Electrocatalytic Reduction of Nitrogen Oxyanions with a Redox-Active Cobalt Macrocycle Complex
Electrocatalytic Reduction of Nitrogen Oxyanions with a Redox-Active Cobalt Macrocycle Complex
复制标题
用氧化还原活性钴大环配合物电催化还原氮氧阴离子
DOI：
10.1021/acs.inorgchem.2c00199
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发表时间：
2022
影响因子：
4.6
通讯作者：
Smith, Jeremy M.
中科院分区：
文献类型：
--
作者：
Partovi, Sheyda;Xiong, Ziqing;Kulesa, Krista M.;Smith, Jeremy M.
钴配合物 [Co(CR)Br2]+（其中 CR 是氧化还原活性大环 2,12-二甲基-3,7,11,17-四氮杂双环-[11.3.1]-十七-1(17),2,11,13,15-戊烯）已被研究用于水性 NO2– 和 NO3– 的电催化还原。在中性 pH 值下，溴化物配体水解，提供 [Co(CR)(OH2)(OH)]2+ 作为水溶液中的主要物质。在亚硝酸盐存在的情况下，[Co(CR)(NO2)2]+ 作为溶液中的主要物质形成，并且是电催化还原 NO2– 的前体，NO2– 选择性地转化为具有高法拉第效率的铵。有证据表明均相和非均相电催化。尽管没有观察到类似的 NO3 结合，但也会发生电催化还原成铵，尽管法拉第效率较低。在这种情况下，NO2– 作为 NO3– 还原的中间产物而生成。
The cobalt complex, [Co(CR)Br2]+, where CR is the redox-active macrocycle 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(17),2,11,13,15-pentaene, has been investigated for the electrocatalytic reduction of aqueous NO2–and NO3–. At neutral pH, the bromide ligands are hydrolyzed, providing [Co(CR)(OH2)(OH)]2+as the major species in aqueous solution. In the presence of nitrite, [Co(CR)(NO2)2]+is formed as the major species in solution and is a precursor to the electrocatalytic reduction of NO2–, which is selectively converted to ammonium with high Faradaic efficiency. There is evidence for both homogeneous and heterogeneous electrocatalysis. Although similar NO3–binding is not observed, electrocatalytic reduction to ammonium also occurs, albeit with a lower Faradaic efficiency. In this case, NO2–is generated as an intermediate product of NO3–reduction.