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 journalArticlepeer-review

8 Citations (Scopus)
4 Downloads (Pure)

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 languageEnglish
Pages (from-to)19972-19983
Number of pages12
JournalInternational Journal of Hydrogen Energy
Volume48
Issue number52
Early online date3 Mar 2023
DOIs
Publication statusPublished - 22 Jun 2023

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