Highly Efficient Electrochemical Reduction of Nitrogen to Ammonia on Surface Termination Modified Ti3C2Tx MXene Nanosheets

Ying GUO; Tairan WANG; Qi YANG; Xinliang LI; Hongfei LI; Yukun WANG; Tianpeng JIAO; Zhaodong HUANG; Binbin DONG; Wenjun ZHANG; Jun FAN; Chunyi ZHI

doi:10.1021/acsnano.0c04284

Highly Efficient Electrochemical Reduction of Nitrogen to Ammonia on Surface Termination Modified Ti₃C₂T_xMXene Nanosheets

Ying GUO, Tairan WANG, Qi YANG, Xinliang LI, Hongfei LI, Yukun WANG, Tianpeng JIAO, Zhaodong HUANG, Binbin DONG, Wenjun ZHANG, Jun FAN, Chunyi ZHI^*

^*Corresponding author for this work

Research output: Journal Publications › Journal Article (refereed) › peer-review

163 Citations (Scopus)

Abstract

MXene-based catalysts exhibit extraordinary advantages for many catalysis reactions, such as the hydrogen evolution and oxygen reduction reactions. However, MXenes exhibit inadequate catalytic activity for the electrochemical nitrogen reduction reaction (NRR) because they are typically terminated with inactive functional groups, F* and OH*, which mask the active metal sites for N₂ binding. Here we modified the surface termination of MXene (Ti₃C₂T_x) nanosheets to achieve high surface catalytic reactivity for the NRR by ironing out inactive F*/OH* terminals to expose more active sites and by introducing Fe to greatly reduce the surface work function. The optimally performing catalyst (MXene/TiFeO_x-700) achieved excellent Faradaic efficiency of 25.44% and an NH₃ yield rate of 2.19 μg/cm²·h (21.9 μg/mg_cat·h), outperforming all reported MXene-based NRR catalysts. Our work provides a feasible strategy for rationally improving the surface reactivity of MXene-based catalysts for efficient electrochemical conversion of N₂ to NH₃.

Original language	English
Pages (from-to)	9089-9097
Number of pages	9
Journal	ACS Nano
Volume	14
Issue number	7
Early online date	18 Jun 2020
DOIs	https://doi.org/10.1021/acsnano.0c04284
Publication status	Published - 28 Jul 2020
Externally published	Yes

Bibliographical note

We thank Dr. M. K. TSE from Department of Chemistry of City University of Hong Kong for NMR measurements.

Funding

The authors acknowledge funding from the GRF Scheme under Project CityU 11305218 and the Science Technology and Innovation Committee of Shenzhen Municipality (Grant No. JCYJ20170818103435068) and a grant from City University of Hong Kong (Grant No. 9667165).

Keywords

electrochemical nitrogen reduction
inactive terminals
MXene nanosheets
surface catalytic reactivity
surface work function

Access to Document

10.1021/acsnano.0c04284

Cite this

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title = "Highly Efficient Electrochemical Reduction of Nitrogen to Ammonia on Surface Termination Modified Ti3C2Tx MXene Nanosheets",

abstract = " MXene-based catalysts exhibit extraordinary advantages for many catalysis reactions, such as the hydrogen evolution and oxygen reduction reactions. However, MXenes exhibit inadequate catalytic activity for the electrochemical nitrogen reduction reaction (NRR) because they are typically terminated with inactive functional groups, F* and OH*, which mask the active metal sites for N2 binding. Here we modified the surface termination of MXene (Ti3C2Tx) nanosheets to achieve high surface catalytic reactivity for the NRR by ironing out inactive F*/OH* terminals to expose more active sites and by introducing Fe to greatly reduce the surface work function. The optimally performing catalyst (MXene/TiFeOx-700) achieved excellent Faradaic efficiency of 25.44% and an NH3 yield rate of 2.19 μg/cm2·h (21.9 μg/mgcat·h), outperforming all reported MXene-based NRR catalysts. Our work provides a feasible strategy for rationally improving the surface reactivity of MXene-based catalysts for efficient electrochemical conversion of N2 to NH3. ",

keywords = "electrochemical nitrogen reduction, inactive terminals, MXene nanosheets, surface catalytic reactivity, surface work function",

author = "Ying GUO and Tairan WANG and Qi YANG and Xinliang LI and Hongfei LI and Yukun WANG and Tianpeng JIAO and Zhaodong HUANG and Binbin DONG and Wenjun ZHANG and Jun FAN and Chunyi ZHI",

note = "We thank Dr. M. K. TSE from Department of Chemistry of City University of Hong Kong for NMR measurements.",

year = "2020",

month = jul,

day = "28",

doi = "10.1021/acsnano.0c04284",

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T1 - Highly Efficient Electrochemical Reduction of Nitrogen to Ammonia on Surface Termination Modified Ti3C2Tx MXene Nanosheets

AU - GUO, Ying

AU - WANG, Tairan

AU - YANG, Qi

AU - LI, Xinliang

AU - LI, Hongfei

AU - WANG, Yukun

AU - JIAO, Tianpeng

AU - HUANG, Zhaodong

AU - DONG, Binbin

AU - ZHANG, Wenjun

AU - FAN, Jun

AU - ZHI, Chunyi

N1 - We thank Dr. M. K. TSE from Department of Chemistry of City University of Hong Kong for NMR measurements.

PY - 2020/7/28

Y1 - 2020/7/28

N2 - MXene-based catalysts exhibit extraordinary advantages for many catalysis reactions, such as the hydrogen evolution and oxygen reduction reactions. However, MXenes exhibit inadequate catalytic activity for the electrochemical nitrogen reduction reaction (NRR) because they are typically terminated with inactive functional groups, F* and OH*, which mask the active metal sites for N2 binding. Here we modified the surface termination of MXene (Ti3C2Tx) nanosheets to achieve high surface catalytic reactivity for the NRR by ironing out inactive F*/OH* terminals to expose more active sites and by introducing Fe to greatly reduce the surface work function. The optimally performing catalyst (MXene/TiFeOx-700) achieved excellent Faradaic efficiency of 25.44% and an NH3 yield rate of 2.19 μg/cm2·h (21.9 μg/mgcat·h), outperforming all reported MXene-based NRR catalysts. Our work provides a feasible strategy for rationally improving the surface reactivity of MXene-based catalysts for efficient electrochemical conversion of N2 to NH3.

AB - MXene-based catalysts exhibit extraordinary advantages for many catalysis reactions, such as the hydrogen evolution and oxygen reduction reactions. However, MXenes exhibit inadequate catalytic activity for the electrochemical nitrogen reduction reaction (NRR) because they are typically terminated with inactive functional groups, F* and OH*, which mask the active metal sites for N2 binding. Here we modified the surface termination of MXene (Ti3C2Tx) nanosheets to achieve high surface catalytic reactivity for the NRR by ironing out inactive F*/OH* terminals to expose more active sites and by introducing Fe to greatly reduce the surface work function. The optimally performing catalyst (MXene/TiFeOx-700) achieved excellent Faradaic efficiency of 25.44% and an NH3 yield rate of 2.19 μg/cm2·h (21.9 μg/mgcat·h), outperforming all reported MXene-based NRR catalysts. Our work provides a feasible strategy for rationally improving the surface reactivity of MXene-based catalysts for efficient electrochemical conversion of N2 to NH3.

KW - electrochemical nitrogen reduction

KW - inactive terminals

KW - MXene nanosheets

KW - surface catalytic reactivity

KW - surface work function

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DO - 10.1021/acsnano.0c04284

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