N-2 electrochemical reduction on two dimensional transition metal monoborides: A density functional theory study
N-2 electrochemical reduction on two dimensional transition metal monoborides: A density functional theory study
复制标题
二维过渡金属硼化物上的 N-2 电化学还原：密度泛函理论研究
DOI：
10.1002/qua.26548
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发表时间：
2021
影响因子：
2.2
通讯作者：
Sun Qiao
中科院分区：
文献类型：
--
作者：
Xu Shaohua;Qin Gangqiang;Jiang Quan;Cui Qianyi;Du Aijun;Zhao Chongjun;Sun Qiao
N2在环境条件下的电化学还原正在成为一种有前途的途径，并且可以由可持续能源提供动力。大的过电位和竞争析氢反应（HER）是与N2还原相关的两个主要问题。因此，开发具有低过电位的高效电催化剂对电化学氮还原反应（NRR）具有重要意义。在这项理论研究中，我们报告了一个有价值的见解对一个新的二维（2D）过渡金属一硼化物（TMB）材料具有高效的电催化剂应用NRR，研究了密度泛函理论方法。通过系统研究N2在不同TMB（TM = Cr，Mn，Fe，Co，Ni和Mo）纳米片上的吸附吉布斯自由能，以及N2 H和NH 2物种在这些催化剂上的吸附能，发现MoB纳米片可能是NRR电催化剂的最佳选择。此外，我们的结果还表明，通过酶促途径在MoB纳米片上的NRR是最有利的途径，*NH*NH → *NH* NH 2是具有0.14 V的非常低的施加过电位的电位限制步骤。此外，NRR（-0.30 V）和HER（-0.48 V）在MoB纳米片上的极限电位表明NRR更倾向于发生在催化剂上。总体而言，这项研究表明，MoB纳米片作为一种新型的二维单层，这可能是一个有效的电催化剂NRR在环境条件下。
Electrochemical reduction of N2at ambient conditions is emerging as a promising route and can be powered by sustainable energies. Large overpotential and the competing hydrogen evolution reaction (HER) are the two major issues associated with the N2reduction. Thus, the development of efficient electrocatalysts with low overpotential is of utmost significance for electrochemical nitrogen reduction reaction (NRR). In this theoretical study, we report a valuable insight toward a novel two dimensional (2D) transition metal monoboride (TMB) material possessing efficient electrocatalysts application for NRR, investigated by density functional theory method. Through systematically exploring the Gibbs free energy of N2adsorption on the different TMB (TM = Cr, Mn, Fe, Co, Ni and Mo) nanosheets and analyzing adsorption energy of N2H and NH2species on these catalysts, we found MoB nanosheets may be the optimum choice as an electrocatalyst for NRR. Moreover, our results also indicate that NRR on MoB nanosheets via the enzymatic pathway is the most favored pathway and *NH*NH → *NH*NH2is potential‐limiting step with a very low applied overpotential of 0.14 V. In addition, the limiting potentials of NRR (−0.30 V) and HER (−0.48 V) on MoB nanosheet suggest that NRR is prefer to happen on the catalyst. Overall, this study demonstrates that MoB nanosheets as a novel 2D monolayer, which might be utilized as an efficient electrocatalyst for NRR at ambient conditions.