Modulating the Leverage Relationship in Nitrogen Fixation Through Hydrogen-Bond-Regulated Proton Transfer

Shaoce Zhang; Hu Hong; Rong Zhang; Zhiquan Wei; Yiqiao Wang; Dong Chen; Chuan Li; Pei Li; Huilin Cui; Yue Hou; Shengnan Wang; Johnny C. Ho; Ying Guo; Zhaodong Huang; Chunyi Zhi

doi:10.1002/anie.202412830

Modulating the Leverage Relationship in Nitrogen Fixation Through Hydrogen-Bond-Regulated Proton Transfer

Shaoce Zhang (Co-first Author), Hu Hong (Co-first Author), Rong Zhang, Zhiquan Wei, Yiqiao Wang, Dong Chen, Chuan Li, Pei Li, Huilin Cui, Yue Hou, Shengnan Wang, Johnny C. Ho, Ying Guo^*, Zhaodong Huang, Chunyi Zhi^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

12 Citations (Scopus)

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Abstract

In the electrochemical nitrogen reduction reaction (NRR), a leverage relationship exists between NH₃-producing activity and selectivity because of the competing hydrogen evolution reaction (HER), which means that high activity with strong protons adsorption causes low product selectivity. Herein, we design a novel metal-organic hydrogen bonding framework (MOHBF) material to modulate this leverage relationship by a hydrogen-bond-regulated proton transfer pathway. The MOHBF material was composited with reduced graphene oxide (rGO) to form a Ni-N₂O₂ molecular catalyst (Ni-N₂O₂/rGO). The unique structure of O atoms in Ni-O-C and N-O-H could form hydrogen bonds with H₂O molecules to interfere with protons being directly adsorbed onto Ni active sites, thus regulating the proton transfer mechanism and slowing the HER kinetics, thereby modulating the leverage relationship. Moreover, this catalyst has abundant Ni-single-atom sites enriched with Ni-N/O coordination, conducive to the adsorption and activation of N₂. The Ni-N₂O₂/rGO exhibits simultaneously enhanced activity and selectivity of NH₃ production with a maximum NH₃ yield rate of 209.7 μg h^-1 mg_cat.^-1 and a Faradaic efficiency of 45.7 %, outperforming other reported single-atom NRR catalysts.

© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Original language	English
Article number	e202412830
Number of pages	8
Journal	Angewandte Chemie (International Edition)
Volume	64
Issue number	1
Online published	19 Aug 2024
DOIs	https://doi.org/10.1002/anie.202412830
Publication status	Published - 2 Jan 2025

Funding

This work is supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region, China [Project No. T23-713/22-R] and InnoHK Project on [Project 1.3-Flexible and Stretchable Technologies (FAST) for monitoring of CVD risk factors: Sensing and Applications] at Hong Kong Centre for Cerebro-cardiovascular Health Engineering (COCHE). BL11B is acknowledged for its support in measurements and data analyses.

UN SDGs

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

SDG 7 Affordable and Clean Energy

Research Keywords

electrochemical nitrogen reduction reaction
leverage relationship
hydrogen bond
proton transfer
molecular catalyst

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This full text is made available under CC-BY 4.0. https://creativecommons.org/licenses/by/4.0/

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RGC-funded

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10.1002/anie.202412830

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@article{0737bc54391a45c9a6ef626251d038cd,

title = "Modulating the Leverage Relationship in Nitrogen Fixation Through Hydrogen-Bond-Regulated Proton Transfer",

abstract = "In the electrochemical nitrogen reduction reaction (NRR), a leverage relationship exists between NH3-producing activity and selectivity because of the competing hydrogen evolution reaction (HER), which means that high activity with strong protons adsorption causes low product selectivity. Herein, we design a novel metal-organic hydrogen bonding framework (MOHBF) material to modulate this leverage relationship by a hydrogen-bond-regulated proton transfer pathway. The MOHBF material was composited with reduced graphene oxide (rGO) to form a Ni-N2O2 molecular catalyst (Ni-N2O2/rGO). The unique structure of O atoms in Ni-O-C and N-O-H could form hydrogen bonds with H2O molecules to interfere with protons being directly adsorbed onto Ni active sites, thus regulating the proton transfer mechanism and slowing the HER kinetics, thereby modulating the leverage relationship. Moreover, this catalyst has abundant Ni-single-atom sites enriched with Ni-N/O coordination, conducive to the adsorption and activation of N2. The Ni-N2O2/rGO exhibits simultaneously enhanced activity and selectivity of NH3 production with a maximum NH3 yield rate of 209.7 μg h-1 mgcat.-1 and a Faradaic efficiency of 45.7 %, outperforming other reported single-atom NRR catalysts.{\textcopyright} 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

keywords = "electrochemical nitrogen reduction reaction, leverage relationship, hydrogen bond, proton transfer, molecular catalyst",

author = "Shaoce Zhang and Hu Hong and Rong Zhang and Zhiquan Wei and Yiqiao Wang and Dong Chen and Chuan Li and Pei Li and Huilin Cui and Yue Hou and Shengnan Wang and Ho, {Johnny C.} and Ying Guo and Zhaodong Huang and Chunyi Zhi",

year = "2025",

month = jan,

day = "2",

doi = "10.1002/anie.202412830",

language = "English",

volume = "64",

journal = "Angewandte Chemie (International Edition)",

issn = "1433-7851",

publisher = "John Wiley & Sons",

number = "1",

}

Modulating the Leverage Relationship in Nitrogen Fixation Through Hydrogen-Bond-Regulated Proton Transfer. / Zhang, Shaoce (Co-first Author); Hong, Hu (Co-first Author); Zhang, Rong et al.
In: Angewandte Chemie (International Edition), Vol. 64, No. 1, e202412830, 02.01.2025.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Modulating the Leverage Relationship in Nitrogen Fixation Through Hydrogen-Bond-Regulated Proton Transfer

