Covalent functionalization of 1D and 2D sp²-carbon nanoallotropes - twelve years of progress (2011-2023)

Carbon nanoallotropes have attracted significant attention in the field of materials science due to their unique combination of physicochemical and biological properties, with numerous applications. One-dimensional (1D) and two-dimensional (2D) sp²-carbon nanoallotropes, such as carbon nanohorns (CNHs), carbon nanotubes (CNTs), and graphene, have emerged as prominent candidates for a variety of technological advancements. To fully exploit their exceptional characteristics, the covalent functionalization of these nanostructures may alleviate the problems with the processing and final performance. This route of the carbon nanoallotrope functionalization is based on a covalent attachment of functional groups or molecules (via linkers of various strengths) to their surfaces, enabling precise control over physical, chemical, biological, and electronic properties. Such an approach opens up new avenues for tailoring the nanoallotrope characteristics, such as solubility/dispersibility, reactivity, and interactions with other materials. Over more than the last decade, significant progress has been made in the covalent functionalization of both 1D and 2D sp²-carbon nanoallotropes, paving the way for diverse applications in the nanoelectronics, energy storage, sensing, and biomedical fields. In this comprehensive review, we provide state-of-the-art advancements and achievements in the covalent functionalization of 1D and 2D sp²-carbon nanoallotropes during the past dozen years. We aim to highlight the key strategies, methodologies, and breakthroughs that have significantly contributed to this field. Eventually, we discuss the implications of those advancements and explore the opportunities for future research and applications.