Investigating the Thermodynamics and Kinetics of Catechin Pyrolysis for Environmentally Friendly Binders

Abstract

The thermodynamics and kinetics of the pyrolysis of (+)-catechin, a building block of the condensed tannins found in recipes for sustainable binders, are evaluated at the DLPNO-CCSD(T) level and compared to other methods from quantum chemistry. Using the climbing image nudged elastic band method coupled with transition state optimization, minimum energy paths and highest-energy transition states are identified for the first two pyrolysis steps, a catechol split-off with subsequent dehydrogenation. While the catechol split-off path was very smooth, the dehydrogenation featured an additional transition state in the form of an OH group rotation. The combined reaction was judged endothermic in the range of 0 to 1250 K and exergonic at 1000 K and above. It is shown that the catechol split-off is the rate-determining step of the pyrolysis of catechin, which is equivalent to kinetic inhibition at all investigated temperatures.