Considerations when determining Counter-diffusion constants in liquid phase catalytic reactions using the Zero Length column (ZLC) method

Abstract

The confusion with diffusion: In heterogeneous catalysis often, the catalytic material is housed within a porous support structure. It is important therefore to determine whether this support structure exerts limiting behaviors. In this paper, desorption and diffusion effects are separated under reactions conditions, to provide accurate effective diffusion constants in swelling and gate-opening catalysts. • A Zero Length Column (ZLC) method was developed using liquid chromatography. • Diffusion in porous catalyst pellets as small as 5 mg can be directly characterised. • Reactant counter-diffusion coefficients were determined for the Heck reaction. • Clear differences in diffusion rates for reactants versus non-reactant species. A Zero Length Column (ZLC) method was developed using a liquid chromatographic system to calculate reactant counter-diffusion coefficients in porous, solvent swollen catalytic pellets and gate-opening support materials. Reactant diffusivities within these porous materials were determined at the reaction conditions of 80 °C and 0.3–0.75 mL min −1 . For all materials, molecules of a similar size to the pore apertures, or molecules with strong interactions with the material surfaces, catalysts, were observable by the ZLC method, with both micro and macropore diffusion observed. Differences between Pd(II) and Pd(0) forms of the EnCat30 catalyst were examined to determine the effects of catalytic deactivation. The deactivated catalyst showed iodobenzene macroporous diffusion constants similar to the relatively inert toluene molecules. Finally, pulse field gradient NMR was utilised to compare and validate ZLC diffusion measurements for solvent swollen reaction systems. This study presents much needed novel findings on diffusivity data for liquid phase catalytic systems.