Copper-zirconia interfaces in UiO-66 enable selective catalytic hydrogenation of CO2 to methanol

Yifeng Zhu; Jian Zheng; Jingyun Ye; Yanran Cui; Katherine Koh; Libor Kovarik; Donald M Camaioni; John L Fulton; Donald G Truhlar; Matthew Neurock; Christopher J Cramer; Oliver Y Gutiérrez; Johannes A Lercher

doi:10.1038/s41467-020-19438-w

Copper-zirconia interfaces in UiO-66 enable selective catalytic hydrogenation of CO₂ to methanol

Nat Commun. 2020 Nov 18;11(1):5849. doi: 10.1038/s41467-020-19438-w.

Authors

Affiliations

¹ Institute for Integrated Catalysis, and Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, 99354, USA.
² Department of Chemistry, Minnesota Supercomputing Institute, Chemical Theory Center, and Inorganometallic Catalyst Design Center, University of Minnesota, Minneapolis, MN, 55455, USA.
³ Department of Chemistry and Biomolecular Science, Clarkson University, Potsdam, NY, 13699, USA.
⁴ William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, 99354, USA.
⁵ Institute for Integrated Catalysis, and Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, 99354, USA. oliver.gutierrez@pnnl.gov.
⁶ Institute for Integrated Catalysis, and Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, 99354, USA. johannes.lercher@pnnl.gov.

Abstract

Molecular interactions with both oxides and metals are essential for heterogenous catalysis, leading to remarkable synergistic impacts on activity and selectivity. Here, we show that the direct link between the two phases (and not merely being together) is required to selectively hydrogenate CO₂ to methanol on catalysts containing Cu and ZrO₂. Materials consisting of isolated Cu particles or atomically dispersed Cu-O-Zr sites only catalyze the reverse water-gas shift reaction. In contrast, a metal organic framework structure (UiO-66) with Cu nanoparticles occupying missing-linker defects maximizes the fraction of metallic Cu interfaced to ZrO₂ nodes leading to a material with high adsorption capacity for CO₂ and high activity and selectivity for low-temperature methanol synthesis.