Florent Héroguel

Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization

Formaldehyde protects and serves The lignin found in plants is a desirable renewable feedstock for fuels and other useful compounds. Breaking down such a strong, energy-dense polymer, however, requires pretreatment of plant biomass under harsh conditions. These pretreatment steps often cause side reactions within the polymer itself, which lower the overall yields of lignin monomers. Shuai et al. used formaldehyde during pretreatment to block the reactive groups that lead to carbon-carbon linkages in lignin. This simple step stabilized lignin during pretreatment, resulting in dramatically improved yields. Science, this issue p. 329 Using formaldehyde protects lignin from the cross-reactions that lower yields during biomass processing. Practical, high-yield lignin depolymerization methods could greatly increase biorefinery productivity and profitability. However, development of these methods is limited by the presence of interunit carbon-carbon bonds within native lignin, and further by formation of such linkages during lignin extraction. We report that adding formaldehyde during biomass pretreatment produces a soluble lignin fraction that can be converted to guaiacyl and syringyl monomers at near theoretical yields during subsequent hydrogenolysis (47 mole % of Klason lignin for beech and 78 mole % for a high-syringyl transgenic poplar). These yields were three to seven times those obtained without formaldehyde, which prevented lignin condensation by forming 1,3-dioxane structures with lignin side-chain hydroxyl groups. By depolymerizing cellulose, hemicelluloses, and lignin separately, monomer yields were between 76 and 90 mole % for these three major biomass fractions.

Improving Heterogeneous Catalyst Stability for Liquid-phase Biomass Conversion and Reforming

Biomass is a possible renewable alternative to fossil carbon sources. Today, many bio-resources can be converted to direct substitutes or suitable alternatives to fossil-based fuels and chemicals. However, catalyst deactivation under the harsh, often liquid-phase reaction conditions required for biomass treatment is a major obstacle to developing processes that can compete with the petrochemical industry. This review presents recently developed strategies to limit reversible and irreversible catalyst deactivation such as metal sintering and leaching, metal poisoning and support collapse. Methods aiming to increase catalyst lifetime include passivation of low-stability atoms by overcoating, creation of microenvironments hostile to poisons, improvement of metal stability, or reduction of deactivation by process engineering.

Densely Packed, Ultra Small SnO Nanoparticles for Enhanced Activity and Selectivity in Electrochemical CO2 Reduction

Controlling the selectivity in electrochemical CO2 reduction is an unsolved challenge. While tin (Sn) has emerged as a promising non-precious catalyst for CO2 electroreduction, most Sn-based catalysts produce formate as the major product, which is less desirable than CO in terms of separation and further use. Tin monoxide (SnO) nanoparticles supported on carbon black were synthesized and assembled and their application in CO2 reduction was studied. Remarkably high selectivity and partial current densities for CO formation were obtained using these SnO nanoparticles compared to other Sn catalysts. The high activity is attributed to the ultra-small size of the nanoparticles (2.6 nm), while the high selectivity is attributed to a local pH effect arising from the dense packing of nanoparticles in the conductive carbon black matrix.

Slowing the Kinetics of Alumina Sol-Gel Chemistry for Controlled Catalyst Overcoating and Improved Catalyst Stability and Selectivity

Catalyst overcoating is an emerging approach to engineer surface functionalities on supported metal catalyst and improve catalyst selectivity and durability. Alumina deposition on high surface area material by sol-gel chemistry is traditionally difficult to control due to the fast hydrolysis kinetics of aluminum-alkoxide precursors. Here, sol-gel chemistry methods are adapted to slow down these kinetics and deposit nanometer-scale alumina overcoats. The alumina overcoats are comparable in conformality and thickness control to overcoats prepared by atomic layer deposition even on high surface area substrates. The strategy relies on regulating the hydrolysis/condensation kinetics of Al(s BuO)3 by either adding a chelating agent or using nonhydrolytic sol-gel chemistry. These two approaches produce overcoats with similar chemical properties but distinct physical textures. With chelation chemistry, a mild method compatible with supported base metal catalysts, a conformal yet porous overcoat leads to a highly sintering-resistant Cu catalyst for liquid-phase furfural hydrogenation. With the nonhydrolytic sol-gel route, a denser Al2 O3 overcoat can be deposited to create a high density of Lewis acid-metal interface sites over Pt on mesoporous silica. The resulting material has a substantially increased hydrodeoxygenation activity for the conversion of lignin-derived 4-propylguaiacol into propylcyclohexane with up to 87% selectivity.