Catalytic reduction of dinitrogen to ammonia using molybdenum porphyrin complexes
Catalytic reduction of dinitrogen to ammonia using molybdenum porphyrin complexes
复制标题
使用钼卟啉配合物催化还原二氮生成氨
DOI：
10.1039/d2fd00166g
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发表时间：
2023
影响因子：
3.4
通讯作者：
Holland, Patrick L.
中科院分区：
文献类型：
--
作者：
Hegg, Alexander S.;Mercado, Brandon Q.;Miller, Alexander J. M.;Holland, Patrick L.
卟啉配合物在O2和CO2还原中是众所周知的，但在N2还原中的应用还不太发达。本文通过15N2标记研究和其他对照实验验证了四甲基卟啉（TMP）负载的钼的氧和氮配合物是催化N2还原成氨的有效预催化剂。光谱和电化学研究阐明了相关热力学参数，包括（TMP）MoNH的N-H键解离自由能（43±2 kcal mol−1）。我们将这些结果置于其他均相N2还原催化工作的背景下。
Porphyrin complexes are well-known in O2 and CO2 reduction, but their application to N2 reduction is less developed. Here, we show that oxo and nitrido complexes of molybdenum supported by tetramesitylporphyrin (TMP) are effective precatalysts for catalytic N2 reduction to ammonia, verified by 15N2 labeling studies and other control experiments. Spectroscopic and electrochemical studies illuminate some relevant thermodynamic parameters, including the N–H bond dissociation free energy of (TMP)MoNH (43 ± 2 kcal mol−1). We place these results in the context of other work on homogeneous N2 reduction catalysis.