Atomic Layers of B2 CuPd on Cu Nanocubes as Catalysts for Selective Hydrogenation

Gao, Qiang; Yan, Zihao; Zhang, Weijie; Pillai, Hemanth Somarajan; Yao, Bingqing; Zang, Wenjie; Liu, Yuanqi; Han, Xue; Min, Bokki; Zhou, Hua; Ma, Lu; Anaclet, Bukuru; Zhang, Sen; Xin, Hongliang; He, Qian; Zhu, Huiyuan

doi:10.1021/jacs.3c06514

Atomic Layers of B2 CuPd on Cu Nanocubes as Catalysts for Selective Hydrogenation

Journal Article · Thu Aug 31 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c06514· OSTI ID:2404946

Gao, Qiang ^[1]; ^[1]; Zhang, Weijie ^[1]; ^[2]; Yao, Bingqing ^[3]; Zang, Wenjie ^[3]; Liu, Yuanqi ^[1]; Han, Xue ^[2]; Min, Bokki ^[1]; ^[4]; Ma, Lu ^[5]; Anaclet, Bukuru ^[1]; ^[1]; ^[2]; He, Qian ^[3]; ^[1]

Univ. of Virginia, Charlottesville, VA (United States)
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
National Univ. of Singapore (Singapore)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

The search for highly active and selective catalysts with high precious metal atom utilization efficiency has attracted increasing interest in both the fundamental synthesis of materials and important industrial reactions. Here, in this work, we report the synthesis of Pd–Cu nanocubes with a Cu core and an ordered B2 intermetallic CuPd shell with controllable atomic layers on the surface (denoted as Cu/B2 CuPd), which can efficiently and robustly catalyze the selective hydrogenation of acetylene (C₂H₂) to ethylene (C₂H₄) under mild conditions. The optimized Cu/B2 CuPd with a Pd loading of 9.5 at. % exhibited outstanding performance in the C₂H₂ semi-hydrogenation with 100% C₂H₂ conversion and 95.2% C₂H₄ selectivity at 90 °C. We attributed this outstanding performance to the core/shell structure with a high surface density of active Pd sites isolated by Cu in the B2 intermetallic matrix, representing a structural motif of single-atom alloys (SAAs) on the surface. The combined experimental and computational studies further revealed that the electronic states of Pd and Cu are modulated by SAAs from the synergistic effect between Pd and Cu, leading to enhanced performance compared with pristine Pd and Cu catalysts. This study provides a new synthetic methodology for making single-atom catalysts with high precious metal atom utilization efficiency, enabling simultaneous tuning of both geometric and electronic structures of Pd active sites for enhanced catalysis.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 2404946

Alternate ID(s):: OSTI ID: 2432583

Report Number(s):: BNL--225968-2024-JAAM; 184183

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 36 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (40)

