Competing effects of pH, cation identity, H2O saturation, and N2 concentration on the activity and selectivity of electrochemical reduction of N2 to NH3 on electrodeposited Cu at ambient conditions

Nishithan C. Kani; Aditya Prajapati; Brianna A Collins; Jason D. Goodpaster; Meenesh R. Singh

doi:10.1021/acscatal.0c04864

Competing effects of pH, cation identity, H₂O saturation, and N₂ concentration on the activity and selectivity of electrochemical reduction of N₂ to NH₃ on electrodeposited Cu at ambient conditions

Nishithan C. Kani, Aditya Prajapati, Brianna A Collins, Jason D. Goodpaster, Meenesh R. Singh

Chemistry (Twin Cities)

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

53 Scopus citations

Abstract

The electrochemical reduction of N₂ to produce NH₃ at ambient conditions is an effective and sustainable route to store and carry hydrogen, balance the nitrogen cycle, and provide means to produce on-demand fertilizers. The efficient electrosynthesis of NH₃ is challenging because of the lower activation of N₂ and higher activity toward the hydrogen evolution reaction (HER). Here, we propose theory-guided activity descriptors to identify an efficient N₂ reduction reaction (NRR) catalyst, followed by its implementation in a flow-through gas diffusion electrode (GDE) to quantify the effects of pH, cation identity, H₂O saturation, and N₂ concentration on the kinetics of the NRR. The identified Cu catalyst with dominant (111) facets electrodeposited on a carbon paper provides optimal active sites to obtain maximum NH₃ faradaic efficiency (FE) of 18 ± 3% at −0.3 V vs RHE and the maximum NH₃ current density of 0.25 ± 0.03 mA cm⁻² (0.86 nmol·cm⁻²·s⁻¹) at −0.5 V vs RHE in alkaline medium. The electrolyte pH mostly affects the HER by pH-induced binding of *H and reorganization of H₂O, which favor the NRR at an optimal pH of 13.5. Increasing the size of monovalent cations stabilizes NRR intermediates and increases the NH₃ current density from Li⁺ to K⁺. However, increasing the size of the cation from K⁺ to Rb⁺ reduces the FE of NRR, which is due to a direct reduction of H₂O in the solvation shell of larger cations to produce H₂. Another strategy to improve NH₃ FE is to reduce the H₂O saturation on the catalyst, which can be achieved by sparging the reactant gas directly through the GDE. Increasing the N_2(g) flow rate not only increases the gas−liquid mass transfer coefficient but also reduces the H₂O saturation in the pores of the GDE, which primarily suppresses the HER. The fixed potential DFT calculations reveal an associative distal mechanism for the NRR over Cu(111), where the hydrogenation of *N₂ is the rate-limiting step. This finding also corroborates with the measured reaction order with respect to N₂

Original language	English (US)
Pages (from-to)	14592-14603
Number of pages	12
Journal	ACS Catalysis
Volume	10
Issue number	24
DOIs	https://doi.org/10.1021/acscatal.0c04864
State	Published - Dec 18 2020

Bibliographical note

Funding Information:
This material is based on the work performed in the Materials and Systems Engineering Laboratory at the University of Illinois at Chicago, in collaboration with J.D.G. at the University of Minnesota. B.A.C. and J.D.G. acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, for providing resources that contributed to the results reported within this paper. This work made use of the EPIC and Keck-II facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-1542205), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). XRD studies were performed at the Nanotechnology Core Facility (NCF) of the University of Illinois at Chicago. NMR studies were performed at the NMR core of Research Resources Center (RRC) of the University of Illinois at Chicago.

Publisher Copyright:
© 2020 American Chemical Society

Keywords

Density functional theory
Electrochemical N reduction
Electrolyte effects
Gas-diffusion electrode
Renewable ammonia synthesis

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This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acscatal.0c04864

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Competing effects of pH, cation identity, H₂O saturation, and N₂ concentration on the activity and selectivity of electrochemical reduction of N₂ to NH₃ on electrodeposited Cu at ambient conditions. / Kani, Nishithan C.; Prajapati, Aditya; Collins, Brianna A et al.
In: ACS Catalysis, Vol. 10, No. 24, 18.12.2020, p. 14592-14603.

