Molybdenum Based 2D Conductive Metal–Organic Frameworks as Efficient Single-atom Electrocatalysts for N2 Reduction: A Density Functional Theory Study

Yongxiu Sun; Wenwu Shi; Mengxuan Sun; Qisheng Fang; Xiaohe Ren; Yijun Yan; Ziwei Gan; Yongqing Fu; Ahmed Elmarakbi; Zhijie Li; Zhiguo Wang

doi:10.1016/j.ijhydene.2023.02.039

Molybdenum Based 2D Conductive Metal–Organic Frameworks as Efficient Single-atom Electrocatalysts for N2 Reduction: A Density Functional Theory Study

Yongxiu Sun, Wenwu Shi, Mengxuan Sun, Qisheng Fang, Xiaohe Ren, Yijun Yan, Ziwei Gan, Yongqing Fu, Ahmed Elmarakbi, Zhijie Li^*, Zhiguo Wang^*

^*Corresponding author for this work

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

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Abstract

Electrocatalytic nitrogen reduction reaction (NRR) is a sustainable and eco-friendly process to generate ammonia (NH ₃). However, there are significant challenges including low catalytic performance, instability, and poor selectivity, which hinder its rapid development. Herein, a series of two-dimensional (2D) conductive metal-organic frameworks (i.e., TM ₃(HHTT) ₂, TM = Sc, Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu and Zn) are investigated as single-atom catalysts (SACs) for NRR process by the density functional theory (DFT). The obtained results of Gibbs free energies of adsorption for N ₂, ∗NNH, ∗NH ₃, which are commonly used as activity descriptors to screen the effectiveness of catalysts, show that the Mo ₃(HHTT) ₂ monolayer (among all the TM ₃(HHTT) ₂ ones) can activate N[tbnd]N bonds, stabilize the adsorbed ∗NNH, and achieve the desorption of NH ₃. The Mo ₃(HHTT) ₂ monolayer also exhibits an excellent structural stability (with values of E _f = −2.96 eV and U _diss = 1.28 V). N ₂ can be effectively reduced into NH ₃ on the Mo ₃(HHTT) ₂ monolayer with a low limiting potential of −0.60 V along the distal pathway. Furthermore, the σ-donation and π∗ back-donation of N ₂ adsorbed onto the Mo ₃(HHTT) ₂ monolayer indicates an excellent electrical conductivity of Mo ₃(HHTT) ₂, which is beneficial for the effective electron transfer during the NRR process. Furthermore, the Mo ₃(HHTT) ₂ monolayer exhibits considerable selectivity for the NRR process over the hydrogen evolution reaction. Our study proved that this 2D c-MOFs carrying TM of the Mo ₃(HHTT) ₂ monolayer can be used as a promising catalyst for nitrogen fixation.

Original language	English
Pages (from-to)	19972-19983
Number of pages	12
Journal	International Journal of Hydrogen Energy
Volume	48
Issue number	52
Early online date	3 Mar 2023
DOIs	https://doi.org/10.1016/j.ijhydene.2023.02.039
Publication status	Published - 22 Jun 2023

UN SDGs

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

SDG 7 Affordable and Clean Energy

Keywords

single-atom catalysts
metal-organic frameworks
density functional theory
nitrogen reduction reaction

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10.1016/j.ijhydene.2023.02.039

Accepted Manuscript Int J Hydrogen EnergyAccepted author manuscript, 1.43 MBLicence: CC BY-NC-ND

Cite this

Sun, Y., Shi, W., Sun, M., Fang, Q., Ren, X., Yan, Y., Gan, Z., Fu, Y., Elmarakbi, A., Li, Z., & Wang, Z. (2023). Molybdenum Based 2D Conductive Metal–Organic Frameworks as Efficient Single-atom Electrocatalysts for N2 Reduction: A Density Functional Theory Study. International Journal of Hydrogen Energy, 48(52), 19972-19983. https://doi.org/10.1016/j.ijhydene.2023.02.039

