Lela K Manis,Jiankai Ge,Changhae Andrew Kim,Emmanuel Ejiogu,Ziqiu Chen,Ryan D Yappert,Baron Peters
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引用次数: 0
Abstract
ConspectusThe ongoing accumulation of plastic waste in landfills and in the environment is driving research on chemical processes and catalysts to recycle polymers. Traditional modeling strategies are not applicable to these processes because they involve too many reactants and intermediates, one for each molecular weight and each functionalization. To model the kinetics, we have developed population balance models (PBMs) that account for macromolecular reactants in the bulk and macromolecular catalytic intermediates. These PBMs couple to each other through polymer adsorption and desorption models and to traditional rate equations for small molecule products and co-reactants (like hydrogen or ethylene). The models, in combination with experimental data, are being used in many ways: (i) to test mechanistic hypotheses, (ii) to extract rate parameters, (iii) to quantitatively compare catalyst activities, (iv) to account for mass transfer and vapor-liquid partitioning in two-phase reactors, and (v) to design novel support architectures and catalysts that mimic the processive action of natural depolymerization enzymes. Some key theoretical advances allow PBMs to be constructed from elementary rates and mechanisms, as opposed to traditional formulations with pseudoelementary rate parameters invoked as fitting parameters. We discuss ways to build these models "bottom-up" from first-principles calculations and ways to extract model parameters from "top down" analyses of rate data. The combination provides a quantitative bridge between first-principles calculations and the kinetics of complex macromolecular transformations for polymer upcycling and beyond.
期刊介绍:
Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance.
Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.