Jeffrey Camacho-Bunquin

Well-defined organoplatinum(IV) sites were grafted on a Zn(II)-modified SiO₂ support via surface organometallic chemistry in toluene at room temperature. Solid-state spectroscopies including XAS, DRIFTS, DRUV–vis, and solid-state (SS) NMR enhanced by dynamic nuclear polarization (DNP), as well as TPR-H₂ and TEM techniques revealed highly dispersed (methylcyclopentadienyl)methylplatinum(IV) sites on the surface ((MeCp)PtMe/Zn/SiO₂, 1). In addition, computational modeling suggests that the surface reaction of (MeCp)PtMe₃ with Zn(II)-modified SiO₂ support is thermodynamically favorable (ΔG = −12.4 kcal/mol), likely due to the increased acidity of the hydroxyl group, as indicated by NH₃-TPD and DNP-enhanced ¹⁷O{¹H} SSNMR. In situ DRIFTS and XAS hydrogenation experiments reveal the probable formation of a surface Pt(IV)-H upon hydrogenolysis of Pt-Me groups. The heterogenized organoplatinum(IV)-hydride sites catalyze the selective partial hydrogenation of 1,3-butadiene to butenes (up to 95%) and the reduction of nitrobenzene derivatives to anilines (up to 99%) with excellent tolerance of reduction-sensitive functional groups (olefin, carbonyl, nitrile, halogens) under mild reaction conditions.

Well-defined, isolated, single-site organovanadium(iii) catalyst on SiO₂ for unprecedented liquid- and gas-phase hydrogenation of alkenes and alkynes under mild conditions.

Ga( iii )-alkyl and alkoxide model compounds demonstrate XANES edge energy shifts similar to those in Ga dehydrogenation catalysts without a change in Ga oxidation state.

An integrated atomic layer deposition synthesis-catalysis (I-ALD-CAT) tool was developed. It combines an ALD manifold in-line with a plug-flow reactor system for the synthesis of supported catalytic materials by ALD and immediate evaluation of catalyst reactivity using gas-phase probe reactions. The I-ALD-CAT delivery system consists of 12 different metal ALD precursor channels, 4 oxidizing or reducing agents, and 4 catalytic reaction feeds to either of the two plug-flow reactors. The system can employ reactor pressures and temperatures in the range of 10⁻³ to 1 bar and 300–1000 K, respectively. The instrument is also equipped with a gas chromatograph and a mass spectrometer unit for the detection and quantification of volatile species from ALD and catalytic reactions. In this report, we demonstrate the use of the I-ALD-CAT tool for the synthesis of platinum active sites and Al₂O₃ overcoats, and evaluation of catalyst propylene hydrogenation activity.