Cu Evolution over Bimetallic Cu-Y/Beta Zeolite Under H2 and Ethanol Atmospheres: Unveiling the Role of Diatomic Metal–Metal Interactions

Junyan Zhang; Stephen C. Purdy; Mingze Zheng; Meijun Li; Nohor “River” Samad; James W. Harris; Kinga Unocic; Evan C. Wegener; Shan Jiang; Wenbo Li; Jeffrey T. Miller; Felipe Polo-Garzon; Dongxia Liu; Theodore R. Krause; Zili Wu; Andrew Sutton; Pengfei Xie; Yanran Cui; Sheng Dai; Brandon C. Bukowski; Zhenglong Li

doi:10.1002/anie.202514920

Cu Evolution over Bimetallic Cu-Y/Beta Zeolite Under H₂ and Ethanol Atmospheres: Unveiling the Role of Diatomic Metal–Metal Interactions

Junyan Zhang, Stephen C. Purdy, Mingze Zheng, Meijun Li, Nohor “River” Samad, James W. Harris, Kinga Unocic, Evan C. Wegener, Shan Jiang, Wenbo Li, Jeffrey T. Miller, Felipe Polo-Garzon, Dongxia Liu, Theodore R. Krause, Zili Wu, Andrew Sutton, Pengfei Xie, Yanran Cui, Sheng Dai, Brandon C. BukowskiZhenglong Li

Research output: Contribution to journal › Article › peer-review

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 H₂ 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 H₂ 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 H₂ 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.

Original language	English
Journal	Angewandte Chemie - International Edition
DOIs	https://doi.org/10.1002/anie.202514920
State	Accepted/In press - 2025

Funding

P.X., Y.C., and Z.L. acknowledge the financial support from the National Key R&D Program of China (2023YFA1508103) and the National Natural Science Foundation of China (22478339). M.Z., J.W.H., and B.C.C. acknowledge support from the Department of Energy EERE BETO DE‐EE0010304. M.L. and A.S. also acknowledges funding from Center for Bioenergy Innovation (CBI), which is a U.S. Department of Energy Bioenergy Research Center supported by the Office of Biological and Environmental Research in the DOE Office of Science. This manuscript has been authored by Oak Ridge National Laboratory, operated by UT‐Battelle, LLC, under contract DE‐AC05‐00OR22725 with the US Department of Energy (DOE). This research is sponsored by the U.S. DOE Office of Energy Efficiency and Renewable Energy Bioenergy Technologies Office in collaboration with the Chemical Catalysis for Bioenergy (ChemCatBio) Consortium, a member of the Energy Materials Network (EMN). Part of the work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. MRCAT operations and beamline 10‐BM are supported by the Department of Energy and the MRCAT member institutions. This research used beamline 8‐ID of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE‐SC0012704. Microscopy characterization was supported by the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. The authors thank Shawn K. Reeves for assistance with TEM sample preparation. Notice: This manuscript has been authored by UT‐Battelle, LLC, under Contract DE‐AC05‐76RL01830 with the US Department of Energy (DOE). The US government retains, and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid‐up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan.

Keywords

Copper
Dehydrogenation
Dual atom catalysts
Metal–metal interaction
Zeolites

Access to Document

10.1002/anie.202514920

Cite this

Zhang, J., Purdy, S. C., Zheng, M., Li, M., Samad, N. R., Harris, J. W., Unocic, K., Wegener, E. C., Jiang, S., Li, W., Miller, J. T., Polo-Garzon, F., Liu, D., Krause, T. R., Wu, Z., Sutton, A., Xie, P., Cui, Y., Dai, S., ... Li, Z. (Accepted/In press). Cu Evolution over Bimetallic Cu-Y/Beta Zeolite Under H₂ and Ethanol Atmospheres: Unveiling the Role of Diatomic Metal–Metal Interactions. Angewandte Chemie - International Edition. https://doi.org/10.1002/anie.202514920

@article{3b571c6f77d54a3ca017768e943e39da,

title = "Cu Evolution over Bimetallic Cu-Y/Beta Zeolite Under H2 and Ethanol Atmospheres: Unveiling the Role of Diatomic Metal–Metal Interactions",

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 H2 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 H2 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 H2 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.",

keywords = "Copper, Dehydrogenation, Dual atom catalysts, Metal–metal interaction, Zeolites",

author = "Junyan Zhang and Purdy, \{Stephen C.\} and Mingze Zheng and Meijun Li and Samad, \{Nohor “River”\} and Harris, \{James W.\} and Kinga Unocic and Wegener, \{Evan C.\} and Shan Jiang and Wenbo Li and Miller, \{Jeffrey T.\} and Felipe Polo-Garzon and Dongxia Liu and Krause, \{Theodore R.\} and Zili Wu and Andrew Sutton and Pengfei Xie and Yanran Cui and Sheng Dai and Bukowski, \{Brandon C.\} and Zhenglong Li",

note = "Publisher Copyright: {\textcopyright} 2025 Wiley-VCH GmbH.",

year = "2025",

doi = "10.1002/anie.202514920",

language = "English",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "wiley",

}

Zhang, J, Purdy, SC, Zheng, M, Li, M, Samad, NR, Harris, JW, Unocic, K, Wegener, EC, Jiang, S, Li, W, Miller, JT, Polo-Garzon, F, Liu, D, Krause, TR, Wu, Z, Sutton, A, Xie, P, Cui, Y, Dai, S, Bukowski, BC & Li, Z 2025, 'Cu Evolution over Bimetallic Cu-Y/Beta Zeolite Under H₂ and Ethanol Atmospheres: Unveiling the Role of Diatomic Metal–Metal Interactions', Angewandte Chemie - International Edition. https://doi.org/10.1002/anie.202514920

TY - JOUR

T1 - Cu Evolution over Bimetallic Cu-Y/Beta Zeolite Under H2 and Ethanol Atmospheres

T2 - Unveiling the Role of Diatomic Metal–Metal Interactions

AU - Zhang, Junyan

AU - Purdy, Stephen C.

AU - Zheng, Mingze

AU - Li, Meijun

AU - Samad, Nohor “River”

AU - Harris, James W.

AU - Unocic, Kinga

AU - Wegener, Evan C.

AU - Jiang, Shan

AU - Li, Wenbo

AU - Miller, Jeffrey T.

AU - Polo-Garzon, Felipe

AU - Liu, Dongxia

AU - Krause, Theodore R.

AU - Wu, Zili

AU - Sutton, Andrew

AU - Xie, Pengfei

AU - Cui, Yanran

AU - Dai, Sheng

AU - Bukowski, Brandon C.

AU - Li, Zhenglong

PY - 2025

Y1 - 2025

N2 - 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 H2 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 H2 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 H2 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.

AB - 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 H2 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 H2 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 H2 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.

KW - Copper

KW - Dehydrogenation

KW - Dual atom catalysts

KW - Metal–metal interaction

KW - Zeolites

UR - https://www.scopus.com/pages/publications/105018026376

U2 - 10.1002/anie.202514920

DO - 10.1002/anie.202514920

M3 - Article

AN - SCOPUS:105018026376

SN - 1433-7851

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

ER -