Thermally Regulated Recyclable Carbene Catalysts for Upgrading of Biomass Furaldehydes
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Lignin is the only large-volume renewable source of aromatic chemicals. Efficient depolymerization and deoxygenation of lignin while retaining the aromatic functionality are attractive but extremely challenging. Here we report the selective production of arenes via direct hydrodeoxygenation of organosolv lignin over a porous Ru/Nb 2 O 5 catalyst that enabled the complete removal of the oxygen content from lignin. The conversion of birch lignin to monomer C7–C9 hydrocarbons is nearly quantitative based on its monomer content, with a total mass yield of 35.5 wt% and an exceptional arene selectivity of 71 wt%. Inelastic neutron scattering and DFT calculations confirm that the Nb 2 O 5 support is catalytically unique compared with other traditional oxide supports, and the disassociation energy of Caromatic–OH bonds in phenolics is significantly reduced upon adsorption on Nb 2 O 5 , resulting in its distinct selectivity to arenes. This one-pot process provides a promising approach for improved lignin valorization with general applicability.
State programs to improve energy affordability and reduce energy burden (the share of income spent on energy) could mitigate concerns about rising electricity prices. Many states offer bill assistance and rebates for weatherization and rooftop solar to income-qualifying households. Here, we analyse how these approaches may complement one another to improve energy affordability. Results illustrate trade offs between program costs and energy burden reduction, as well as between a program’s upfront and ongoing costs. Generally, the three strategies complement one another to improve energy affordability at lower net present cost than bill assistance alone, with varying effects across regions. Weatherization can reduce the solar installation capacity needed, and both together can reduce or eliminate ongoing reliance on bill assistance. Under full uptake among cost-effective households, fully rebated weatherization and solar rebated at $0.48/Watt, combined with bill assistance, yield the same modelled net present cost as bill assistance alone while reducing the share of low-income owner-occupied households with high energy burdens from 66% to 19%, compared with 34% under bill assistance alone. Absent tax credits, weatherization still reduces energy burden and bill assistance program costs, whereas solar may not be cost-competitive.
It is now possible to efficiently fix flue gas CO/CO 2 into ethanol using acetogens, thereby making carbon negative ethanol. While the ethanol could be burned as a fuel, returning the CO 2 to the atmosphere, it might also be possible to use the fixed carbon in more diverse chemicals, thereby keeping it fixed. Here we describe a simple synthetic biochemistry approach for converting carbon negative ethanol into the synthetic building block chemical 1,3 butanediol (1,3-BDO). The pathway completely conserves carbon from ethanol and can ultimately be powered electrochemically via formate oxidation. Our proof-of-principle system reached a maximum productivity of 0.16 g/L/h and, with replenishment of feedstock and enzymes, achieved a titer of 7.7 g/L. We identify a number of elements that can be addressed in future work to improve both cell-free and cell-based production of 1,3-BDO.
The original PDF and HTML versions of this Article contained an error in the Acknowledgements section. In the Acknowledgements section MEG Energy Corp. was incorrectly acknowledged for financial support.
It is challenging to obtain high-value hydrocarbons that are longer than C 3 via electrochemical CO 2 /CO reduction. Integrating electrochemical CO 2 /CO electrolysers with a downstream bioreactor is one solution for obtaining high-value long-chain products, but the electrolytes in these two systems are mismatched, preventing smooth integration. Furthermore we demonstrate a porous solid electrolyte reactor that produces highly selective and electrolyte-free acetate and couple it with a biosynthesis system for generating C 4+ polyhydroxybutyrate bioplastic. A finely tuned electrolyte containing biocompatible salt medium with acetate can be directly injected into the downstream bioreactor without any separation or salt-mixing processes. In the optimized coupled platform, Ralstonia eutropha bacteria can grow with acetate generated from the CO electrocatalytic reduction reactor, and produce bioplastic as the final value-added product.
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In the late 1850s, Charles Friedel's dry distillation of calcium acetate gave the world a novel route to the commercial production of acetone, a process that would later be referred to as decarboxylative dehydration (ketonization). While the subsequent development of the petrochemical industry made this route to acetone uncompetitive, today there is considerable interest in ketonization as means for converting biomass-derived fatty acids to produce longer-chained ketones, which could serve as precursors to fuels and lubricants. However, the lack of strategies beyond direct hydrogenation of the ketones into hydrocarbons has limited the practical application of ketonization for producing biofuels. In this paper, we describe here integrated catalytic sequences for converting a range of biomass-derived carboxylic acids, sourced through fermentation of sugars, hydrolysis of lipids, or biomass pyrolysis, to compounds that are fully compatible with the existing energy infrastructure and require minimal hydrogen input.