Volume 63, Issue 14 e202317167

Research Article

Descriptor-Based Volcano Relations Predict Single Atoms for Hydroxylamine Electrosynthesis

Rong Yang,

Rong Yang

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

These authors contributed equally to this work.

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Dr. Yuting Wang,

Dr. Yuting Wang

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

These authors contributed equally to this work.

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Hongjiao Li,

Hongjiao Li

School of Chemical Engineering, Sichuan University, Chengdu, 610065 Sichuan, China

These authors contributed equally to this work.

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Jin Zhou,

Jin Zhou

School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China

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Zeyuan Gao,

Zeyuan Gao

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

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Dr. Cuibo Liu,

Dr. Cuibo Liu

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

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Prof. Bin Zhang,

Corresponding Author

Prof. Bin Zhang

[email protected]

orcid.org/0000-0003-0542-1819

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Frontiers Science Center for Synthetic Biology (Ministry of Education), Tianjin, 300192 China

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Rong Yang,

Rong Yang

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

These authors contributed equally to this work.

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Dr. Yuting Wang,

Dr. Yuting Wang

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

These authors contributed equally to this work.

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Hongjiao Li,

Hongjiao Li

School of Chemical Engineering, Sichuan University, Chengdu, 610065 Sichuan, China

These authors contributed equally to this work.

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Jin Zhou,

Jin Zhou

School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072 China

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Zeyuan Gao,

Zeyuan Gao

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

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Dr. Cuibo Liu,

Dr. Cuibo Liu

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

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Prof. Bin Zhang,

Corresponding Author

Prof. Bin Zhang

[email protected]

orcid.org/0000-0003-0542-1819

Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072 China

Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Frontiers Science Center for Synthetic Biology (Ministry of Education), Tianjin, 300192 China

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First published: 07 February 2024

https://doi.org/10.1002/anie.202317167

Citations: 23

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Graphical Abstract

A weak *NH₂OH binding affinity and a favorable reaction pathway (*NHO pathway) jointly enable single-atom catalysts (SACs) with superior hydroxylamine (NH₂OH) selectivity. Then, an activity volcano plot of G_ad(*NHO) is established to predict Mn SACs as optimal electrocatalysts that exhibit pH-dependent activity. Furthermore, Mn−Co geminal-atom catalysts are predicted to optimize G_ad(*NHO) and are experimentally proven to enhance NH₂OH formation.

Abstract

Hydroxylamine (NH₂OH) is an important feedstock in fuels, pharmaceuticals, and agrochemicals. Nanostructured electrocatalysts drive green electrosynthesis of hydroxylamine from nitrogen oxide species in water. However, current electrocatalysts still suffer from low selectivity and manpower-consuming trial-and-error modes, leaving unclear selectivity/activity origins and a lack of catalyst design principles. Herein, we theoretically analyze key determinants of selectivity/activity and propose the adsorption energy of NHO (G_ad(*NHO)) as a performance descriptor. A weak *NH₂OH binding affinity and a favorable reaction pathway (*NHO pathway) jointly enable single-atom catalysts (SACs) with superior NH₂OH selectivity. Then, an activity volcano plot of G_ad(*NHO) is established to predict a series of SACs and discover Mn SACs as optimal electrocatalysts that exhibit pH-dependent activity. These theoretical prediction results are also confirmed by experimental results, rationalizing our G_ad(*NHO) descriptor. Furthermore, Mn−Co geminal-atom catalysts (GACs) are predicted to optimize G_ad(*NHO) and are experimentally proved to enhance NH₂OH formation.

Conflict of interests

The authors declare no conflict of interest.

Open Research

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Supporting Information

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Volume63, Issue14

April 2, 2024

e202317167

Descriptor-Based Volcano Relations Predict Single Atoms for Hydroxylamine Electrosynthesis

Graphical Abstract

Abstract

Conflict of interests

Open Research

Data Availability Statement

Supporting Information

References

Citing Literature

References

Information

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Descriptor-Based Volcano Relations Predict Single Atoms for Hydroxylamine Electrosynthesis

Graphical Abstract

Abstract

Conflict of interests

Open Research

Data Availability Statement

Supporting Information

References

Citing Literature

References

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