轨道对称性匹配: MXene基体上的单原子催化以实现优异的氮还原反应

doi:10.1016/S1872-2067(20)63643-9

摘要/Abstract

摘要：

氨作为一种可被植物直接吸收用以合成其他有机物的重要成分, 在化学化工及含氮化合物的生产当中起着至关重要的作用. 传统工业生产氨气采用Haber-Bosch工艺, 将空气中丰富的氮气转化为氨气, 但该工艺需要较高的压强和温度来促进氮气分解, 因此会消耗大量能源. 近年来, 电催化反应发展迅速. 在电催化工艺中, 通过控制操作电位及电解质便可提高生产效率, 降低能源消耗. 基于这种策略, 各种针对能源环境的催化研究应运而生, 如二氧化碳还原、水分解反应等. 其中, 对于氮还原的催化研究尤其是电催化设计领域研究相对较少. 研究发现, 在电催化剂中, 异构掺杂及原子尺度的调控可以极大地影响催化剂的催化活性. 其中, 单原子催化(SAC)因其在催化活性和催化选择性上的优势受到广泛关注. MXene是一种二维过渡金属碳化物或氮化物, 其优异的化学性能和稳定的表面构型可以对单原子起到良好的锚定与支撑作用, 是一种更具潜力的单原子催化基体. 本文基于上述思想, 利用密度泛函第一性原理等模拟软件, 设计并研究了以MXene为基体的28种过渡金属单原子催化体系, 计算并分析了各SAC@MXene体系对氮还原反应的催化效果, 从限制电势、催化路径、反应机制等方面探索了其催化性能. 并对体系进行了态密度、晶体轨道哈密顿量、差分电荷密度等电子结构分析, 找到了适用于MXene体系的单原子催化设计原则.
通过对限制电势的计算表明, Ni@MXene和Co@MXene体系具有很低的限制电势(-0.13和-0.17 V), 说明这些体系在较低的启动电压下即可发生氮还原反应. 研究发现了一种新型适用于SAC@MXene氮催化体系的酶促-远端反应机制. 电子结构分析得到SAC原子与MXene基体的Ti原子在催化过程中存在一种协同作用. 态密度及晶体轨道哈密顿量也显示出SAC原子与MXene基体Ti之间的一种轨道对称性匹配关系, 揭示了这种协同作用对催化反应的积极作用. 计算的氢析出反应(HER)结果也显示, 在相同化学环境下, SAC@MXene体系氮还原反应相对于氢析出反应更易发生.

关键词: 轨道对称性匹配, 单原子催化剂, 氮还原反应, MXene基体, 电位决速步

Abstract:

The nitrogen reduction reaction (NRR) under ambient conditions is still challenging due to the inertness of N₂. Herein, we report a series of superior NRR catalysts identified by examining Ti₂NO₂ MXenes embedded with 28 different single-atom catalysts using first-principles calculations. The stability of this system was first verified using formation energies, and it is discovered that N₂ can be effectively adsorbed due to the synergistic effect between single atom catalysis and the Ti atoms. Examination of the electronic structure demonstrated that this design satisfies orbital symmetry matching where “acceptor-donor” interaction scenario can be realized. A new “enzymatic-distal” reaction mechanism that is a mixture of the enzymatic and distal pathways was also discovered. Among all of the candidates, Ni anchored on MXene system achieves an onset potential as low as -0.13 V, which to the best of our knowledge is the lowest onset potential value reported to date. This work elucidates the significance of orbital symmetry matching and provides theoretical guidance for future studies.

Key words: Orbital symmetry matching, Single atom catalysis, Nitrogen reduction reaction, MXene substrate, Potential determining step

曲家乐, 肖杰文, 陈和田, 刘晓鹏, 王天帅, 张千帆. 轨道对称性匹配: MXene基体上的单原子催化以实现优异的氮还原反应[J]. 催化学报, 2021, 42(2): 288-296.

Jiale Qu, Jiewen Xiao, Hetian Chen, Xiaopeng Liu, Tianshuai Wang, Qianfan Zhang. Orbital symmetry matching: Achieving superior nitrogen reduction reaction over single-atom catalysts anchored on Mxene substrates[J]. Chinese Journal of Catalysis, 2021, 42(2): 288-296.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63643-9

https://www.cjcatal.com/CN/Y2021/V42/I2/288

图/表 5

Fig. 1. (a) Side and top views of the atomic configurations of the SAC@MXene design (upper panel) and the general features of the partial density of states (lower panel); (b) 28 kinds of single-atom catalysts (cyan) considered for screening and the corresponding formation energies.

Fig. 2. N2 binding strength for the (a) side-on and (e) end-on adsorption patterns. Partial density of states (PDOS) for the (b) side-on and (f) end-on adsorption patterns. Crystal occupation Hamiltonian population (COHP) for the (c) side-on and (g) end-on adsorption patterns. Spatial charge distribution for the (d) side-on and (h) end-on adsorption patterns. The adsorption configuration is shown in the inset of the left panel.

Fig. 3. Free energy evolution process for the (a) distal, (b) alternating, (c) enzymatic-distal, and (d) enzymatic reaction mechanisms, where structural evolution is shown in the top bar of each panel.

Fig. 4. (a) Free energy evolution for the HER process, where the H adsorption configuration is shown in the inset. (b) Comparison of the electrochemical performances of the NRR and HER processes. The dashed line represents equal onset potentials for HER and NRR, while for the elements below this line, NRR is preferred to HER.

Fig. 5. COHP and partial density of states for the (a) *NH2 adsorption system in the enzymatic-distal reaction path and (c) *NNH adsorption system in the distal reaction path, where the spatial charge distribution in each energy interval is shown in the inset with the isosurface set to 0.008 e/?3. The scaling relations between the onset potential and the binding strength of a single N atom for the (b) enzymatic-distal reaction and (d) distal reaction.

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