Deng Peiji, Liu Yixian, Liu Yunliang, Li Yaxi, Wu Ruqiang, Meng Lijun, Liang Kang, Gan Yixiang, Qiao Fen, Liu Naiyun, Kang Zhenhui, Li Haitao
School of Chemistry and Chemical Engineering, Institute for Energy Research of Jiangsu University, Zhenjiang 212013, Jiangsu, China.
Guangxi Key Laboratory of Electrochemical Energy Materials, Guangxi University, Nanning 530004, China.
ACS Appl Mater Interfaces. 2023 Sep 27;15(38):44809-44819. doi: 10.1021/acsami.3c06037. Epub 2023 Sep 12.
More than 90% of the global NH synthesis is dominated by the Haber-Bosch process, which consumes 2% of the worldwide energy and generates 1.44% of the global carbon emission. The electrochemical N reduction reaction (NRR) is regarded as an attractive alternative route to produce NH under mild reaction conditions, but the electrocatalysts suffer from the difficulty of N≡N cleavage. In this work, we report a leaf-like MOF-derived Ni/Zn bimetallic co-doped nitrogen-coordinated porous carbon (Ni/Zn-NPC) as a cost-effective NH synthesis electrocatalyst. The resultant electrocatalyst achieved a high NH production rate of 22.68 μg h mg at -1.0 V vs a reversible hydrogen electrode (RHE) in a 0.1 M NaSO electrolyte. The Ni/Zn-NPC material can be called a microwave regenerable catalyst because microwave treatment has proven to be a crucial part of the multi-field coupling to detoxify and make the catalyst reactive, further improving its stability. Density functional theory (DFT) was chosen to explore the mechanism of Ni/Zn-NPC for NRR, providing a profound prediction of the structure of the active site and related reaction pathways and revealing that trace Ni doping optimizes the local coordination environment and N adsorption of Zn atoms.
全球超过90%的氨合成由哈伯-博施法主导，该方法消耗全球2%的能源并产生1.44%的全球碳排放。电化学氮还原反应（NRR）被认为是在温和反应条件下生产氨的一种有吸引力的替代途径，但电催化剂存在N≡N键断裂困难的问题。在这项工作中，我们报道了一种叶状的金属有机框架衍生的镍/锌双金属共掺杂氮配位多孔碳（Ni/Zn-NPC）作为一种具有成本效益的氨合成电催化剂。在0.1 M NaSO电解质中，相对于可逆氢电极（RHE），所得电催化剂在-1.0 V时实现了22.68 μg h mg的高氨产率。Ni/Zn-NPC材料可被称为微波可再生催化剂，因为微波处理已被证明是多场耦合解毒并使催化剂具有活性的关键部分，进一步提高了其稳定性。选择密度泛函理论（DFT）来探索Ni/Zn-NPC用于NRR的机理，对活性位点的结构和相关反应途径进行了深入预测，并揭示了微量镍掺杂优化了锌原子的局部配位环境和氮吸附。