@article{e4495e8907434b5eb9c1270565f321c2,

title = "Molybdenum Based 2D Conductive Metal–Organic Frameworks as Efficient Single-atom Electrocatalysts for N2 Reduction: A Density Functional Theory Study",

abstract = "Electrocatalytic nitrogen reduction reaction (NRR) is a sustainable and eco-friendly process to generate ammonia (NH 3). However, there are significant challenges including low catalytic performance, instability, and poor selectivity, which hinder its rapid development. Herein, a series of two-dimensional (2D) conductive metal-organic frameworks (i.e., TM 3(HHTT) 2, TM = Sc, Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu and Zn) are investigated as single-atom catalysts (SACs) for NRR process by the density functional theory (DFT). The obtained results of Gibbs free energies of adsorption for N 2, ∗NNH, ∗NH 3, which are commonly used as activity descriptors to screen the effectiveness of catalysts, show that the Mo 3(HHTT) 2 monolayer (among all the TM 3(HHTT) 2 ones) can activate N[tbnd]N bonds, stabilize the adsorbed ∗NNH, and achieve the desorption of NH 3. The Mo 3(HHTT) 2 monolayer also exhibits an excellent structural stability (with values of E f = −2.96 eV and U diss = 1.28 V). N 2 can be effectively reduced into NH 3 on the Mo 3(HHTT) 2 monolayer with a low limiting potential of −0.60 V along the distal pathway. Furthermore, the σ-donation and π∗ back-donation of N 2 adsorbed onto the Mo 3(HHTT) 2 monolayer indicates an excellent electrical conductivity of Mo 3(HHTT) 2, which is beneficial for the effective electron transfer during the NRR process. Furthermore, the Mo 3(HHTT) 2 monolayer exhibits considerable selectivity for the NRR process over the hydrogen evolution reaction. Our study proved that this 2D c-MOFs carrying TM of the Mo 3(HHTT) 2 monolayer can be used as a promising catalyst for nitrogen fixation.",

keywords = "single-atom catalysts, metal-organic frameworks, density functional theory, nitrogen reduction reaction",

author = "Yongxiu Sun and Wenwu Shi and Mengxuan Sun and Qisheng Fang and Xiaohe Ren and Yijun Yan and Ziwei Gan and Yongqing Fu and Ahmed Elmarakbi and Zhijie Li and Zhiguo Wang",

note = "Funding information: This work was supported by International Exchange Grant (IEC/NSFC/201078) through the National Natural Science Foundation of China and Royal Society UK.",

year = "2023",

month = jun,

day = "22",

doi = "10.1016/j.ijhydene.2023.02.039",

language = "English",

volume = "48",

pages = "19972--19983",

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issn = "0360-3199",

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number = "52",

}

Sun, Y, Shi, W, Sun, M, Fang, Q, Ren, X, Yan, Y, Gan, Z, Fu, Y , Elmarakbi, A, Li, Z & Wang, Z 2023, 'Molybdenum Based 2D Conductive Metal–Organic Frameworks as Efficient Single-atom Electrocatalysts for N2 Reduction: A Density Functional Theory Study', International Journal of Hydrogen Energy, vol. 48, no. 52, pp. 19972-19983. https://doi.org/10.1016/j.ijhydene.2023.02.039

TY - JOUR

T1 - Molybdenum Based 2D Conductive Metal–Organic Frameworks as Efficient Single-atom Electrocatalysts for N2 Reduction

T2 - A Density Functional Theory Study

AU - Sun, Yongxiu

AU - Shi, Wenwu

AU - Sun, Mengxuan

AU - Fang, Qisheng

AU - Ren, Xiaohe

AU - Yan, Yijun

AU - Gan, Ziwei

AU - Fu, Yongqing

AU - Elmarakbi, Ahmed

AU - Li, Zhijie

AU - Wang, Zhiguo

N1 - Funding information: This work was supported by International Exchange Grant (IEC/NSFC/201078) through the National Natural Science Foundation of China and Royal Society UK.

