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

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

doi:10.1021/acscatal.3c01285

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

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

Chemical Process Scale Up

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Abstract

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. This study establishes the performance and mechanistic differences of SAA and nanoalloys for T-NRR versus E-NRR.

Original language	English
Pages (from-to)	6804-6812
Number of pages	9
Journal	ACS Catalysis
Volume	13
Issue number	10
DOIs	https://doi.org/10.1021/acscatal.3c01285
State	Published - May 19 2023

Funding

This study was partly supported by NSF Division of Chemical, Bioengineering, Environmental, and Transport Systems (CBET) Grant #1955793 and the National Science Foundation (NSF) Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment (EEC-1449500). We would like to acknowledge the Yale West Campus Materials Characterization Core (MCC) for use of XRD. This research used ISS 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. This work utilized computational resources from the ASU High Performance Computing Agave System.

Keywords

copper
electrocatalysis
nitrate reduction
palladium
single atom alloy
thermocatalysis

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10.1021/acscatal.3c01285

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title = "Contrasting Capability of Single Atom Palladium for Thermocatalytic versus Electrocatalytic Nitrate Reduction Reaction",

abstract = "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 (TOFPd = 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. This study establishes the performance and mechanistic differences of SAA and nanoalloys for T-NRR versus E-NRR.",

keywords = "copper, electrocatalysis, nitrate reduction, palladium, single atom alloy, thermocatalysis",

author = "Xuanhao Wu and Mohammadreza Nazemi and Srishti Gupta and Adam Chismar and Kiheon Hong and Hunter Jacobs and Wenqing Zhang and Kali Rigby and Tayler Hedtke and Qingxiao Wang and Eli Stavitski and Wong, \{Michael S.\} and Christopher Muhich and Kim, \{Jae Hong\}",

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AU - Wu, Xuanhao

AU - Nazemi, Mohammadreza

AU - Gupta, Srishti

AU - Chismar, Adam

AU - Hong, Kiheon

AU - Jacobs, Hunter

AU - Zhang, Wenqing

AU - Rigby, Kali

AU - Hedtke, Tayler

AU - Wang, Qingxiao

AU - Stavitski, Eli

AU - Wong, Michael S.

AU - Muhich, Christopher

AU - Kim, Jae Hong

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N2 - 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 (TOFPd = 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. This study establishes the performance and mechanistic differences of SAA and nanoalloys for T-NRR versus E-NRR.

AB - 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 (TOFPd = 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. This study establishes the performance and mechanistic differences of SAA and nanoalloys for T-NRR versus E-NRR.

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

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