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

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title = "Competing effects of pH, cation identity, H2O saturation, and N2 concentration on the activity and selectivity of electrochemical reduction of N2 to NH3 on electrodeposited Cu at ambient conditions",

abstract = "The electrochemical reduction of N2 to produce NH3 at ambient conditions is an effective and sustainable route to store and carry hydrogen, balance the nitrogen cycle, and provide means to produce on-demand fertilizers. The efficient electrosynthesis of NH3 is challenging because of the lower activation of N2 and higher activity toward the hydrogen evolution reaction (HER). Here, we propose theory-guided activity descriptors to identify an efficient N2 reduction reaction (NRR) catalyst, followed by its implementation in a flow-through gas diffusion electrode (GDE) to quantify the effects of pH, cation identity, H2O saturation, and N2 concentration on the kinetics of the NRR. The identified Cu catalyst with dominant (111) facets electrodeposited on a carbon paper provides optimal active sites to obtain maximum NH3 faradaic efficiency (FE) of 18 ± 3% at −0.3 V vs RHE and the maximum NH3 current density of 0.25 ± 0.03 mA cm−2 (0.86 nmol·cm−2·s−1) at −0.5 V vs RHE in alkaline medium. The electrolyte pH mostly affects the HER by pH-induced binding of *H and reorganization of H2O, which favor the NRR at an optimal pH of 13.5. Increasing the size of monovalent cations stabilizes NRR intermediates and increases the NH3 current density from Li+ to K+. However, increasing the size of the cation from K+ to Rb+ reduces the FE of NRR, which is due to a direct reduction of H2O in the solvation shell of larger cations to produce H2. Another strategy to improve NH3 FE is to reduce the H2O saturation on the catalyst, which can be achieved by sparging the reactant gas directly through the GDE. Increasing the N2(g) flow rate not only increases the gas−liquid mass transfer coefficient but also reduces the H2O saturation in the pores of the GDE, which primarily suppresses the HER. The fixed potential DFT calculations reveal an associative distal mechanism for the NRR over Cu(111), where the hydrogenation of *N2 is the rate-limiting step. This finding also corroborates with the measured reaction order with respect to N2",

keywords = "Density functional theory, Electrochemical N reduction, Electrolyte effects, Gas-diffusion electrode, Renewable ammonia synthesis",

author = "Kani, {Nishithan C.} and Aditya Prajapati and Collins, {Brianna A} and Goodpaster, {Jason D.} and Singh, {Meenesh R.}",

note = "Funding Information: This material is based on the work performed in the Materials and Systems Engineering Laboratory at the University of Illinois at Chicago, in collaboration with J.D.G. at the University of Minnesota. B.A.C. and J.D.G. acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, for providing resources that contributed to the results reported within this paper. This work made use of the EPIC and Keck-II facility of Northwestern University{\textquoteright}s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-1542205), the IIN, and Northwestern{\textquoteright}s MRSEC program (NSF DMR-1720139). XRD studies were performed at the Nanotechnology Core Facility (NCF) of the University of Illinois at Chicago. NMR studies were performed at the NMR core of Research Resources Center (RRC) of the University of Illinois at Chicago. Publisher Copyright: {\textcopyright} 2020 American Chemical Society",

year = "2020",

month = dec,

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doi = "10.1021/acscatal.0c04864",

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T1 - Competing effects of pH, cation identity, H2O saturation, and N2 concentration on the activity and selectivity of electrochemical reduction of N2 to NH3 on electrodeposited Cu at ambient conditions

AU - Kani, Nishithan C.

AU - Prajapati, Aditya

AU - Collins, Brianna A

AU - Goodpaster, Jason D.

AU - Singh, Meenesh R.

