Contrasting Capability of Single Atom Palladium for Thermocatalytic versus Electrocatalytic Nitrate Reduction Reaction

Wu, Xuanhao; Nazemi, Mohammadreza; Gupta, Srishti; Chismar, Adam; Hong, Kiheon; Jacobs, Hunter; Zhang, Wenqing; Rigby, Kali; Hedtke, Tayler; Wang, Qingxiao; Stavitski, Eli; Wong, Michael S.; Muhich, Christopher; Kim, Jae-Hong

doi:10.1021/acscatal.3c01285

Title: Contrasting Capability of Single Atom Palladium for Thermocatalytic versus Electrocatalytic Nitrate Reduction Reaction

Journal Article · 03 May 2023 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.3c01285 · OSTI ID:1996200

Wu, Xuanhao ^[1]; Nazemi, Mohammadreza ^[2]; Gupta, Srishti ^[3]; Chismar, Adam ^[3]; Hong, Kiheon ^[4]; Jacobs, Hunter ^[4]; Zhang, Wenqing ^[4]; Rigby, Kali ^[2]; Hedtke, Tayler ^[2]; Wang, Qingxiao ^[5]; Stavitski, Eli ^[6]; Wong, Michael S. ^[4]; Muhich, Christopher ^[3]; Kim, Jae-Hong ^[2]

Zhejiang University (China); Yale Univ., New Haven, CT (United States)
Yale Univ., New Haven, CT (United States)
Arizona State Univ., Tempe, AZ (United States)
Rice Univ., Houston, TX (United States)
King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

The occurrence of high concentrations of nitrate in various water resources is a significant environmental and human health threat, demanding effective removal technologies. Single atom alloys (SAAs) have emerged as a promising bimetallic material architecture in various thermocatalytic and electrocatalytic schemes including nitrate reduction reaction (NRR). This study suggests that there exists a stark contrast between thermocatalytic (T-NRR) and electrocatalytic (E-NRR) pathways that resulted in dramatic differences in SAA performances. Among Pd/Cu nanoalloys with varying Pd–Cu ratios from 1:100 to 100:1, Pd/Cu_(1:100) SAA exhibited the greatest activity (TOF_Pd = 2 min^–1) and highest N₂ selectivity (94%) for E-NRR, while the same SAA performed poorly for T-NRR as compared to other nanoalloy counterparts. DFT calculations demonstrate that the improved performance and N₂ selectivity of Pd/Cu_(1:100) in E-NRR compared to T-NRR originate from the higher stability of NO₃* in electrocatalysis and a lower N₂ formation barrier than NH due to localized pH effects and the ability to extract protons from water. Here, this study establishes the performance and mechanistic differences of SAA and nanoalloys for T-NRR versus E-NRR.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; CBET-1955793; EEC-1449500

OSTI ID:: 1996200

Report Number(s):: BNL-224681-2023-JAAM

Journal Information:: ACS Catalysis, Vol. 13, Issue 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (54)

