Solvent‐enabled intensification of liquid–liquid heterogeneous catalysis exemplified by direct hydration of cyclohexene

Abstract A strategy of adding solvents to adjust liquid–liquid equilibrium for intensifying liquid–liquid heterogeneous catalytic reactions is presented. A systematic framework involving computational and experimental procedures is proposed for solvent screening and exemplified by the direct hydration of cyclohexene. The solvents that are stable, nonreactive, inert to catalyst, and easily recovered are first filtered out. Besides, two tailored key performance indicators are defined and computed to find the solvents that can promote mutual solubility of reactants and reaction conversion. Potential solvents are sent to test their effects on product yield via experiment. m‐Cresol is found to have the highest cyclohexanol yield of 47.5% and its explicit roles for enhancing the reaction is revealed by rigorous liquid–liquid equilibrium. The mechanism of why the resulted solvents can intensify the reaction is theoretically explored. By a comparative study, an additional heuristic is found to serve for expediting solvent screening.