A DFT study of furan hydrogenation and ring opening on Pd(111)
文献信息
Shengguang Wang, Vassili Vorotnikov, Dionisios G. Vlachos
The reaction energies and the corresponding energy barriers of hydrogenation and ring opening of furan on Pd(111) for the formation of tetrahydrofuran (THF), 1-butanol and small hydrocarbons were studied using density functional theory (DFT). THF forms via sequential hydrogenation of carbon atoms of the furan ring in the order of α-carbon, adjacent β-carbon, second β-carbon, and the remaining α-carbon. Upon hydrogenation of the α-carbon of furan, ring opening becomes facile. Thus, hydrofuran (HF) is a reactive intermediate in both hydrogenation and ring opening. The fate of HF determines the selectivity of the overall reaction. A simple kinetic analysis indicates that coverage effects are important and the hydrogen partial pressure is a key factor in controlling selectivity. Dihydrofuran (DHF) was found to be a stable intermediate, consistent with experimental findings. Once DHF is formed, ring opening is not favored due to the high energy barriers of ring opening of DHF, trihydrofuran (TriHF) and THF. 1-Butanol is a thermodynamically favored product, while THF is kinetically preferred. Our theoretical work agrees well with experimental observations that 1-butanol is a major product at high temperatures whereas THF is a major product at low temperatures. Insights gained into selectivity toward ring hydrogenation and ring opening can assist future studies in catalyst selection.
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Green Chemistry

Green Chemistry provides a unique forum for the publication of innovative research on the development of alternative green and sustainable technologies. The scope of Green Chemistry is based on, but not limited to, the definition proposed by Anastas and Warner (Green Chemistry: Theory and Practice, P T Anastas and J C Warner, Oxford University Press, Oxford, 1998). Green chemistry is the utilisation of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. Green Chemistry is at the frontiers of this continuously-evolving interdisciplinary science and publishes research that attempts to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. Submissions on all aspects of research relating to the endeavour are welcome. The journal publishes original and significant cutting-edge research that is likely to be of wide general appeal. To be published, work must present a significant advance in green chemistry. Papers must contain a comparison with existing methods and demonstrate advantages over those methods before publication can be considered. For more information please see this Editorial. Coverage includes the following, but is not limited to: Design (e.g. biomimicry, design for degradation/recycling/reduced toxicity…) Reagents & Feedstocks (e.g. renewables, CO2, solvents, auxiliary agents, waste utilization…) Synthesis (e.g. organic, inorganic, synthetic biology…) Catalysis (e.g. homogeneous, heterogeneous, enzyme, whole cell…) Process (e.g. process design, intensification, separations, recycling, efficiency…) Energy (e.g. renewable energy, fuels, photovoltaics, fuel cells, energy storage, energy carriers…) Applications (e.g. electronics, dyes, consumer products, coatings, pharmaceuticals, preservatives, building materials, chemicals for industry/agriculture/mining…) Impact (e.g. safety, metrics, LCA, sustainability, (eco)toxicology…) Green chemistry is, by definition, a continuously-evolving frontier. Therefore, the inclusion of a particular material or technology does not, of itself, guarantee that a paper is suitable for the journal. To be suitable, the novel advance should have the potential for reduced environmental impact relative to the state of the art. Green Chemistry does not normally deal with research associated with 'end-of-pipe' or remediation issues.














