important for the construction of efficient electrocatalysts for selective nitrate reduction to ammonia. The origin of the prominent activity enhancement for CuO (Faradaic efficiency: 95.8 %, Selectivity: 81.2 %) toward selective nitrate electroreduction to ammonia was probed. 15 N isotope labeling experiments showed that ammonia originated from nitrate reduction. 1 H NMR spectroscopy and colorimetric methods
在反应条件下揭示催化材料的活性相对于构建用于将硝酸盐选择性还原为氨的有效电催化剂很重要。探究了CuO对选择性硝酸盐电解还原成氨的显着活性增强(法拉第效率:95.8%,选择性:81.2%)的起源。15 N同位素标记实验表明氨源自硝酸盐还原。进行1 H NMR光谱和比色法以定量氨。原位拉曼和非原位实验表明,CuO被电化学转化为Cu / Cu2 O,并作为活性相。
The influences of carbon donor ligands on biomimetic multi-iron complexes for N<sub>2</sub> reduction
作者:Alexandra L. Nagelski、Majed S. Fataftah、Melissa M. Bollmeyer、Sean F. McWilliams、Samantha N. MacMillan、Brandon Q. Mercado、Kyle M. Lancaster、Patrick L. Holland
DOI:10.1039/d0sc03447a
日期:——
report the first example of a diiron complex that is bridged by an alkylidene and a sulfide, which serves as a high-fidelity structural and spectroscopic model of a two-iron portion of the active-site cluster (FeMoco) in the resting state of Mo-nitrogenase. The model complexes have antiferromagnetically coupled pairs of high-spin iron centers, and sulfur K-edge X-ray absorption spectroscopy shows comparable
固氮酶的活性位点簇拥有生物学中唯一的碳化物例子。这些是唯一能够将N 2还原为NH 4 +的生物FeS簇,表明中心碳及其与Fe的相互作用在N 2还原机制中非常重要。这个生物学问题激发了研究碳供体对不饱和高自旋铁中心的电子结构和反应性的影响。在这里,我们提出了功能和结构模型,用于测试碳供体和硫化物供体在更简单的铁化合物中的影响。我们报告了第一个由亚烷基和硫化物桥接的二铁配合物的例子,它作为静止状态下活性位点簇(FeMoco)的双铁部分的高保真结构和光谱模型Mo-固氮酶。该模型配合物具有反铁磁耦合的高自旋铁中心对,硫 K 边 X 射线吸收光谱显示 C 和 S 桥接物质的硫化物具有可比的共价性。即使在还原时,硫桥化合物也不与N 2相互作用,但在去除硫化物后,它能够通过添加质子和电子将N 2还原为NH 4 + 。这为固氮酶辅因子激活中的硫化物挤出提供了合成支持。
The in-built bionic “MoFe cofactor” in Fe-doped two-dimensional MoTe<sub>2</sub> nanosheets for boosting the photocatalytic nitrogen reduction performance
The bionic “MoFe cofactor” in 2D Fe–MoTe2 effectively facilitates the transport and separation of photogenerated carriers by one- and two-electron redox reactions.
Reduction of Dinitrogen to Ammonia and Hydrazine on Low-Valent Ruthenium Complexes
作者:Leslie D. Field、Hsiu L. Li、P. Manohari Abeysinghe、Mohan Bhadbhade、Scott J. Dalgarno、Ruaraidh D. McIntosh
DOI:10.1021/acs.inorgchem.8b02850
日期:2019.2.4
The ruthenium(0) dinitrogen complexes [Ru(N2)(PP3R)] [PP3R = P(CH2CH2PR2)3; R = iPr or Cy] react with triflic acid and other strong acids to afford mixtures of ammonia and hydrazine. In this reaction, Ru(0) is oxidized to Ru(II), and depending on the solvent, Ru(II) benzene or triflate complexes are isolated and characterized from the reactions with triflic acid as the final metal-containing products
Dinitrogen Reduction to Ammonium at Rhenium Utilizing Light and Proton-Coupled Electron Transfer
作者:Quinton J. Bruch、Gannon P. Connor、Chun-Hsing Chen、Patrick L. Holland、James M. Mayer、Faraj Hasanayn、Alexander J. M. Miller
DOI:10.1021/jacs.9b10031
日期:2019.12.26
inert to photolytic N2 cleavage. In striking contrast, illumination of the trans,cis and cis,cis-isomers with blue light (405 nm) affords the octahedral nitridecomplex cis-(PONOP)Re(N)Cl2 in 47% spectroscopic yield and 11% quantum yield. The photon energy drives an N2 splitting reaction that is thermodynamically unfavorable under standard conditions, producing a nitrido complex that reacts with SmI2/H2O