Nitrite Reduction Mechanism on a Pd Surface Shin, Hyeyoung; Jung, Sungyoon; Bae, Sungjun Environmental Science & Technology, Vol. 48, Issue 21 https://doi.org/10.1021/es503772x	journal	October 2014
Anodic dissolution of palladium + copper alloys Petró, J.; Mallát, T.; Szabó, S. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 160, Issue 1-2 https://doi.org/10.1016/S0022-0728(84)80132-1	journal	January 1984
Controlling Selectivity in Unsaturated Aldehyde Hydrogenation Using Single-Site Alloy Catalysts Cao, Yueqiang; Chen, Bo; Guerrero-Sánchez, Jonathan ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b02547	journal	September 2019
Cu-Based Single-Atom Catalysts Boost Electroreduction of CO ₂ to CH ₃ OH: First-Principles Predictions Zhao, Zhonglong; Lu, Gang The Journal of Physical Chemistry C, Vol. 123, Issue 7 https://doi.org/10.1021/acs.jpcc.8b12449	journal	January 2019
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
Development of Pd–Cu/Hematite Catalyst for Selective Nitrate Reduction Jung, Sungyoon; Bae, Sungjun; Lee, Woojin Environmental Science & Technology, Vol. 48, Issue 16 https://doi.org/10.1021/es502263p	journal	August 2014
Electrocatalytic Reduction of Nitrate on a Pt Electrode Modified by p-Block Metal Adatoms in Acid Solution Yang, Jian; Calle-Vallejo, Federico; Duca, Matteo ChemCatChem, Vol. 5, Issue 7 https://doi.org/10.1002/cctc.201300075	journal	May 2013
High-Throughput Screening of a Single-Atom Alloy for Electroreduction of Dinitrogen to Ammonia Zheng, Guokui; Li, Yanle; Qian, Xu ACS Applied Materials & Interfaces, Vol. 13, Issue 14 https://doi.org/10.1021/acsami.1c01098	journal	April 2021
Electrochemical Reduction of Nitrate on Pyrolytic Graphite-Supported Cu and Pd–Cu Electrocatalysts Ghodbane, Ouassim; Sarrazin, Mathieu; Roué, Lionel Journal of The Electrochemical Society, Vol. 155, Issue 6 https://doi.org/10.1149/1.2900094	journal	January 2008
Electrochemical-catalytic reduction of nitrate over Pd–Cu/γAl 2 O 3 catalyst in cathode chamber: Enhanced removal efficiency and N 2 selectivity Zhang, Zhiqiang; Xu, Yongpeng; Shi, Wenxin Chemical Engineering Journal, Vol. 290 https://doi.org/10.1016/j.cej.2016.01.063	journal	April 2016
Elaboration of Cu−Pd Films by Coelectrodeposition: Application to Nitrate Electroreduction Reyter, David; Bélanger, Daniel; Roué, Lionel The Journal of Physical Chemistry C, Vol. 113, Issue 1 https://doi.org/10.1021/jp805484t	journal	November 2008
Erste Schritte auf dem Weg zur edelmetallkatalysierten Nitrat- und Nitrit-Entfernung aus Trinkwasser Vorlop, Klaus-Dieter; Tacke, Thomas Chemie Ingenieur Technik, Vol. 61, Issue 10 https://doi.org/10.1002/cite.330611023	journal	October 1989
Breaking the scaling relationship via thermally stable Pt/Cu single atom alloys for catalytic dehydrogenation Sun, Guodong; Zhao, Zhi-Jian; Mu, Rentao Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06967-8	journal	October 2018
Reaction Pathways for Reduction of Nitrate Ions on Platinum, Rhodium, and Platinum−Rhodium Alloy Electrodes da Cunha, M. C. P. M.; De Souza, J. P. I.; Nart, F. C. Langmuir, Vol. 16, Issue 2 https://doi.org/10.1021/la990638s	journal	November 1999
Electrocatalytic reduction of nitrate at low concentration on coinage and transition-metal electrodes in acid solutions Dima, G. E.; de Vooys, A. C. A.; Koper, M. T. M. Journal of Electroanalytical Chemistry, Vol. 554-555 https://doi.org/10.1016/S0022-0728(02)01443-2	journal	September 2003
Appropriate conditions or maximizing catalytic reduction efficiency of nitrate into nitrogen gas in groundwater Chen, Ying-Xue; Zhang, Yan; Chen, Guang-Hao Water Research, Vol. 37, Issue 10 https://doi.org/10.1016/S0043-1354(03)00028-9	journal	May 2003
Highly Durable Platinum Single-Atom Alloy Catalyst for Electrochemical Reactions Kim, Jiwhan; Roh, Chi-Woo; Sahoo, Suman Kalyan Advanced Energy Materials, Vol. 8, Issue 1 https://doi.org/10.1002/aenm.201701476	journal	September 2017
CO adsorption on Pd(111): the effects of temperature and pressure Kuhn, W. Kevin; Szanyi, János; Goodman, D. Wayne Surface Science, Vol. 274, Issue 3 https://doi.org/10.1016/0039-6028(92)90834-S	journal	August 1992
Nitrate reduction by maghemite supported Cu-Pd bimetallic catalyst Jung, Junyoung; Bae, Sungjun; Lee, Woojin Applied Catalysis B: Environmental, Vol. 127 https://doi.org/10.1016/j.apcatb.2012.08.017	journal	October 2012
