Value-Added Bio-Chemicals Commodities from Catalytic Conversion of Biomass Derived Furan-Compounds

The depletion of fossil resources in the near future and the need to decrease greenhouse gas emissions lead to the investigation of using alternative renewable resources as raw materials. One of the most promising options is the conversion of lignocellulosic biomass (like forestry residues) into bioenergy, biofuels and biochemicals. Among these products, the production of intermediate biochemicals has become an important goal since the petrochemical industry needs to find sustainable alternatives. In this way, the chemical industry competitiveness could be improved as bioproducts have a great potential market. Thus, the main objective of this review is to describe the production processes under study (reaction conditions, type of catalysts, solvents, etc.) of some promising intermediate biochemicals, such as; alcohols (1,2,6-hexanetriol, 1,6-hexanetriol and pentanediols (1,2 and 1,5-pentanediol)), maleic anhydride and 5-alkoxymethylfuran. These compounds can be produced using 5-hydroxymethylfurfural and/or furfural, which they both are considered one of the main biomass derived building blocks.This work was supported by funds from University of the Basque Country (UPV/EHU), Spanish Ministry of Economy and Innovation (Projects: RTI2018-094918-B-C43), and Basque Country Government (Project: IT993-16)

Fully lignocellulose-based PET analogues for the circular economy

Polyethylene terephthalate is one of the most abundantly used polymers, but also a significant pollutant in oceans. Due to growing environmental concerns, polyethylene terephthalate alternatives are highly sought after. Here we present readily recyclable polyethylene terephthalate analogues, made entirely from woody biomass. Central to the concept is a two-step noble metal free catalytic sequence (Cu20-PMO catalyzed reductive catalytic fractionation and Raney Ni mediated catalytic funneling) that allows for obtaining a single aliphatic diol 4-(3-hydroxypropyl) cyclohexan-1-ol in high isolated yield (11.7 wt% on lignin basis), as well as other product streams that are converted to fuels, achieving a total carbon yield of 29.5%. The diol 4-(3-hydroxypropyl) cyclohexan-1-ol is co-polymerized with methyl esters of terephthalic acid and furan dicarboxylic acid, both of which can be derived from the cellulose residues, to obtain polyesters with competitive Mw and thermal properties (Tg of 70–90 °C). The polymers show excellent chemical recyclability in methanol and are thus promising candidates for the circular economy.</p

Electrolyzer Design for Flexible Decoupled Water Splitting and Organic Upgrading with Electron Reservoirs

The Bigger Picture Electrocatalytic water splitting is a green approach to producing clean H2 fuel, especially when it is driven by renewable energy sources. Conventional water electrolysis always produces H2 and O2 simultaneously under corrosive acidic or alkaline conditions with large voltage inputs, posing safety concerns of H2/O2 mixing. Therefore, it is desirable to develop a new electrolyzer design for decoupled water splitting in an eco-friendly neutral solution with small voltage inputs to enable separated H2 and O2 evolution. Herein, we report (ferrocenylmethyl)trimethylammonium chloride and Na4[Fe(CN)6] as proton-independent electron reservoirs for achieving separated H2 and O2 evolution in near-neutral solution driven by electricity or solar cells under sunlight irradiation. Na4[Fe(CN)6] can also integrate H2 evolution with organic oxidation to yield H2 and high-value organic products. This work offers promising economic and safety advantages for sustainable H2 production and organic transformation

The application of green chemistry and engineering to novel sustainable solvents and processes

The implementation of sustainable solvents and processes is critical to new developments in reducing environmental impact, improving net efficiency, and securing economic profitability in the chemical and pharmaceutical industries. In order to address the challenge of sustainability, researchers have used switchable solvents for both reaction and separation by utilizing a built-in switch to undergo a step change in chemical and physical properties. This allows us to facilitate reactions in the solvent then activate the switch to enable separation and facile product recovery. Subsequently, we can recover the solvent for reuse and avoid energy- or waste-intensive separation processes; thus we are developing and using these switchable solvents as sustainable and environmentally benign alternatives to traditional processes. In this research, we enable the sustainable scale-up of a switchable solvent - piperylene sulfone - a "volatile" and recyclable DMSO replacement. In the development of this process, we improved the reaction performances and developed a green purification method. Furthermore, we enable and demonstrate the implementation of a Meerwein-Ponndorf-Verley (MPV) reduction, a pharmaceutically relevant reaction, into a continuous flow platform. The innovation of continuous flow processes can replace traditional batch reaction technology, and is indeed a key research area that has been acknowledged by the pharmaceutical industry. Additionally, we utilize the switchable sulfone solvents, piperylene and butadiene sulfone, for reaction and separation of HMF produced from monosaccharides as an alternative to a process which has been limited by an inefficient separation step.PhDCommittee Chair: Eckert, Charles; Committee Co-Chair: Liotta, Charles; Committee Member: Fernandez, Facundo; Committee Member: Meredith, Carson; Committee Member: Teja, Amy