N1 - Funding Information: This material is based on the work performed in the Materials and Systems Engineering Laboratory at the University of Illinois at Chicago, in collaboration with J.D.G. at the University of Minnesota. B.A.C. and J.D.G. acknowledge the Minnesota Supercomputing Institute (MSI) at the University of Minnesota and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, for providing resources that contributed to the results reported within this paper. This work made use of the EPIC and Keck-II facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-1542205), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). XRD studies were performed at the Nanotechnology Core Facility (NCF) of the University of Illinois at Chicago. NMR studies were performed at the NMR core of Research Resources Center (RRC) of the University of Illinois at Chicago. Publisher Copyright: © 2020 American Chemical Society

PY - 2020/12/18

Y1 - 2020/12/18

N2 - The electrochemical reduction of N2 to produce NH3 at ambient conditions is an effective and sustainable route to store and carry hydrogen, balance the nitrogen cycle, and provide means to produce on-demand fertilizers. The efficient electrosynthesis of NH3 is challenging because of the lower activation of N2 and higher activity toward the hydrogen evolution reaction (HER). Here, we propose theory-guided activity descriptors to identify an efficient N2 reduction reaction (NRR) catalyst, followed by its implementation in a flow-through gas diffusion electrode (GDE) to quantify the effects of pH, cation identity, H2O saturation, and N2 concentration on the kinetics of the NRR. The identified Cu catalyst with dominant (111) facets electrodeposited on a carbon paper provides optimal active sites to obtain maximum NH3 faradaic efficiency (FE) of 18 ± 3% at −0.3 V vs RHE and the maximum NH3 current density of 0.25 ± 0.03 mA cm−2 (0.86 nmol·cm−2·s−1) at −0.5 V vs RHE in alkaline medium. The electrolyte pH mostly affects the HER by pH-induced binding of *H and reorganization of H2O, which favor the NRR at an optimal pH of 13.5. Increasing the size of monovalent cations stabilizes NRR intermediates and increases the NH3 current density from Li+ to K+. However, increasing the size of the cation from K+ to Rb+ reduces the FE of NRR, which is due to a direct reduction of H2O in the solvation shell of larger cations to produce H2. Another strategy to improve NH3 FE is to reduce the H2O saturation on the catalyst, which can be achieved by sparging the reactant gas directly through the GDE. Increasing the N2(g) flow rate not only increases the gas−liquid mass transfer coefficient but also reduces the H2O saturation in the pores of the GDE, which primarily suppresses the HER. The fixed potential DFT calculations reveal an associative distal mechanism for the NRR over Cu(111), where the hydrogenation of *N2 is the rate-limiting step. This finding also corroborates with the measured reaction order with respect to N2

AB - The electrochemical reduction of N2 to produce NH3 at ambient conditions is an effective and sustainable route to store and carry hydrogen, balance the nitrogen cycle, and provide means to produce on-demand fertilizers. The efficient electrosynthesis of NH3 is challenging because of the lower activation of N2 and higher activity toward the hydrogen evolution reaction (HER). Here, we propose theory-guided activity descriptors to identify an efficient N2 reduction reaction (NRR) catalyst, followed by its implementation in a flow-through gas diffusion electrode (GDE) to quantify the effects of pH, cation identity, H2O saturation, and N2 concentration on the kinetics of the NRR. The identified Cu catalyst with dominant (111) facets electrodeposited on a carbon paper provides optimal active sites to obtain maximum NH3 faradaic efficiency (FE) of 18 ± 3% at −0.3 V vs RHE and the maximum NH3 current density of 0.25 ± 0.03 mA cm−2 (0.86 nmol·cm−2·s−1) at −0.5 V vs RHE in alkaline medium. The electrolyte pH mostly affects the HER by pH-induced binding of *H and reorganization of H2O, which favor the NRR at an optimal pH of 13.5. Increasing the size of monovalent cations stabilizes NRR intermediates and increases the NH3 current density from Li+ to K+. However, increasing the size of the cation from K+ to Rb+ reduces the FE of NRR, which is due to a direct reduction of H2O in the solvation shell of larger cations to produce H2. Another strategy to improve NH3 FE is to reduce the H2O saturation on the catalyst, which can be achieved by sparging the reactant gas directly through the GDE. Increasing the N2(g) flow rate not only increases the gas−liquid mass transfer coefficient but also reduces the H2O saturation in the pores of the GDE, which primarily suppresses the HER. The fixed potential DFT calculations reveal an associative distal mechanism for the NRR over Cu(111), where the hydrogenation of *N2 is the rate-limiting step. This finding also corroborates with the measured reaction order with respect to N2

KW - Density functional theory

KW - Electrochemical N reduction

KW - Electrolyte effects

KW - Gas-diffusion electrode

KW - Renewable ammonia synthesis

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