Bioinspired Activation of N2 on Asymmetrical Coordinated Fe Grafted 1T MoS2 at Room Temperature
Bioinspired Activation of N2 on Asymmetrical Coordinated Fe Grafted 1T MoS2 at Room Temperature
复制标题
室温下 N2 对不对称配位 Fe 接枝 1T MoS2 的仿生活化
DOI：
10.1002/cjoc.202000675
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发表时间：
2021
影响因子：
5.4
通讯作者：
Qian Xuefeng
中科院分区：
文献类型：
--
作者：
Guo Jiaojiao;Wang Maoyu;Xu Liang;Li Xiaomin;Iqbal Asma;Sterbinsky George E.;Yang Hao;Xie Miao;Zai Jiantao;Feng Zhenxing;Cheng Tao;Qian Xuefeng
主要观察与结论受MoFe固氮酶固氮过程的启发，成功地将不对称配位Fe接枝到1 T MoS 2上。这种不对称配位的富电子结构使1 T Fe0.1Mo0.9S2层状材料在室温和常压下与水和氮发生了积极的反应。随后，氨可以以约800 μmol（NH 4+）g−1的产率（12.5%摩尔产率）生产。同位素标记实验证实了双氮的活化、固定和还原。通过X射线吸收光谱分析，进一步确定了Fe-Mo-S中接枝Fe的位置和特定的配位环境。我们的工作表明，在没有任何化学和电化学辅助的情况下，在室温下对氨的固氮和还原明显不同于传统的仿生固氮过程。通过密度泛函理论计算和拉曼光谱进一步研究了N2的活化和还原机理。与1 T MoS 2相比，Fe-Mo-S材料中Fe的富集电子性质和不对称配位在环境条件下N2的生物激发活化中起关键作用。
Main observation and conclusionInspired by the nitrogen fixation process on MoFe nitrogenase, asymmetrical coordinated Fe grafted onto 1T MoS2were successfully synthesized. The unique electron‐rich structure with asymmetrical coordination made the 1T Fe0.1Mo0.9S2layered material actively react with water and dinitrogen at room temperature and atmosphere pressure. Subsequently, ammonia can be produced with a yield of ~800 μmol (NH4+) g−1(12.5% yield in mole). The activation, fixation and reduction of dinitrogen were confirmed by isotopically labeled experiments. The location and the specific coordination environment of grafted Fe in Fe‐Mo‐S were further determined by X‐ray absorption spectroscopy analysis. Our work demonstrates that the nitrogen fixation and reduction for ammonia at room temperature without any chemical and electrochemical assistance is distinctly different from traditional bionic‐inspired nitrogen fixation process. The mechanism of the activation and reduction of N2was further investigated by density functional theory calculation and Raman spectra. Compared with 1T MoS2, the enriched electron nature and asymmetrical coordination of Fe in Fe‐Mo‐S materials play a critical role in the bioinspired activation of N2at ambient condition.