Recent Advances of Single‐Atom‐Alloy for Energy Electrocatalysis Shen, Tao; Wang, Shuang; Zhao, Tonghui Advanced Energy Materials, Vol. 12, Issue 39 https://doi.org/10.1002/aenm.202201823	journal	August 2022
How Absorbed Hydrogen Affects the Catalytic Activity of Transition Metals Aleksandrov, Hristiyan A.; Kozlov, Sergey M.; Schauermann, Swetlana Angewandte Chemie International Edition, Vol. 53, Issue 49 https://doi.org/10.1002/anie.201405738	journal	October 2014
Shape-Controlled Synthesis of Monodisperse PdCu Nanocubes and Their Electrocatalytic Properties Gao, Qiang; Ju, Yi-Ming; An, Duo ChemSusChem, Vol. 6, Issue 10 https://doi.org/10.1002/cssc.201300404	journal	August 2013
Recent advances in selective acetylene hydrogenation using palladium containing catalysts McCue, Alan J.; Anderson, James A. Frontiers of Chemical Science and Engineering, Vol. 9, Issue 2 https://doi.org/10.1007/s11705-015-1516-4	journal	June 2015
Enhancing both selectivity and coking-resistance of a single-atom Pd1/C3N4 catalyst for acetylene hydrogenation Huang, Xiaohui; Xia, Yujia; Cao, Yuanjie Nano Research, Vol. 10, Issue 4 https://doi.org/10.1007/s12274-016-1416-z	journal	February 2017
50 ppm of Pd dispersed on Ni(OH)2 nanosheets catalyzing semi-hydrogenation of acetylene with high activity and selectivity Hu, Mingzhen; Zhang, Jian; Zhu, Wei Nano Research, Vol. 11, Issue 2 https://doi.org/10.1007/s12274-017-1701-5	journal	August 2017
Mechanism and kinetics of the selective hydrogenation of ethyne and ethene Bos, A. N. R.; Westerterp, K. R. Chemical Engineering and Processing: Process Intensification, Vol. 32, Issue 1 https://doi.org/10.1016/0255-2701(93)87001-b	journal	February 1993
Performance of Cu-promoted Pd catalysts prepared by adding Cu using a surface redox method in acetylene hydrogenation Kim, Seok Ki; Lee, Ji Hoon; Ahn, In Young Applied Catalysis A: General, Vol. 401, Issue 1-2 https://doi.org/10.1016/j.apcata.2011.04.048	journal	July 2011
Single-Atom Alloy Catalysis Hannagan, Ryan T.; Giannakakis, Georgios; Flytzani-Stephanopoulos, Maria Chemical Reviews https://doi.org/10.1021/acs.chemrev.0c00078	journal	June 2020
Selective Hydrogenation over Supported Metal Catalysts: From Nanoparticles to Single Atoms Zhang, Leilei; Zhou, Maoxiang; Wang, Aiqin Chemical Reviews, Vol. 120, Issue 2 https://doi.org/10.1021/acs.chemrev.9b00230	journal	September 2019
Metal–Metal Oxide Catalytic Interface Formation and Structural Evolution: A Discovery of Strong Metal–Support Bonding, Ordered Intermetallics, and Single Atoms Yan, Zihao; Yao, Bingqing; Hall, Connor Nano Letters, Vol. 22, Issue 20 https://doi.org/10.1021/acs.nanolett.2c02568	journal	October 2022
Charge-Separated Pd^δ−–Cu^δ+ Atom Pairs Promote CO₂ Reduction to C₂ Zhang, Zedong; Chen, Shenghua; Zhu, Jiexin Nano Letters, Vol. 23, Issue 6 https://doi.org/10.1021/acs.nanolett.2c05112	journal	March 2023
Ag Alloyed Pd Single-Atom Catalysts for Efficient Selective Hydrogenation of Acetylene to Ethylene in Excess Ethylene Pei, Guang Xian; Liu, Xiao Yan; Wang, Aiqin ACS Catalysis, Vol. 5, Issue 6 https://doi.org/10.1021/acscatal.5b00700	journal	May 2015
Rational Design of Bi Nanoparticles for Efficient Electrochemical CO ₂ Reduction: The Elucidation of Size and Surface Condition Effects Zhang, Zhiyong; Chi, Miaofang; Veith, Gabriel M. ACS Catalysis, Vol. 6, Issue 9 https://doi.org/10.1021/acscatal.6b01297	journal	August 2016
Performance of Cu-Alloyed Pd Single-Atom Catalyst for Semihydrogenation of Acetylene under Simulated Front-End Conditions Pei, Guang Xian; Liu, Xiao Yan; Yang, Xiaofeng ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b03293	journal	January 2017
Selective Hydrogenation of Acetylene over Pd-In/Al ₂ O ₃ Catalyst: Promotional Effect of Indium and Composition-Dependent Performance Cao, Yueqiang; Sui, Zhijun; Zhu, Yian ACS Catalysis, Vol. 7, Issue 11 https://doi.org/10.1021/acscatal.7b01745	journal	October 2017
Selective Hydrogenation of Acetylene to Ethylene in the Presence of a Carbonaceous Surface Layer on a Pd/Cu(111) Single-Atom Alloy Kruppe, Christopher M.; Krooswyk, Joel D.; Trenary, Michael ACS Catalysis, Vol. 7, Issue 12 https://doi.org/10.1021/acscatal.7b02862	journal	October 2017
Stabilizing High Metal Loadings of Thermally Stable Platinum Single Atoms on an Industrial Catalyst Support Kunwar, Deepak; Zhou, Shulan; DeLaRiva, Andrew ACS Catalysis, Vol. 9, Issue 5 https://doi.org/10.1021/acscatal.8b04885	journal	February 2019
Overwhelming the Performance of Single Atoms with Atomic Clusters for Platinum-Catalyzed Hydrogen Evolution Sun, Minghao; Ji, Jiapeng; Hu, Mingyu ACS Catalysis, Vol. 9, Issue 9 https://doi.org/10.1021/acscatal.9b02305	journal	July 2019