Carbon supported Pd–Cu nanoalloys: support and valence band structure influence on reduction and oxidation reactions Castegnaro, Marcus V.; Gorgeski, Andreia; Alves, Maria C. M. Nanoscale Advances, Vol. 3, Issue 21 https://doi.org/10.1039/D1NA00537E	journal	January 2021
Electrochemical reduction of nitrate and nitrite in alkaline media at CuNi alloy electrodes Mattarozzi, Luca; Cattarin, Sandro; Comisso, Nicola Electrochimica Acta, Vol. 89 https://doi.org/10.1016/j.electacta.2012.11.074	journal	February 2013
Catalytic activity of Pd-doped Cu nanoparticles for hydrogenation as a single-atom-alloy catalyst Cao, Xinrui; Fu, Qiang; Luo, Yi Phys. Chem. Chem. Phys., Vol. 16, Issue 18 https://doi.org/10.1039/C4CP00399C	journal	January 2014
Electroreduction of nitrate ions at a platinum-copper electrode in an alkaline medium: Influence of sodium inositol phytate Amertharaj, S.; Hasnat, M. A.; Mohamed, N. Electrochimica Acta, Vol. 136 https://doi.org/10.1016/j.electacta.2014.05.128	journal	August 2014
Development of catalysts for a selective nitrate and nitrite removal from drinking water Hörold, S.; Vorlop, K. -D.; Tacke, T. Catalysis Today, Vol. 17, Issue 1-2 https://doi.org/10.1016/0920-5861(93)80004-K	journal	May 1993
Advances in the catalytic reduction of nitrate by metallic catalysts for high efficiency and N2 selectivity: A review Tokazhanov, Galym; Ramazanova, Elmira; Hamid, Shanawar Chemical Engineering Journal, Vol. 384 https://doi.org/10.1016/j.cej.2019.123252	journal	March 2020
Surface Oxygen Atom as a Cooperative Ligand in Pd Nanoparticle Catalysis for Selective Hydration of Nitriles to Amides in Water: Experimental and Theoretical Studies Shimizu, Ken-ichi; Kubo, Takahiro; Satsuma, Atsushi ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs3006154	journal	October 2012
Electrocatalytic reduction of nitrate: Fundamentals to full-scale water treatment applications Garcia-Segura, Sergi; Lanzarini-Lopes, Mariana; Hristovski, Kiril Applied Catalysis B: Environmental, Vol. 236 https://doi.org/10.1016/j.apcatb.2018.05.041	journal	November 2018
A Cu–Pd single-atom alloy catalyst for highly efficient NO reduction Xing, Feilong; Jeon, Jaewan; Toyao, Takashi Chemical Science, Vol. 10, Issue 36 https://doi.org/10.1039/C9SC03172C	journal	January 2019
Drinking Water Nitrate and the Risk of Non-Hodgkinʼs Lymphoma Ward, Mary H.; Mark, Steven D.; Cantor, Kenneth P. Epidemiology, Vol. 7, Issue 5 https://doi.org/10.1097/00001648-199609000-00003	journal	September 1996
Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst Chen, Feng-Yang; Wu, Zhen-Yu; Gupta, Srishti Nature Nanotechnology, Vol. 17, Issue 7 https://doi.org/10.1038/s41565-022-01121-4	journal	May 2022
Theoretical design and experimental implementation of Ag/Au electrodes for the electrochemical reduction of nitrate Calle-Vallejo, Federico; Huang, Minghua; Henry, John B. Physical Chemistry Chemical Physics, Vol. 15, Issue 9 https://doi.org/10.1039/c2cp44620k	journal	January 2013
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
Heats of Adsorption of CO on a Cu/Al₂O₃ Catalyst Using FTIR Spectroscopy at High Temperatures and under Adsorption Equilibrium Conditions Dulaurent, Olivier; Courtois, Xavier; Perrichon, Vincent The Journal of Physical Chemistry B, Vol. 104, Issue 25 https://doi.org/10.1021/jp9943629	journal	June 2000
Forecasting monthly copper price: A comparative study of various machine learning-based methods Zhang, Hong; Nguyen, Hoang; Vu, Diep-Anh Resources Policy, Vol. 73 https://doi.org/10.1016/j.resourpol.2021.102189	journal	October 2021
Municipal Drinking Water Nitrate Level and Cancer Risk in Older Women: The Iowa Women’s Health Study Weyer, Peter J.; Cerhan, James R.; Kross, Burton C. Epidemiology, Vol. 12, Issue 3 https://doi.org/10.1097/00001648-200105000-00013	journal	May 2001
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
How nitrate leaching from agricultural lands provokes phosphate eutrophication in groundwater fed wetlands: the sulphur bridge Smolders, Alfons J. P.; Lucassen, Esther C. H. E. T.; Bobbink, Roland Biogeochemistry, Vol. 98, Issue 1-3 https://doi.org/10.1007/s10533-009-9387-8	journal	November 2009
