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Ball, Madelyn R.

Publications and source records attributed to Ball, Madelyn R..

Recommendations for improving rigor and reproducibility in site specific characterization

Heterogeneous catalysis is driven by the interaction of reactant molecules and the catalyst surface. The locus of this interaction as well as the surrounding ensemble of atoms is referred to as the catalyst active site. Active site characterization attempts to distinguish active catalytic sites from inactive surface sites, to elucidate the structural and chemical nature of active sites, and to quantify active site concentration. Numerous techniques have been demonstrated to provide compositional and structural information about the active sites within a catalyst. However, each technique has its own limitations and experimental pitfalls that can lead to data misinterpretation or irreproducible results. Further, this work aims to provide an overview of the types of data that can be collected, to outline common experimental challenges and how to avoid them, and to assemble relevant references for the most used active site characterization techniques. More broadly, we aim to outline best practices for researchers to collect, interpret, and report active site characterization data in a way that provides the most benefit to the broader catalysis community. Increasing the rigor and reproducibility of active site characterization offers a strategy to better link properties with catalytic performance and to enable the community to develop consensus concerning these relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Citral Hydrogenation over Dilute Alloy Catalysts

Dilute alloy CuPt and NiPt catalysts are studied in the hydrogenation of citral, a model α,β-unsaturated aldehyde. In situ and ex situ characterization is used to demonstrate that the Pt species within these nanoparticles are well dispersed and approach a single atom alloy structure. The distribution of Pt varies between the two host metal systems; under a hydrogen environment, the nanoparticle surface and near-surface region of the NiPt nanoparticles is Pt rich, while the Pt is more uniformly distributed throughout the CuPt nanoparticles. When used for citral hydrogenation reactions, a rate enhancement is observed upon the addition of Pt to the Cu or Ni host catalysts, however this enhancement is determined to be due to the presence of additional metal and not a synergistic effect of the two metals. The Pt structure does, nonetheless, influence the observed selectivity trends. NiPt/SiO 2 catalysts have high selectivity to the unsaturated aldehyde citronellal while the CuPt/SiO 2 catalysts have increased selectivity to unsaturated alcohol products. Further, this increased selectivity is attributed to a combination of hydrogen dissociation over Pt sites and a decrease in size of Cu ensembles due to the presence of Pt, which favors binding and hydrogenation of C=O rather than C=C bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO 2 methanation reaction pathways over unpromoted and NaNO 3 -promoted Ru/Al 2 O 3 catalysts

Catalytic CO 2 sorbents, materials that adsorb and pre-concentrate CO 2 on the catalyst surface prior to subsequent conversion, are becoming important materials in CO 2 capture and utilization. In this work, a prototypical CO 2 methanation catalyst – Ru/Al 2 O 3 – and a related catalytic sorbent – NaNO 3 /Ru/Al 2 O 3 – are used for CO 2 methanation in flowing hydrogen in a fixed bed reactor at temperatures ranging from 220 to 280 °C. Activation energies for the NaNO 3 /Ru/Al 2 O 3 material are slightly higher than unpromoted Ru/Al 2 O 3 catalysts, and the reaction orders vary more significantly. In situ IR spectroscopy and steady-state isotopic kinetic analysis (SSITKA) using in situ IR/MS spectroscopy show that bicarbonate and linear carbonyl species are the likely reaction intermediates over unpromoted Ru/Al 2 O 3 , while bidentate carbonate, formate and linear carbonyl species are among likely reaction intermediates over NaNO 3 /Ru/Al 2 O 3 . Rate laws consistent with the obtained experimental data are proposed after kinetic modeling of multiple plausible reaction pathways. In conclusion, results suggest that the pathway over the NaNO 3 /Ru/Al 2 O 3 catalyst likely has an additional kinetically relevant irreversible step in the CO 2 methanation reaction pathway.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