Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products

Yuwei Yang; Jodie A. Yuwono; Todd Whittaker; Marc Manyé Ibáñez; Bingliang Wang; Changmin Kim; Albina Y. Borisevich; Stephanie Chua; Jhair Pena Prada; Xichu Wang; Pierre Olivier Autran; Raymond R. Unocic; Liming Dai; Adam Holewinski; Nicholas M. Bedford

doi:10.1002/adma.202403187

Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products

Yuwei Yang, Jodie A. Yuwono, Todd Whittaker, Marc Manyé Ibáñez, Bingliang Wang, Changmin Kim, Albina Y. Borisevich, Stephanie Chua, Jhair Pena Prada, Xichu Wang, Pierre Olivier Autran, Raymond R. Unocic, Liming Dai, Adam Holewinski, Nicholas M. Bedford

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

Abstract

Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure-selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N₂, reaching a current density of 20 mA cm_geo⁻² at 1.04 V – 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in-situ spectroscopies and scattering experiments reveal a unique in situ generated Cu^(2-x)+-OO^−• active sites in CuCo, which initiates nucleophilic substitution of NH₂ from the amide, leading to N-N coupling between ^*NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high-valence Ni³⁺ and Ni⁴⁺, which facilitates N-H activation. This process, in conjunction with the excessive accumulation of OH⁻ ions on Jahn-Teller (JT) distorted Co sites, leads to the generation of NO₂⁻ as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.

Original language	English
Article number	2403187
Journal	Advanced Materials
Volume	36
Issue number	35
DOIs	https://doi.org/10.1002/adma.202403187
State	Published - Aug 28 2024

Funding

Y.Y. and N.M.B would like to acknowledge support from the Faculty of Engineering at UNSW and the Australian Renewable Energy Agency (ARENA) Hydrogen Program (2018/RND015). L.D, N.M.B, and Y.Y would like to acknowledge support from ARC CoE\u2010CSI (CE230100032). A.H would like to acknowledge the support from DOE BES Grant #DE\u2010SC0023322. XAS measurements were performed at the XAS (Ni, Co, and Cu K\u2010edge) and SXR (O K\u2010edge, metal L\u2010edges) beamlines of the Australian Synchrotron, part of ANSTO. The authors would like to thank Drs Jessica Hamilton and Burce Cowie for their assistance with experiments at XAS and SXR respectively. The authors acknowledge the European Synchrotron Radiation Facility (ESRF) for the provision of synchrotron radiation facilities for in\u2010situ HE\u2010XRD/PDF measurements at the ID11 beamline. The authors acknowledge the use of the facilities and the scientific and technical assistance of the ORNL's Center for Nanophase Materials Sciences (CNMS), Mark Wainwright Analytical Centre (MWAC), and the Electron Microscope Unit (EMU) at UNSW, Sydney. N.M.B. would like to acknowledge support from the UNSW Digital Grid Futures Institute. The research was undertaken with the assistance of computational resources provided by National Computational Infrastructure (NCI) Australia.

Funders	Funder number
UNSW Digital Grid Futures Institute
UNSW
Australian Renewable Energy Agency	2018/RND015
Australian Renewable Energy Agency
ARC CoE‐CSI	CE230100032
DOE BES	‐SC0023322

Keywords

Cu-based hydroxide
Ni-based hydroxide
X-ray absorption spectroscopy
electron and proton transfer processes
structural evolution
urea electrooxidation

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Yang, Y., Yuwono, J. A., Whittaker, T., Ibáñez, M. M., Wang, B., Kim, C., Borisevich, A. Y., Chua, S., Prada, J. P., Wang, X., Autran, P. O., Unocic, R. R., Dai, L., Holewinski, A., & Bedford, N. M. (2024). Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products. Advanced Materials, 36(35), Article 2403187. https://doi.org/10.1002/adma.202403187

