Acid catalysis has
long been used to depolymerize plant cell wall
polysaccharides, and the mechanisms by which acid affects carbohydrates
have been extensively studied. Lignin depolymerization, however, is
not as well understood, primarily due to the heterogeneity and reactivity
of lignin. We present an experimental and theoretical study of acid-catalyzed
cleavage of two non-phenolic and two phenolic dimers that exhibit
the β-O-4 ether linkage, the most common intermonomer bond in
lignin. This work demonstrates that the rate of acid-catalyzed β-O-4
cleavage in dimers exhibiting a phenolic hydroxyl group is 2 orders
of magnitude faster than in non-phenolic dimers. The experiments suggest
that the major product distribution is similar for all model compounds,
but a stable phenyl-dihydrobenzofuran species is observed in the acidolysis
of two of the γ-carbinol containing model compounds. The presence
of a methoxy substituent, commonly found in native lignin, prevents
the formation of this intermediate. Reaction pathways were examined
with quantum mechanical calculations, which aid in explaining the
substantial differences in reactivity. Moreover, we use a radical
scavenger to show that the commonly proposed homolytic cleavage pathway
of phenolic β-O-4 linkages is unlikely in acidolysis conditions.
Overall, this study explains the disparity between rates of β-O-4
cleavage seen in model compound experiments and acid pretreatment
of biomass, and implies that depolymerization of lignin during acid-catalyzed
pretreatment or fractionation will proceed via a heterolytic, unzipping
mechanism wherein β-O-4 linkages are cleaved from the phenolic
ends of branched, polymer chains inward toward the core of the polymer.
Anion exchange membranes (AEMs) are of interest as hydroxide conducting polymer electrolytes in electrochemical devices like fuel cells and electrolyzers. AEMs require hydroxide stable covalently tetherable cations to ensure required conductivity. Benzyltrimethylammonium (BTMA) has been the covalently tetherable cation that has been most often employed in anion exchange membranes because it is reasonably basic, compact (limited number of atoms per charge), and easily/cheaply synthesized. Several reports exist that have investigated hydroxide stability of BTMA under specific conditions, but consistency within these reports and comparisons between them have not yet been made. While the hydroxide stability of BTMA has been believed to be a limitation for AEMs, this stability has not been thoroughly reported. We have found that several methods reported have inherent flaws in their findings due to the difficulty of performing degradation experiments at high temperature and high pH. In order to address these shortcomings, we have developed a reliable, standardized method of determining cation degradation under conditions similar/relevant to those expected in electrochemical devices. The experimental method has been employed to determine BTMA stabilities at varying cation concentrations and elevated temperatures, and has resulted in improved experimental accuracy and reproducibility. Alkaline membrane fuel cells (AMFCs) employing anion exchange membranes (AEMs) are of increasing interest in fuel cell research as they potentially enable the use of non-Pt fuel cell catalysts, a primary cost limitation of proton exchange membrane fuel cells.
Lignocellulosic biomass offers a vast, renewable resource for the sustainable production of fuels and chemicals. To date, a commonly employed approach to depolymerize the polysaccharides in plant cell walls employs mineral acids, and upgrading strategies for the resulting sugars are under intense development. While the behavior of cellulose and hemicellulose are reasonably well understood, a more thorough understanding of lignin depolymerization mechanisms in acid environments is necessary to understand the fate of lignin under such conditions and ultimately to potentially make lignin a viable feedstock. To this end, dilute acid hydrolysis experiments were performed on two lignin model compounds containing the α-O-4 ether linkage at two temperatures concomitant with dilute acid pretreatment. Both primary and secondary products were tracked over time, giving insight into the reaction kinetics. The only difference between the two model compounds was the presence or absence of a methyl group on the α-carbon, with the former being typical of native lignin. It was found that methylation of the α-carbon increases the rate of reaction by an order of magnitude. Density functional theory calculations were performed on a proposed mechanism initiated by a nucleophilic attack on the α-carbon by water with a commensurate protonation of the ether oxygen. The values for the thermodynamics and kinetics derived from these calculations were used as the basis for a microkinetic model of the reaction. Results from this model are in good agreement with the experimental kinetic data for both lignin model compounds and provide useful insight into the primary pathways of α-O-4 scission reactions in acid-catalyzed lignin depolymerization. The distribution of primary and secondary products is interpreted as a function of two barriers of formation exhibiting opposite trends upon methylation of the α-carbon (one barrier is lowered while the other is increased). Such insights will be needed to construct a comprehensive model of how lignin behaves in a common deconstruction approach.
Anion exchange membranes (AEMs) are of high interest for a number of electrochemical device applications including fuel cells, electrolyzers, and flow batteries. Perfluorinated sulfonic acid polymers have been the standard polymer used in the much more established area of proton exchange membrane based devices due to specific advantageous attributes including chemical stability, high conductivity, high water mobility, and the ability to create high performance electrodes. These attributes would make for desirable AEMs, but synthesizing perfluorinated AEMs has been limited and has significant challenges. Here, we report our efforts to develop novel synthesis routes to sulfonamide-linked alkyl ammonium perfluorinated AEMs. We have demonstrated the ability to achieve both high levels of ion exchange and membrane conductivity. We have achieved improved durability by extending the length of the alkyl tether from 3 to 6 carbons, and we have demonstrated the ability to process these polymers into membranes, ionomer solutions/dispersions, and fuel cells with reasonable performance.
The increased interest in the use of anion exchange membranes (AEMs) for applications in electrochemical devices has prompted significant efforts in designing materials with robust stability in alkaline media. Most reported AEMs suffer from polymer backbone degradation as well as cation functional group degradation. In this report, we provide comprehensive experimental investigations for the analysis of cation functional group stability under alkaline media. A silver oxide-mediated ion exchange method and an accelerated stability test in aqueous KOH solutions at elevated temperatures using a Parr reactor were used to evaluate a broad scope of quaternary ammonium (QA) cationic model compound structures, particularly focusing on alkyl-tethered cations. Additionally, byproduct analysis was employed to gain better understanding of degradation pathways and trends of alkaline stability. Experimental results under different conditions gave consistent trends in the order of cation stability of various QA small molecule model compounds. Overall, cations that are benzyl-substituted or that are near to electronegative atoms (such as oxygen) degrade faster in alkaline media in comparison to alkyl-tethered QAs. These comprehensive model compound stability studies provide valuable information regarding the relative stability of various cation structures and can help guide researchers towards designing new and promising candidates for AEM materials.
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