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 - http://www.scopus.com/inward/record.url?scp=85149744566&partnerID=8YFLogxK
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 -