Structure Sensitivity of Acetylene Semi-Hydrogenation on Pt Single Atoms and Subnanometer Clusters Kuo, Chun-Te; Lu, Yubing; Kovarik, Libor ACS Catalysis, Vol. 9, Issue 12 https://doi.org/10.1021/acscatal.9b02840	journal	October 2019
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar300361m	journal	April 2013
Introduction of π-Complexation into Porous Aromatic Framework for Highly Selective Adsorption of Ethylene over Ethane Li, Baiyan; Zhang, Yiming; Krishna, Rajamani Journal of the American Chemical Society, Vol. 136, Issue 24 https://doi.org/10.1021/ja502119z	journal	June 2014
Selective Interactions between Free-Atom-like d -States in Single-Atom Alloy Catalysts and Near-Frontier Molecular Orbitals Spivey, Taylor D.; Holewinski, Adam Journal of the American Chemical Society, Vol. 143, Issue 31 https://doi.org/10.1021/jacs.1c04234	journal	July 2021
Isolated Single-Atom Pd Sites in Intermetallic Nanostructures: High Catalytic Selectivity for Semihydrogenation of Alkynes Feng, Quanchen; Zhao, Shu; Wang, Yu Journal of the American Chemical Society, Vol. 139, Issue 21 https://doi.org/10.1021/jacs.7b01471	journal	May 2017
Single-atom catalysis of CO oxidation using Pt1/FeOx Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng Nature Chemistry, Vol. 3, Issue 8 https://doi.org/10.1038/nchem.1095	journal	July 2011
Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9550	journal	October 2015
Interfacial electronic effects control the reaction selectivity of platinum catalysts Chen, Guangxu; Xu, Chaofa; Huang, Xiaoqing Nature Materials, Vol. 15, Issue 5 https://doi.org/10.1038/nmat4555	journal	January 2016
Harnessing strong metal–support interactions via a reverse route Wu, Peiwen; Tan, Shuai; Moon, Jisue Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16674-y	journal	June 2020
Atomic overlayer of permeable microporous cuprous oxide on palladium promotes hydrogenation catalysis Liu, Kunlong; Jiang, Lizhi; Huang, Wugen Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-30327-2	journal	May 2022
Free-atom-like d states in single-atom alloy catalysts Greiner, M. T.; Jones, T. E.; Beeg, S. Nature Chemistry, Vol. 10, Issue 10 https://doi.org/10.1038/s41557-018-0125-5	journal	August 2018
Heterogeneous single-atom catalysis Wang, Aiqin; Li, Jun; Zhang, Tao Nature Reviews Chemistry, Vol. 2, Issue 6 https://doi.org/10.1038/s41570-018-0010-1	journal	May 2018
Structural selectivity of supported Pd nanoparticles for catalytic NH3 oxidation resolved using combined operando spectroscopy Dann, Ellie K.; Gibson, Emma K.; Blackmore, Rachel H. Nature Catalysis, Vol. 2, Issue 2 https://doi.org/10.1038/s41929-018-0213-3	journal	January 2019
Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia Gao, Qiang; Yao, Bingqing; Pillai, Hemanth Somarajan Nature Synthesis, Vol. 2, Issue 7 https://doi.org/10.1038/s44160-023-00258-x	journal	March 2023
An in situ DRIFTS mechanistic study of CeO ₂ -catalyzed acetylene semihydrogenation reaction Cao, Tian; You, Rui; Zhang, Xuanyu Physical Chemistry Chemical Physics, Vol. 20, Issue 14 https://doi.org/10.1039/c8cp00668g	journal	January 2018
Sustainable Hydrogen Production Turner, J. A. Science, Vol. 305, Issue 5686 https://doi.org/10.1126/science.1103197	journal	August 2004
The Roles of Subsurface Carbon and Hydrogen in Palladium-Catalyzed Alkyne Hydrogenation Teschner, D.; Borsodi, J.; Wootsch, A. Science, Vol. 320, Issue 5872 https://doi.org/10.1126/science.1155200	journal	April 2008
Identification of Non-Precious Metal Alloy Catalysts for Selective Hydrogenation of Acetylene Studt, F.; Abild-Pedersen, F.; Bligaard, T. Science, Vol. 320, Issue 5881 https://doi.org/10.1126/science.1156660	journal	June 2008
Isolated Metal Atom Geometries as a Strategy for Selective Heterogeneous Hydrogenations Kyriakou, Georgios; Boucher, Matthew B.; Jewell, April D. Science, Vol. 335, Issue 6073 https://doi.org/10.1126/science.1215864	journal	March 2012
Control of Metal Nanocrystal Size Reveals Metal-Support Interface Role for Ceria Catalysts Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R. Science, Vol. 341, Issue 6147 https://doi.org/10.1126/science.1240148	journal	July 2013
Photochemical route for synthesizing atomically dispersed palladium catalysts Liu, P.; Zhao, Y.; Qin, R. Science, Vol. 352, Issue 6287 https://doi.org/10.1126/science.aaf5251	journal	May 2016

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Atomic Layers of B2 CuPd on Cu Nanocubes as Catalysts for Selective Hydrogenation

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