Biopolymers, especially cellulose, are vital to transitioning to a circular economy and reducing our reliance on fossil fuels. However, for many applications a high degree of cellulose hydroxyl modification is necessary. The challenge is that the chemical features of the hydroxyls of cellulose and water are similar. Therefore, chemical modification of cellulose is often explored under non-aqueous conditions with systems that result in high hydroxyl accessibility and reduce cellulose aggregation. Unfortunately, these systems depend on hazardous and complex solvents from fossil resources, which diverge from the initial sustainability objectives. To address this, we developed three new betaine-based ionic liquids that are fully bio-based, scalable, and green. We found that a specific ionic liquid had the perfect chemical features for the chemical activation of cellulose without disturbing its crystalline ordering. The high activation in heterogeneous conditions was exemplified by reacting cellulose with succinic anhydride, resulting in more than 30 % conversion of all hydroxyls on cellulose. Overall, this work opens new perspectives for the derivatization of cellulosic materials while simultaneously "keeping it green".

The shift towards sustainable feedstocks for platform chemicals requires new routes to access functional molecules that contain heteroatoms, but there are limited bio-derived feedstocks that lead to heteroatoms in platform chemicals. Combining renewable molecules of different origins could be a solution to optimize the use of atoms from renewable sources. However, the lack of retrosynthetic tools makes it challenging to examine the extensive reaction networks of various platform molecules focusing on multiple bio-based feedstocks. In this study, a protocol was developed to identify potential transformation pathways that allow for the use of feedstocks from different origins. By analyzing existing knowledge on chemical reactions in large databases, several promising synthetic routes were shortlisted, with the reaction of D-glucosamine and pyruvic acid being the most interesting to make pyrrole-2-carboxylic acid (PCA). The optimized synthetic conditions resulted in 50% yield of PCA, with insights gained from temperature variant NMR studies. The use of substrates obtained from two different bio-feedstock bases, namely cellulose and chitin, allowed for the establishment of a PCA-based chemical space.

Commercialization of photoelectrochemical (PEC) water-splitting devices requires the development of large-area, low-cost photoanodes with high efficiency and photostability. Herein, we address these challenges by using scalable fabrication techniques and porous transport layer (PTLs) electrode supports. We demonstrate the deposition of W-doped BiVO4 on Ti PTLs using successive-ionic-layer-adsorption-and-reaction methods followed by boron treatment and chemical bath deposition of NiFeOOH co-catalyst. The use of PTLs that facilitate efficient mass and charge transfer, allowed the scaling of the photoanodes (100 cm2) while maintaining ~90% of the performance obtained with 1 cm2 photoanodes for oxygen evolution reaction i.e. 2.10 mA cm-2 at 1.23 V vs. RHE. This is the highest reported performance to date. Integration with a polycrystalline Si PV cell leads to bias-free water splitting with a stable photocurrent of 208 mA for 6 h and 2.2% solar-to-hydrogen efficiency. Our findings highlight the importance of photoelectrode design towards scalable PEC device development.