14390-96-6Relevant articles and documents
Stability of H, D, 14N, and 15N atoms in solid ammonia above 100 K
DeMarco,Brill,Crabb
, p. 1423 - 1428 (1998)
The measurements reported below quantify the stability and decay of hydrogen, deuterium, and nitrogen atoms in frozen ammonia above 100 K. The decay of H atoms is observed on a time scale of minutes in the range of 100-110 K and follows first-order kinetics. Analogous decays of D and N atoms are observed in the ranges 105-120 and 140-160 K, respectively. Activation energies for the decay processes range from 0.1 to 0.4 eV.
Amorphization engineered VSe2-: Xnanosheets with abundant Se-vacancies for enhanced N2electroreduction
Chu, Ke,Li, Qingqing,Liu, Yaping,Luo, Yaojing,Tian, Ye
supporting information, p. 1742 - 1749 (2022/02/02)
Electrochemical N2 fixation through the nitrogen reduction reaction (NRR) is a promising route for sustainable NH3 synthesis, while exploring high-performance NRR catalysts lies at the heart of achieving high-efficiency NRR electrocatalysis. Herein, we reported the structural regulation of VSe2 by amorphization engineering, which simultaneously triggered the enriched Se-vacancies. The developed amorphous VSe2-x nanosheets with abundant Se-vacancies (a-VSe2-x) delivered a much enhanced NRR activity with an NH3 yield of 65.7 μg h-1 mg-1 and a faradaic efficiency of 16.3% at -0.4 V, being 8.8- and 3.5-fold higher than those of their crystalline counterparts, respectively. Density functional theory computations combined with molecular dynamics simulations revealed that the amorphization-triggered Se-vacancies could induce the upraised d-band center of unsaturated V atoms, capable of promoting the binding of key ?N2/?NNH species to result in an energetically favorable NRR process. This journal is
A thiolate-bridged FeIVFeIV μ-nitrido complex and its hydrogenation reactivity toward ammonia formation
Chen, Hui,Mei, Tao,Qu, Jingping,Wang, Baomin,Wang, Junhu,Yang, Dawei,Ye, Shengfa,Zhang, Yixin,Zhao, Jinfeng,Zhou, Yuhan
, p. 46 - 52 (2021/12/27)
Iron nitrides are key intermediates in biological nitrogen fixation and the industrial Haber–Bosch process, used to form ammonia from dinitrogen. However, the proposed successive conversion of nitride to ammonia remains elusive. In this regard, the search for well-described multi-iron nitrido model complexes and investigations on controlling their reactivity towards ammonia formation have long been of great challenge and importance. Here we report a well-defined thiolate-bridged FeIVFeIV μ-nitrido complex featuring an uncommon bent Fe–N–Fe moiety. Remarkably, this complex shows excellent reactivity toward hydrogenation with H2 at ambient conditions, forming ammonia in high yield. Combined experimental and computational studies demonstrate that a thiolate-bridged FeIIIFeIII μ-amido complex is a key intermediate, which is generated through an unusual two-electron oxidation of H2. Moreover, ammonia production was also realized by treating this diiron μ-nitride with electrons and water as a proton source. [Figure not available: see fulltext.].
Dehydrated UiO-66(SH)2: The Zr?O Cluster and Its Photocatalytic Role Mimicking the Biological Nitrogen Fixation
Cheng, Xiyue,Deng, Shuiquan,Fu, Xianzhi,Guo, Binbin,Guo, Wei,Tang, Yu,Wu, Ling
supporting information, (2022/02/17)
This work reports the dehydrated Zr-based MOF UiO-66(SH)2 as a visible-light-driven photocatalyst to mimic the biological N2 fixation process. The 15N2 and other control experiments demonstrated that the new photocatalyst is highly efficient in converting N2 to ammonia. In-situ TGA, XPS, and EXAFS as well as first-principles simulations were used to demonstrate the role of the thermal treatment and the changes of the local structures around Zr due to the dehydration. It was shown that the dehydration opened a gate for the entry of N2 molecules into the [Zr6O6] cluster where the strong N≡N bond was broken stepwise by μ-N?Zr type interactions driven by the photoelectrons aided by the protonation. This mechanism was discussed in comparison with the Lowe–Thorneley mechanism proposed for the MoFe nitrogenase, and with emphasis on the [Zr6O6] cluster effect and the leading role of photoelectrons over the protonation. The results shed new light on understanding the catalytic mechanism of biological N2 fixation and open a new way to fix N2 under mild conditions.
