Li Shaobin, Cheng Kun, Ma Lin, Zhang Li, Li Fengbo, Cheng Qingyu
College of Materials Science and Engineering, Key Laboratory of Polymeric Composite Materials of Heilongjiang Province, Qiqihar University, Qiqihar 161006, P. R. China.
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China.
Inorg Chem. 2024 May 6;63(18):8366-8375. doi: 10.1021/acs.inorgchem.4c00760. Epub 2024 Apr 24.
The electrochemical nitrogen reduction reaction (eNRR) provides a sustainable green development route for the nitrogen-neutral cycle. In this work, bimetallic CoFe-MIL-88A with two active sites (Fe, Co) were immobilized on a 2D VCT MXene surface by in situ growth method to achieve the purpose of the control interface. A large number of heterostructures are formed between small CoFe-MIL-88A and VCT, which regulate the electron transfer between the catalyst interfaces. The adsorption and activation of nitrogen on the active sites were enhanced, and the NRR reaction kinetics was accelerated. CoFe-MIL-88A is tightly arranged on VCT, which makes CoFe-MIL-88A/VCT have better hydrophobicity and can significantly inhibit the hydrogen evolution reaction. The synergistic effect of multicatalytic active sites and multi-interface structure of CoFe-MIL-88A/VCT MXene is propitious to nitrogen efficiently and stably to convert into ammonia under environmental conditions with superior selectivity and good catalytic activity. The NH yield rate is 29.47 μg h mg at -0.3 V vs RHE, and the Faradaic efficiency (FE) is 28.86% at -0.1 V vs RHE. The catalytic mechanism was verified to conform to the distal pathway. This work will provide a new way to develop an MXene-based electrocatalyst for eNRR.
电化学氮还原反应（eNRR）为氮中性循环提供了一条可持续的绿色发展途径。在这项工作中，通过原位生长法将具有两个活性位点（Fe、Co）的双金属CoFe-MIL-88A固定在二维VCT MXene表面，以实现控制界面的目的。在小尺寸的CoFe-MIL-88A与VCT之间形成了大量异质结构，这些异质结构调节了催化剂界面之间的电子转移。增强了活性位点上氮的吸附和活化，加速了NRR反应动力学。CoFe-MIL-88A紧密排列在VCT上，这使得CoFe-MIL-88A/VCT具有更好的疏水性，并能显著抑制析氢反应。CoFe-MIL-88A/VCT MXene的多催化活性位点和多界面结构的协同效应有利于在环境条件下将氮高效稳定地转化为氨，具有优异的选择性和良好的催化活性。在相对于可逆氢电极（RHE）为-0.3 V时，NH产率为29.47 μg h mg，在相对于RHE为-0.1 V时，法拉第效率（FE）为28.86%。验证了催化机理符合远端途径。这项工作将为开发用于eNRR的基于MXene的电催化剂提供一条新途径。