@article{e646de2b56fd48978e5ca8fac95e2ba1,

title = "Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products",

abstract = "Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure-selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N2, reaching a current density of 20 mA cmgeo−2 at 1.04 V – 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in-situ spectroscopies and scattering experiments reveal a unique in situ generated Cu(2-x)+-OO−• active sites in CuCo, which initiates nucleophilic substitution of NH2 from the amide, leading to N-N coupling between *NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high-valence Ni3+ and Ni4+, which facilitates N-H activation. This process, in conjunction with the excessive accumulation of OH− ions on Jahn-Teller (JT) distorted Co sites, leads to the generation of NO2− as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.",

keywords = "Cu-based hydroxide, Ni-based hydroxide, X-ray absorption spectroscopy, electron and proton transfer processes, structural evolution, urea electrooxidation",

author = "Yuwei Yang and Yuwono, {Jodie A.} and Todd Whittaker and Ib{\'a}{\~n}ez, {Marc Many{\'e}} and Bingliang Wang and Changmin Kim and Borisevich, {Albina Y.} and Stephanie Chua and Prada, {Jhair Pena} and Xichu Wang and Autran, {Pierre Olivier} and Unocic, {Raymond R.} and Liming Dai and Adam Holewinski and Bedford, {Nicholas M.}",

note = "Publisher Copyright: {\textcopyright} 2024 The Author(s). Advanced Materials published by Wiley-VCH GmbH.",

year = "2024",

month = aug,

day = "28",

doi = "10.1002/adma.202403187",

language = "English",

volume = "36",

journal = "Advanced Materials",

issn = "0935-9648",

publisher = "wiley",

number = "35",

}

Yang, Y, Yuwono, JA, Whittaker, T, Ibáñez, MM, Wang, B, Kim, C, Borisevich, AY, Chua, S, Prada, JP, Wang, X, Autran, PO, Unocic, RR, Dai, L, Holewinski, A & Bedford, NM 2024, 'Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products', Advanced Materials, vol. 36, no. 35, 2403187. https://doi.org/10.1002/adma.202403187

TY - JOUR

T1 - Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products

AU - Yang, Yuwei

AU - Yuwono, Jodie A.

AU - Whittaker, Todd

AU - Ibáñez, Marc Manyé

AU - Wang, Bingliang

AU - Kim, Changmin

AU - Borisevich, Albina Y.

AU - Chua, Stephanie

AU - Prada, Jhair Pena

AU - Wang, Xichu

AU - Autran, Pierre Olivier

AU - Unocic, Raymond R.

AU - Dai, Liming

AU - Holewinski, Adam

AU - Bedford, Nicholas M.

PY - 2024/8/28

Y1 - 2024/8/28

N2 - Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure-selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N2, reaching a current density of 20 mA cmgeo−2 at 1.04 V – 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in-situ spectroscopies and scattering experiments reveal a unique in situ generated Cu(2-x)+-OO−• active sites in CuCo, which initiates nucleophilic substitution of NH2 from the amide, leading to N-N coupling between *NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high-valence Ni3+ and Ni4+, which facilitates N-H activation. This process, in conjunction with the excessive accumulation of OH− ions on Jahn-Teller (JT) distorted Co sites, leads to the generation of NO2− as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.

AB - Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure-selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N2, reaching a current density of 20 mA cmgeo−2 at 1.04 V – 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in-situ spectroscopies and scattering experiments reveal a unique in situ generated Cu(2-x)+-OO−• active sites in CuCo, which initiates nucleophilic substitution of NH2 from the amide, leading to N-N coupling between *NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high-valence Ni3+ and Ni4+, which facilitates N-H activation. This process, in conjunction with the excessive accumulation of OH− ions on Jahn-Teller (JT) distorted Co sites, leads to the generation of NO2− as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.

KW - Cu-based hydroxide

KW - Ni-based hydroxide

KW - X-ray absorption spectroscopy

KW - electron and proton transfer processes

KW - structural evolution

KW - urea electrooxidation

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U2 - 10.1002/adma.202403187

DO - 10.1002/adma.202403187

M3 - Article

AN - SCOPUS:85198381371

SN - 0935-9648

VL - 36

JO - Advanced Materials

JF - Advanced Materials

IS - 35

M1 - 2403187

ER -

Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products

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