Biomass has received considerable attention as a sustainable feedstock that can replace diminishing fossil fuels for the production of energy, especially for the transportation sector. The overall strategy in the production of hydrocarbon fuels from biomass is (i) to reduce the substantial oxygen content of the parent feedstock to improve energy density and (ii) to create C-C bonds between biomass-derived intermediates to increase the molecular weight of the final hydrocarbon product. We begin this review with a brief overview of first-generation biofuels, specifically bioethanol and biodiesel. We consider the implications of utilizing starchy and triglyceride feedstocks from traditional food crops, and we provide an overview of second-generation technologies to process the major constituents of more abundant lignocellulosic biomass, such as thermochemical routes (gasification, pyrolysis, liquefaction) which directly process whole lignocellulose to upgradeable platforms (e.g., synthesis gas and bio-oil). The primary focus of this review is an overview of catalytic strategies to produce biofuels from aqueous solutions of carbohydrates, which are isolated through biomass pretreatment and hydrolysis. Although hydrolysis-based platforms are associated with higher upstream costs arising from pretreatment and hydrolysis, the aqueous solutions of biomass-derived compounds can be processed selectively to yield hydrocarbons with targeted molecular weights and structures. For example, sugars can be used as reforming feedstocks for the production of renewable hydrogen, or they can be dehydrated to yield furfurals or levulinic acid. For each of the platforms discussed, we have suggested relevant strategies for the formation of C-C bonds, such as aldol condensation of ketones and oligomerization of alkenes, to enable the production of gasoline, jet, and Diesel fuel range hydrocarbons. Finally, we address the importance of hydrogen in biorefining and discuss strategies for managing its consumption to ensure independence from fossil fuels.

Research interest in biomass conversion to fuels and chemicals has increased significantly in the last decade as the necessity for a renewable source of carbon has become more evident. Accordingly, many different reactions and processes to convert biomass into high-value products and fuels have been proposed in the literature. Special attention has been given to the conversion of lignocellulosic biomass, which does not compete with food sources and is widely available as a low cost feedstock. In this review, we start with a brief introduction on lignocellulose and the different chemical structures of its components: cellulose, hemicellulose, and lignin. These three components allow for the production of different chemicals after fractionation. After a brief overview of the main reactions involved in biomass conversion, we focus on those where bimetallic catalysts are playing an important role. Although the reactions are similar for cellulose and hemicellulose, which contain C(6) and C(5) sugars, respectively, different products are obtained, and therefore, they have been reviewed separately. The third major fraction of lignocellulose that we address is lignin, which has significant challenges to overcome, as its structure makes catalytic processing more challenging. Bimetallic catalysts offer the possibility of enabling lignocellulosic processing to become a larger part of the biofuels and renewable chemical industry. This review summarizes recent results published in the literature for biomass upgrading reactions using bimetallic catalysts.

Efficient synthesis of renewable fuels remains a challenging and important line of research. We report a strategy by which aqueous solutions of gamma-valerolactone (GVL), produced from biomass-derived carbohydrates, can be converted to liquid alkenes in the molecular weight range appropriate for transportation fuels by an integrated catalytic system that does not require an external source of hydrogen. The GVL feed undergoes decarboxylation at elevated pressures (e.g., 36 bar) over a silica/alumina catalyst to produce a gas stream composed of equimolar amounts of butene and carbon dioxide. This stream is fed directly to an oligomerization reactor containing an acid catalyst (e.g., H ZSM-5, Amberlyst-70), which couples butene monomers to form condensable alkenes with molecular weights that can be targeted for gasoline and/or jet fuel applications. The effluent gaseous stream of CO2 at elevated pressure can potentially be captured and then treated or sequestered to mitigate greenhouse gas emissions from the process.

Lignocellulosic biomass typically contains more than 50 wt% sugars that can be upgraded to valuable platform molecules, such as levulinic acid (LA) and gamma-valerolactone (GVL). This article focuses on upgrading GVL produced from lignocellulosic biomass to various chemicals and fuels, such as polymers, fuel additives, and jet fuel. We also review the use of GVL as a solvent for biomass processing, which led to significant improvements in product yields and a more simplified process for producing biomassderived chemicals such as LA, furfural, and hydroxymethylfurfural.

Widespread production of biomass-derived fuels and chemicals will require cost-effective processes for breaking down cellulose and hemicellulose into their constituent sugars. Here, we report laboratory-scale production of soluble carbohydrates from corn stover, hardwood, and softwood at high yields (70 to 90%) in a solvent mixture of biomass-derived γ-valerolactone (GVL), water, and dilute acid (0.05 weight percent H2SO4). GVL promotes thermocatalytic saccharification through complete solubilization of the biomass, including the lignin fraction. The carbohydrates can be recovered and concentrated (up to 127 grams per liter) by extraction from GVL into an aqueous phase by addition of NaCl or liquid CO2. This strategy is well suited for catalytic upgrading to furans or fermentative upgrading to ethanol at high titers and near theoretical yield. We estimate through preliminary techno-economic modeling that the overall process could be cost-competitive for ethanol production, with biomass pretreatment followed by enzymatic hydrolysis.