PY - 2023/6/22

Y1 - 2023/6/22

N2 - Electrocatalytic nitrogen reduction reaction (NRR) is a sustainable and eco-friendly process to generate ammonia (NH 3). However, there are significant challenges including low catalytic performance, instability, and poor selectivity, which hinder its rapid development. Herein, a series of two-dimensional (2D) conductive metal-organic frameworks (i.e., TM 3(HHTT) 2, TM = Sc, Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu and Zn) are investigated as single-atom catalysts (SACs) for NRR process by the density functional theory (DFT). The obtained results of Gibbs free energies of adsorption for N 2, ∗NNH, ∗NH 3, which are commonly used as activity descriptors to screen the effectiveness of catalysts, show that the Mo 3(HHTT) 2 monolayer (among all the TM 3(HHTT) 2 ones) can activate N[tbnd]N bonds, stabilize the adsorbed ∗NNH, and achieve the desorption of NH 3. The Mo 3(HHTT) 2 monolayer also exhibits an excellent structural stability (with values of E f = −2.96 eV and U diss = 1.28 V). N 2 can be effectively reduced into NH 3 on the Mo 3(HHTT) 2 monolayer with a low limiting potential of −0.60 V along the distal pathway. Furthermore, the σ-donation and π∗ back-donation of N 2 adsorbed onto the Mo 3(HHTT) 2 monolayer indicates an excellent electrical conductivity of Mo 3(HHTT) 2, which is beneficial for the effective electron transfer during the NRR process. Furthermore, the Mo 3(HHTT) 2 monolayer exhibits considerable selectivity for the NRR process over the hydrogen evolution reaction. Our study proved that this 2D c-MOFs carrying TM of the Mo 3(HHTT) 2 monolayer can be used as a promising catalyst for nitrogen fixation.

AB - Electrocatalytic nitrogen reduction reaction (NRR) is a sustainable and eco-friendly process to generate ammonia (NH 3). However, there are significant challenges including low catalytic performance, instability, and poor selectivity, which hinder its rapid development. Herein, a series of two-dimensional (2D) conductive metal-organic frameworks (i.e., TM 3(HHTT) 2, TM = Sc, Ti, V, Cr, Mo, W, Mn, Fe, Co, Ni, Cu and Zn) are investigated as single-atom catalysts (SACs) for NRR process by the density functional theory (DFT). The obtained results of Gibbs free energies of adsorption for N 2, ∗NNH, ∗NH 3, which are commonly used as activity descriptors to screen the effectiveness of catalysts, show that the Mo 3(HHTT) 2 monolayer (among all the TM 3(HHTT) 2 ones) can activate N[tbnd]N bonds, stabilize the adsorbed ∗NNH, and achieve the desorption of NH 3. The Mo 3(HHTT) 2 monolayer also exhibits an excellent structural stability (with values of E f = −2.96 eV and U diss = 1.28 V). N 2 can be effectively reduced into NH 3 on the Mo 3(HHTT) 2 monolayer with a low limiting potential of −0.60 V along the distal pathway. Furthermore, the σ-donation and π∗ back-donation of N 2 adsorbed onto the Mo 3(HHTT) 2 monolayer indicates an excellent electrical conductivity of Mo 3(HHTT) 2, which is beneficial for the effective electron transfer during the NRR process. Furthermore, the Mo 3(HHTT) 2 monolayer exhibits considerable selectivity for the NRR process over the hydrogen evolution reaction. Our study proved that this 2D c-MOFs carrying TM of the Mo 3(HHTT) 2 monolayer can be used as a promising catalyst for nitrogen fixation.

KW - single-atom catalysts

KW - metal-organic frameworks

KW - density functional theory

KW - nitrogen reduction reaction

UR - https://www.scopus.com/pages/publications/85149744566

U2 - 10.1016/j.ijhydene.2023.02.039

DO - 10.1016/j.ijhydene.2023.02.039

M3 - Article

SN - 0360-3199

VL - 48

SP - 19972

EP - 19983

JO - International Journal of Hydrogen Energy

JF - International Journal of Hydrogen Energy

IS - 52

ER -

Molybdenum Based 2D Conductive Metal–Organic Frameworks as Efficient Single-atom Electrocatalysts for N2 Reduction: A Density Functional Theory Study

Abstract

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Keywords

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