Experimental and theoretical assessment of the mechanism and site requirements for ketonization of carboxylic acids on oxides

• Ketonization turnovers occur on TiO or ZrO pairs saturated with monodentate carboxylates.
• Turnover rates benefit from intermediate strength of acid and base sites and distances that enforce orbital overlap.
• Inactive bidentate carboxylates form slowly and cause site blocking.
• Ketonization is limited by CC coupling of 1-hydroxy enolates with monodentate carboxylates.
• The CC coupling transition state is preferentially stabilized by H-bonds at high coverages.

Ketonization of carboxylic acids removes O-atoms and forms new CC bonds, thus providing routes from sustainable carbon feedstocks to fuels and chemicals. The elementary steps involved and their kinetic relevance, as well as the number and nature of the active sites on active TiO2 and ZrO2 catalysts, remain matters of active discourse. Here, site titrations demonstrate the requirement for coordinatively-unsaturated M-O-M sites (M = Ti, Zr) with specific geometry and intermediate acid-base strength. The measured site densities allow rigorous reactivity comparisons among catalysts based on turnover rates and activation free energies, as well as the benchmarking of mechanistic proposals against theoretical assessments. Kinetic, isotopic, spectroscopic, and theoretical methods show that C2C4 acids react on anatase TiO2 via kinetically-relevant CC coupling between 1-hydroxy enolate species and coadsorbed acids bound at vicinal acid-base pairs saturated with active monodentate carboxylates. Smaller TiTi distances on rutile TiO2 lead to the prevalence of unreactive bidentate carboxylates and lead to its much lower ketonization reactivity than anatase. The prevalent dense monolayers of chemisorbed acid reactants reflect their strong binding at acid-base pairs and their stabilization by H-bonding interactions with surface OH groups derived from the dissociation of the carboxylic acids or the formation of 1-hydroxy enolates; these interactions also stabilize CC coupling transition states preferentially over their carboxylate precursors; high coverages favor sequential dehydration routes of the α-hydroxy-γ-carboxy-alkoxide CC coupling products over previously unrecognized concerted six-membered-ring transition states. Infrared spectra show that ubiquitous deactivation, which has precluded broader deployment of ketonization in practice and unequivocal mechanistic inquiries, reflects the gradual formation of inactive bidentate carboxylates. Their dehydration to ketene-like gaseous species is faster on anatase TiO2 than on ZrO2 and allows the effective scavenging of bidentate carboxylates via ketene hydrogenation to alkanals/alkanols on a Cu function present within diffusion distances. These strategies make anatase TiO2, a more effective catalyst than ZrO2, in spite of its slightly lower initial turnover rates. This study provides details about the mechanism of ketonization of C2C4 carboxylic acids on TiO2 and a rigorous analysis of the sites required and of active and inactive bound species on TiO2 and ZrO2. The preference for specific distances and for intermediate acid-base strength in M-O-M species is consistent with the structure and energy of the proposed transition states and intermediates; their relative stabilities illustrate how densely-covered surfaces, prevalent during ketonization catalysis, represent an essential requirement for the achievement of practical turnover rates.

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