Surface Reactivity of Pd Nanoparticles Supported on Polycrystalline Substrates As Compared to Thin Film Model Catalysts: Infrared Study of CO Adsorption Bertarione, Serena; Scarano, Domenica; Zecchina, Adriano The Journal of Physical Chemistry B, Vol. 108, Issue 11 https://doi.org/10.1021/jp036718t	journal	March 2004
Pd–Cu Alloy Nanoparticles Confined within Mesoporous Hollow Carbon Spheres for the Hydrogenation of CO ₂ to Formate Yang, Guoxiang; Kuwahara, Yasutaka; Mori, Kohsuke The Journal of Physical Chemistry C, Vol. 125, Issue 7 https://doi.org/10.1021/acs.jpcc.0c10962	journal	February 2021
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
On the assessment of electrocatalysts for nitrate reduction Katsounaros, Ioannis Current Opinion in Electrochemistry, Vol. 28 https://doi.org/10.1016/j.coelec.2021.100721	journal	August 2021
High throughput optimisation of PdCu alloy electrocatalysts for the reduction of nitrate ions Anastasopoulos, Alexandros; Hannah, Louise; Hayden, Brian E. Journal of Catalysis, Vol. 305 https://doi.org/10.1016/j.jcat.2013.04.010	journal	September 2013
Nitrate reduction in water catalysed by Pd–Cu on different supports Soares, Olívia Salomé G. P.; Órfão, José J. M.; Pereira, Manuel Fernando R. Desalination, Vol. 279, Issue 1-3 https://doi.org/10.1016/j.desal.2011.06.037	journal	September 2011
Catalytic Converters for Water Treatment Heck, Kimberly N.; Garcia-Segura, Sergi; Westerhoff, Paul Accounts of Chemical Research, Vol. 52, Issue 4 https://doi.org/10.1021/acs.accounts.8b00642	journal	February 2019
The electrochemical reduction of nitrate over micro-architectured metal electrodes with stainless steel scaffold Su, Jenn Fang; Ruzybayev, Inci; Shah, Ismat Applied Catalysis B: Environmental, Vol. 180 https://doi.org/10.1016/j.apcatb.2015.06.028	journal	January 2016
Electrodeposition of Compact and Porous Cu-Zn Alloy Electrodes and Their Use in the Cathodic Reduction of Nitrate Mattarozzi, Luca; Cattarin, Sandro; Comisso, Nicola Journal of The Electrochemical Society, Vol. 162, Issue 6 https://doi.org/10.1149/2.1041506jes	journal	January 2015
Electrocatalytic activity of copper alloys for NO−3 reduction in a weakly alkaline solution Mácová, Z.; Bouzek, K.; Šerák, J. Journal of Applied Electrochemistry, Vol. 37, Issue 5 https://doi.org/10.1007/s10800-006-9287-8	journal	January 2007
Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions Boucher, Matthew B.; Zugic, Branko; Cladaras, George Physical Chemistry Chemical Physics, Vol. 15, Issue 29 https://doi.org/10.1039/c3cp51538a	journal	January 2013
Reduction of nitrate on active carbon supported Pd-Cu catalysts Trawczyński, J.; Gheek, P.; Okal, J. Applied Catalysis A: General, Vol. 409-410 https://doi.org/10.1016/j.apcata.2011.09.020	journal	December 2011
Catalytic reduction of nitrate on Pt-Cu and Pd-Cu on active carbon using continuous reactorThe effect of copper nanoparticles Barrabes, N.; Just, J.; Dafinov, A. Applied Catalysis B: Environmental, Vol. 62, Issue 1-2 https://doi.org/10.1016/j.apcatb.2005.06.015	journal	January 2006
Unoccupied states and charge transfer in Cu-Pd alloys studied by bremsstrahlung isochromat spectroscopy, x-ray photoelectron spectroscopy, andLIIIabsorption spectroscopy Cho, En-Jin; Lee, Seeyeol; Oh, S. -J. Physical Review B, Vol. 52, Issue 23 https://doi.org/10.1103/PhysRevB.52.16443	journal	December 1995
Occurrence of Nitrate in Groundwater—A Review Spalding, R. F.; Exner, M. E. Journal of Environment Quality, Vol. 22, Issue 3 https://doi.org/10.2134/jeq1993.00472425002200030002x	journal	January 1993
Surface Modification of Pt(100) for Electrocatalytic Nitrate Reduction to Dinitrogen in Alkaline Solution Chen, Ting; Li, Hongjiao; Ma, Houyi Langmuir, Vol. 31, Issue 10 https://doi.org/10.1021/acs.langmuir.5b00283	journal	March 2015
Palladium Carbide and Hydride Formation in the Bulk and at the Surface of Palladium Nanoparticles Bugaev, Aram L.; Usoltsev, Oleg A.; Guda, Alexander A. The Journal of Physical Chemistry C, Vol. 122, Issue 22 https://doi.org/10.1021/acs.jpcc.7b11473	journal	February 2018

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36 MATERIALS SCIENCE
single atom alloy
nitrate reduction
thermocatalysis
electrocatalysis
palladium
copper
anions
catalysts
redox reactions
selectivity

Title: Contrasting Capability of Single Atom Palladium for Thermocatalytic versus Electrocatalytic Nitrate Reduction Reaction

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