A new biofuels breakthrough by the research team of Paul Dauenhauer, Chemical Engineering Department, was published in Energy & Environmental Science, Issue 1, 2012, the number-one-ranking journal in the world for its subject matter. The article, entitled “Revealing pyrolysis chemistry for biofuels production: Conversion of cellulose to furans and small oxygenates,” describes the development of a new experimental technique called "thin-film pyrolysis" to study high-temperature biomass chemistry. The article was considered so significant that it was highlighted in another prestigious journal, Nature Chemistry, whose impact factor is first among all primary research journals in chemistry. Read the Nature Chemistry article: http://www.nature.com/nchem/journal/v4/n2/full/nchem.1259.html.
The novel technique led to several discoveries, including a small-molecule surrogate (called ‘cyclodextrin’) of the major wood component, cellulose. This molecule was sufficiently small to permit the first use of computer simulation of the important chemical reactions which produce the chemicals evaporating from wood as it is converted to biofuels.
A video of the discovered chemical reaction to produce furans from cellulose is available online: http://www.youtube.com/watch?v=4MLKyoXvQ5o&feature=youtu.be.
Energy & Environmental Science links all aspects of the chemical, physical, and biotechnological sciences relating to energy conversion and storage, alternative fuel technologies, and environmental science. The article for Energy & Environmental Science (2012, 5, 5414-5424) was written by Matthew S. Mettler, Samir H. Mushrif, Alex D. Paulsen, Ashay D. Javadekar, Dionisios G. Vlachos, and P.J. Dauenhauer.
Now in its fourth volume, Nature Chemistry is a monthly journal dedicated to the most significant and cutting-edge research in all areas of chemistry.
Below is the abstract from Energy & Environmental Science:
Biomass pyrolysis utilizes high temperatures to produce an economically renewable intermediate (pyrolysis oil) that can be integrated with the existing petroleum infrastructure to produce biofuels. The initial chemical reactions in pyrolysis convert solid biopolymers, such as cellulose (up to 60% of biomass), to a short-lived (less than 0.1 s) liquid phase, which subsequently reacts to produce volatile products. In this work, we develop a novel thin-film pyrolysis technique to overcome typical experimental limitations in biopolymer pyrolysis and identify α-cyclodextrin as an appropriate small-molecule surrogate of cellulose. Ab initio molecular dynamics simulations are performed with this surrogate to reveal the long-debated pathways of cellulose pyrolysis and indicate homolytic cleavage of glycosidic linkages and furan formation directly from cellulose without any small-molecule (e.g., glucose) intermediates. Our strategy combines novel experiments and first-principles simulations to allow detailed chemical mechanisms to be constructed for biomass pyrolysis and enable the optimization of next-generation biorefineries. (January 2012)