As the most abundant natural polymer, cellulose is a prime candidate for the preparation of both sustainable and economically viable polymeric products hitherto predominantly produced from oil-based synthetic polymers. However, the utilization of cellulose to its full potential is constrained by its recalcitrance to chemical processing. Both fundamental and applied aspects of cellulose dissolution remain active areas of research and include mechanistic studies on solvent–cellulose interactions, the development of novel solvents and/or solvent systems, the optimization of dissolution conditions, and the preparation of various cellulose-based materials. In this review, we build on existing knowledge on cellulose dissolution, including the structural characteristics of the polymer that are important for dissolution (molecular weight, crystallinity, and effect of hydrophobic interactions), and evaluate widely used non-derivatizing solvents (sodium hydroxide (NaOH)-based systems, N,N-dimethylacetamide (DMAc)/lithium chloride (LiCl), N-methylmorpholine-N-oxide (NMMO), and ionic liquids). We also cover the subsequent regeneration of cellulose solutions from these solvents into various architectures (fibers, films, membranes, beads, aerogels, and hydrogels) and review uses of these materials in specific applications, such as biomedical, sorption, and energy uses.

Petroleum-based synthetic plastics play an important role in our life. As the detrimental health and environmental effects of synthetic plastics continue to increase, the renewable, degradable and recyclable properties of cellulose make subsequent products the “preferred environmentally friendly” alternatives, with a small carbon footprint. Despite the fact that the bioplastic industry is growing rapidly with many innovative discoveries, cellulose-based bioproducts in their natural state face challenges in replacing synthetic plastics. These challenges include scalability issues, high cost of production, and most importantly, limited functionality of cellulosic materials. However, in order for cellulosic materials to be able to compete with synthetic plastics, they must possess properties adequate for the end use and meet performance expectations. In this regard, surface modification of pre-made cellulosic materials preserves the chemical profile of cellulose, its mechanical properties, and biodegradability, while diversifying its possible applications. The review covers numerous techniques for surface functionalization of materials prepared from cellulose such as plasma treatment, surface grafting (including RDRP methods), and chemical vapor and atomic layer deposition techniques. The review also highlights purposeful development of new cellulosic architectures and their utilization, with a specific focus on cellulosic hydrogels, aerogels, beads, membranes, and nanomaterials. The judicious choice of material architecture combined with a specific surface functionalization method will allow us to take full advantage of the polymer’s biocompatibility and biodegradability and improve existing and target novel applications of cellulose, such as proteins and antibodies immobilization, enantiomers separation, and composites preparation.