Non-negligible Axial Ligand Effect on Electrocatalytic CO2 Reduction with Iron Porphyrin Complexes,The Journal of Physical Chemistry Letters

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Non-negligible Axial Ligand Effect on Electrocatalytic CO2 Reduction with Iron Porphyrin Complexes
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2022-12-15 , DOI: 10.1021/acs.jpclett.2c03235
Jiancong Zheng ₁ , Dexia Zhou ₁ , Jinxiu Han ₁ , Jing Liu ₁ , Rui Cao ₁ , Haitao Lei ₁ , Hongtao Bian ₁ , Yu Fang ₁

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Iron(III) porphyrin complexes have been demonstrated as one of the efficient molecular catalysts for the electrochemical reduction of CO₂. However, the role of axial ligands coordinated with a metal center in the complex on the electrochemical CO₂ reduction activity has not been fully explored yet. Herein, iron(III) tetraphenylporphyrin thiocyanate (FeTPP-SCN) is synthesized from a commercially available catalyst of FeTPP-Cl by a counteranion exchanging reaction. Cyclic voltammetry measurements showed that the catalytic activity of FeTPP-SCN is noticeably suppressed in the DMF solutions. The structural dynamics of the axial ligand in FeTPP-SCN are further examined by the FTIR and ultrafast IR spectroscopies, where the SCN ligand is employed as the local vibrational probe. Vibrational relaxation measurements showed that the reorientational dynamics of SCN ligands was strongly restricted in DMF solution, suggesting that the subtle electrostatic interaction between the ligands and metal center in the complex can have a non-negligible effect on its catalytic activity.

中文翻译：

不可忽略的轴向配体对铁卟啉络合物电催化 CO2 还原的影响

铁 (III) 卟啉络合物已被证明是用于电化学还原 CO ₂的有效分子催化剂之一。然而，轴向配体与络合物中的金属中心配位对电化学 CO _2的作用还原活动尚未得到充分探索。在此，四苯基卟啉硫氰酸铁 (III) (FeTPP-SCN) 是由市售的 FeTPP-Cl 催化剂通过抗衡阴离子交换反应合成的。循环伏安法测量表明 FeTPP-SCN 的催化活性在 DMF 溶液中被显着抑制。FTIR 和超快红外光谱进一步研究了 FeTPP-SCN 中轴向配体的结构动力学，其中 SCN 配体用作局部振动探针。振动弛豫测量表明，SCN 配体的重定向动力学在 DMF 溶液中受到强烈限制，这表明配合物中配体和金属中心之间微妙的静电相互作用对其催化活性具有不可忽略的影响。

更新日期：2022-12-15

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