AU - Zhang, Shaoce

AU - Hong, Hu

AU - Zhang, Rong

AU - Wei, Zhiquan

AU - Wang, Yiqiao

AU - Chen, Dong

AU - Li, Chuan

AU - Li, Pei

AU - Cui, Huilin

AU - Hou, Yue

AU - Wang, Shengnan

AU - Ho, Johnny C.

AU - Guo, Ying

AU - Huang, Zhaodong

AU - Zhi, Chunyi

PY - 2025/1/2

Y1 - 2025/1/2

N2 - In the electrochemical nitrogen reduction reaction (NRR), a leverage relationship exists between NH3-producing activity and selectivity because of the competing hydrogen evolution reaction (HER), which means that high activity with strong protons adsorption causes low product selectivity. Herein, we design a novel metal-organic hydrogen bonding framework (MOHBF) material to modulate this leverage relationship by a hydrogen-bond-regulated proton transfer pathway. The MOHBF material was composited with reduced graphene oxide (rGO) to form a Ni-N2O2 molecular catalyst (Ni-N2O2/rGO). The unique structure of O atoms in Ni-O-C and N-O-H could form hydrogen bonds with H2O molecules to interfere with protons being directly adsorbed onto Ni active sites, thus regulating the proton transfer mechanism and slowing the HER kinetics, thereby modulating the leverage relationship. Moreover, this catalyst has abundant Ni-single-atom sites enriched with Ni-N/O coordination, conducive to the adsorption and activation of N2. The Ni-N2O2/rGO exhibits simultaneously enhanced activity and selectivity of NH3 production with a maximum NH3 yield rate of 209.7 μg h-1 mgcat.-1 and a Faradaic efficiency of 45.7 %, outperforming other reported single-atom NRR catalysts.© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

AB - In the electrochemical nitrogen reduction reaction (NRR), a leverage relationship exists between NH3-producing activity and selectivity because of the competing hydrogen evolution reaction (HER), which means that high activity with strong protons adsorption causes low product selectivity. Herein, we design a novel metal-organic hydrogen bonding framework (MOHBF) material to modulate this leverage relationship by a hydrogen-bond-regulated proton transfer pathway. The MOHBF material was composited with reduced graphene oxide (rGO) to form a Ni-N2O2 molecular catalyst (Ni-N2O2/rGO). The unique structure of O atoms in Ni-O-C and N-O-H could form hydrogen bonds with H2O molecules to interfere with protons being directly adsorbed onto Ni active sites, thus regulating the proton transfer mechanism and slowing the HER kinetics, thereby modulating the leverage relationship. Moreover, this catalyst has abundant Ni-single-atom sites enriched with Ni-N/O coordination, conducive to the adsorption and activation of N2. The Ni-N2O2/rGO exhibits simultaneously enhanced activity and selectivity of NH3 production with a maximum NH3 yield rate of 209.7 μg h-1 mgcat.-1 and a Faradaic efficiency of 45.7 %, outperforming other reported single-atom NRR catalysts.© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

KW - electrochemical nitrogen reduction reaction

KW - leverage relationship

KW - hydrogen bond

KW - proton transfer

KW - molecular catalyst

UR - https://www.webofscience.com/wos/woscc/full-record/WOS:001333667500001

U2 - 10.1002/anie.202412830

DO - 10.1002/anie.202412830

M3 - RGC 21 - Publication in refereed journal

SN - 1433-7851

VL - 64

JO - Angewandte Chemie (International Edition)

JF - Angewandte Chemie (International Edition)

IS - 1

M1 - e202412830

ER -

Modulating the Leverage Relationship in Nitrogen Fixation Through Hydrogen-Bond-Regulated Proton Transfer

Abstract

Funding

UN SDGs

Research Keywords

Publisher's Copyright Statement

RGC Funding Information

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TBRS-ExtU-Lead: Towards Carbon Neutrality: Catalysing H2O and CO2 to Green Resource Carriers

Cite this

Modulating the Leverage Relationship in Nitrogen Fixation Through Hydrogen-Bond-Regulated Proton Transfer

Abstract

Funding

UN SDGs

Research Keywords

Publisher's Copyright Statement

RGC Funding Information

Access Output

Other Access Options

Permanent Link

Other Files and Links

Fingerprint

Projects

TBRS-ExtU-Lead: Towards Carbon Neutrality: Catalysing H2O and CO2 to Green Resource Carriers

Cite this