The Catalytic Effect of Fluoroalcohol Mixtures Depends on Domain Formation

• DOI: 10.1021/acscatal.6b03090
• Publication Date: 2017-01-31T20:16:01Z
• Authors: Oldamur Hollóczki; Albrecht Berkessel; Julian Mars; Markus Mezger; Anton Wiebe; Siegfried R. Wald...; Barbara Kirchner
• Keywords: 01 natural sciences; 0104 chemical sciences

In the present contribution, we investigated catalytically active mixtures of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and aqueous H2O2 by molecular dynamics simulations. It is clearly observable that the HFIP molecule strongly binds to the H2O2, which is necessary for the desired catalytic reaction to occur. Upon the addition of the substrate cyclooctene to the solution, this interaction is enhanced, which suggests that the catalytic activity is increased by the presence of the hydrocarbon. We could clearly observe the microheterogeneous structure of the mixture, which is the result of the separation of the hydroxyl groups, water, and H2O2 from the fluorinated alkyl moiety in the form of large domains, which span through large areas of the system. The hydrocarbon, however, does not fit into either one of these two microphases, and it forms separate aggregates in the macroscopically homogeneous liquid, creating thereby a triphilic mixture. The latter kinds of aggregates are mostly surrounded by the fluoro...