performance relationships and regulation strategies in CPDs, guiding the future expansion and application of CPDs.
综述
碳点（CDs）作为一种新型的荧光纳米碳材料，因其优异的光学性能、低毒性和高稳定性，在纳米医学、光电器件以及能量转换/存储领域受到广泛关注。它们可分为石墨烯量子点、碳量子点和碳化聚合物点（CPDs）。其中，CPDs展现出可调节的结构和组分，能够对其光电性能进行精细调控，使其成为近年来最受欢迎的碳点类型之一。然而，CPDs的结构复杂性促使人们深入探索其独特结构与发光性能之间的关系。作为一种有机-无机杂化体系，自限量子态碳核和聚合物杂化壳层的多样性使得理解CPDs的潜在机制和结构-性能关系成为一项极具挑战性的任务。在此背景下，若要实现CPDs的巨大潜力，阐明其结构组成以及影响其光学性能的因素至关重要。通过采用特定的功能化策略实现具有预定义光学性能的可控结构是该领域当前研究人员梦寐以求的目标。
在本综述中，我们描述了我们团队在CPDs的合成、机理分析、结构调控和功能应用方面所做的努力，特别强调了设计具有定制光电性能的CPDs核壳结构以用于光电子和能源领域。具体而言，通过合理选择前驱体、优化反应条件以及对CPDs进行后修饰策略，我们证明了可以同时调控碳核和聚合物壳层，从而在CPDs中实现全光谱发射、高量子产率、持续发光、热激活延迟荧光和激光作用。此外，我们建立了CPDs中的结构-性能关系，并提出了一种用于杂化碳基核与表面微纳米结构之间协同相互作用的通用策略。另外，我们揭示了交联CPDs中的一种新型发光机制，即“交联协同诱导量子态发光”，该机制解决了CPDs在液相和固相中高效圆偏振发光的挑战。随后，引入了强交联、双刚性和有序制备方法，从而开创了从蓝光到近红外波长的可调谐激光发射。此外，我们开发了一种“CPDs受限复合纳米晶体”的新策略，产生了用于水电解的各种高性能析氢催化剂。通过该策略开发的CPDs不仅具有优异的光学性能，还在能量转换领域实现了高效率，从而最大限度地利用了CPDs。最后，我们讨论了CPDs研发中的重要新趋势。总体而言，本综述总结了近年来CPDs的最新进展，提供了案例研究，使人们能够深入理解CPDs中的结构-性能-性能关系和调控策略，指导CPDs未来的扩展和应用。
