Review of the Phosphorylation of Lignocellulosic Fibers: Reaction Products, Characterization, and Potential Applications

Natural fibers are among the most extensively exploited bio-based materials in industry due to their abundance, affordability, and biodegradability. However, their intrinsic properties often require improvement through chemical, mechanical, or enzymatic treatments to expand their applications. Phosphorylation is a highly effective chemical modification that enables the covalent grafting of phosphate groups onto the fiber backbone. These functionalities enhance hydrophilicity, anionic charge density, swelling capacity, and water uptake, while significantly improving flame-retardant performance. In addition, phosphorylation can reduce energy consumption and production costs in the manufacture of functionalized micro- and nanofibrillated fibers, as the increased swelling facilitates fibrillation. Consequently, phosphorylated fibers are suitable for water treatment, biomedical devices, construction materials, and other advanced materials. Dozens of reagents and various synthetic routes have been explored to perform this reaction, each producing materials with distinct properties. Phosphorus content remains the primary parameter used to assess modification efficiency. This literature review examines existing phosphorylation methods, including reagents, substrates, and characterization techniques, and discusses applications such as flame retardancy, thermal insulation, ion exchange, energy storage, electrodes, and battery recycling. It also briefly addresses key challenges, including limited hydroxyl accessibility, control of the degree of substitution, potential cellulose degradation, and scalability constraints.