Crystal Plane Effect of Ceria on Supported Copper Oxide Cluster Catalyst for CO Oxidation: Importance of Metal–Support Interaction

TLDR

Copper–ceria catalysts are highly active for oxidation reactions, and the interaction strength between copper oxides and ceria crystal faces critically influences their redox and catalytic properties. The study investigates how ceria crystal planes affect CO oxidation by comparing Cu oxide catalysts on {111}/{100} nanospheres and {110}/{100} nanorods. The authors prepared 1 wt % Cu oxide on ceria nanospheres and nanorods and used Cs‑STEM, XAFS, and in‑situ DRIFTS to characterize the size, dispersion, and oxidation state of the Cu species. CuOx clusters on the {111} face are more readily reduced to catalytically active Cu(I) sites, leading to higher CO oxidation rates (5.7 × 10⁻⁶ mol CO g_cat⁻¹ s⁻¹ at 104 °C) than the {110} face (1.8 × 10⁻⁶ mol CO g_cat⁻¹ s⁻¹ at 118 °C), demonstrating that the {111} ceria plane promotes more active sites than the traditionally reactive {110} plane.

Abstract

Copper–ceria as one of the very active catalysts for oxidation reactions has been widely investigated in heterogeneous catalysis. In this work, copper oxide (1 wt % Cu loading) deposited on both ceria nanospheres with a {111}/{100}-terminated surface (1CuCe-NS) and with nanorod exposed {110}/{100} faces (1CuCe-NR) have been prepared for the investigation of crystal plane effects on CO oxidation. Various structural characterizations, especially including aberration-corrected scanning transmission electron microscopy (Cs-STEM), X-ray absorption fine structure (XAFS) technique, and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS), were used to precisely determine the structure and status of the catalysts. It is found that the copper oxides were formed as subnanometer clusters and were uniformly dispersed on the surface of the ceria support. The results from XAFS combined with the temperature-programmed reduction technique (H2-TPR) reveal that more reducible CuOx clusters with only Cu–O coordination structure exclusively dominated in the surface of 1CuCe-NS, while the Cu species in 1CuCe-NR existed in both CuOx clusters and strongly interacting Cu-[Ox]-Ce. In situ DRIFTS results demonstrate that the CeO2-{110} face induced a strongly bound Cu-[Ox]-Ce structure in 1CuCe-NR which was adverse to the formation of reduced Cu(I) active sites, resulting in low reactivity in CO oxidation (rCO = 1.8 × 10–6 molCO gcat–1 s–1 at 118 °C); in contrast, CuOx clusters on the CeO2-{111} face were easily reduced to Cu(I) species when they were subjected to interaction with CO, which greatly enhanced the catalytic reactivity (rCO = 5.7 × 10–6 molCO gcat–1 s–1 at 104 °C). Thus, for copper–ceria catalyst, in comparison with the well-known reactive {110}CeO2 plane, {111}CeO2, the most inert plane, exhibits great superiority to induce more catalytically active sites of CuOx clusters. The difference in strength of the interaction between copper oxides and different exposed faces of ceria is intrinsically relevant to the different redox and catalytic properties.