Cu Evolution over Bimetallic Cu‐Y/Beta Zeolite Under H <sub>2</sub> and Ethanol Atmospheres: Unveiling the Role of Diatomic Metal–Metal Interactions
Abstract
Abstract Understanding the dynamic evolution of Cu species under varying environmental conditions is critical for addressing challenges related to the activity and the stability of copper‐based catalysts in thermo‐, photo‐, and electrocatalysis. However, metal–metal interactions between dual single atoms and their effects on Cu evolution after exposure to different environmental molecules remain underexplored. Herein, we synthesized bimetallic Cu‐Y/Beta catalysts with dual single‐atom Cu and Y sites and monometallic Cu‐Beta catalysts with isolated Cu sites in dealuminated Beta zeolites. By varying Cu and Y compositions, diatomic interactions were studied under H 2 and ethanol atmospheres. With 6 wt% Y loading, approximately 0.4 wt% of Cu species in Cu‐Y/Beta remained partially oxidized as Cu(I) after reduction in pure H 2 at 350 °C, in contrast to the full transition to metallic Cu observed in Cu‐Beta. Combining X‐ray absorption spectroscopy with kinetic studies revealed that metallic Cu became the predominant species after reduction with H 2 as Cu loading increased from 0.4 to 1.7 wt%, quadrupling the initial ethanol dehydrogenation rate and demonstrating the dominant role of Cu(0) sites. Scanning transmission electron microscopy and density functional theory simulations indicated spatial proximity between dual single‐atom Cu and Y sites and elucidated Cu speciation controlled by diatomic interactions.
Article Details
Authors (21)
Junyan Zhang
Stephen C. Purdy
Manufacturing Science Division
Mingze Zheng
Department of Chemical and Biomolecular Engineering Johns Hopkins University Baltimore MD 21218 USA
Meijun Li
Nohor “River” Samad
Department of Chemical and Biological Engineering The University of Alabama Tuscaloosa AL 35487 USA
James W. Harris
Department of Chemical and Biological Engineering The University of Alabama Tuscaloosa AL 35487 USA
Kinga A. Unocic
Department of Materials Science and Engineering NC State University Raleigh NC 27695 USA
Evan C. Wegener
Chemical Science and Engineering Division Argonne National Laboratory Lemont IL 60439 USA
Shan Jiang
Wenbo Li
Jeffrey T. Miller
Felipe Polo‐Garzon
Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge Tennessee USA
Dongxia Liu
Department of Chemical and Biomolecular Engineering University of Delaware Newark Delaware USA
Theodore R. Krause
Chemical Science and Engineering Division Argonne National Laboratory Lemont IL 60439 USA
Zili Wu
Chemical Sciences Division
Andrew D. Sutton
Manufacturing Science Division Oak Ridge National Laboratory Oak Ridge TN 37830 USA
Pengfei Xie
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering
Yanran Cui
State Key Laboratory of Biobased Transportation Fuel Technology, College of Biosystems Engineering and Food Science
Sheng Dai
Brandon C. Bukowski
Department of Chemical and Biomolecular Engineering Johns Hopkins University Baltimore MD 21218 USA
Zhenglong Li
State Key Laboratory of Biobased Transportation Fuel Technology, College of Biosystems Engineering and Food Science