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Factors Determining the Rate and Selectivity of 4e–/4H+ Electrocatalytic Reduction of Dioxygen by Iron Porphyrin Complexes
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2017-07-07 00:00:00 , DOI: 10.1021/acs.accounts.7b00192 Sudipta Chatterjee 1 , Kushal Sengupta 1 , Biswajit Mondal 1 , Subal Dey 1 , Abhishek Dey 1
Accounts of Chemical Research ( IF 16.4 ) Pub Date : 2017-07-07 00:00:00 , DOI: 10.1021/acs.accounts.7b00192 Sudipta Chatterjee 1 , Kushal Sengupta 1 , Biswajit Mondal 1 , Subal Dey 1 , Abhishek Dey 1
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Reactivity as well as selectivity are crucial in the activation and electrocatalytic reduction of molecular oxygen. Recent developments in the understanding of the mechanism of electrocatalytic O2 reduction by iron porphyrin complexes in situ using surface enhanced resonance Raman spectroscopy coupled to rotating disc electrochemistry (SERRS-RDE) in conjunction with H/D isotope effects on electrocatalytic current reveals that the rate of O2 reduction, ∼104 to 105 M–1 s–1 for simple iron porphyrins, is limited by the rate of O–O bond cleavage of an intermediate ferric peroxide species (FeIII–OOH). SERRS-RDE probes the system in operando when it is under steady state such that any intermediate species that has a greater rate of formation relative to its rate of decay, including the rate determining species, would accumulate and can be identified. This technique is particularly well suited to investigate iron porphyrin electrocatalysts as the intense symmetric ligand vibrations allow determination of the oxidation and spin states of the bound iron with high fidelity.
中文翻译：
铁卟啉配合物决定4e – / 4H +电催化还原双氧的速率和选择性的因素
反应性和选择性在分子氧的活化和电催化还原中至关重要。使用表面增强共振拉曼光谱结合旋转盘电化学（SERRS-RDE）结合H / D同位素对电催化电流的作用，对铁卟啉配合物原位电催化O 2还原机理的理解的最新进展揭示了该速率O 2还原的数量，对于简单的铁卟啉，约为10 4至10 5 M –1 s –1，这受中间过氧化铁物种（Fe III –OOH）的O–O键裂解速率的限制。SERRS-RDE探测系统在操作中处于稳定状态时，使得相对于其衰变速率具有更大形成速率的任何中间物种（包括确定速率的物种）都会积累并可以被识别。该技术特别适合研究卟啉铁催化剂，因为强烈的对称配体振动可以高保真度确定结合铁的氧化和自旋态。
更新日期：2017-07-07
中文翻译：
铁卟啉配合物决定4e – / 4H +电催化还原双氧的速率和选择性的因素
反应性和选择性在分子氧的活化和电催化还原中至关重要。使用表面增强共振拉曼光谱结合旋转盘电化学（SERRS-RDE）结合H / D同位素对电催化电流的作用，对铁卟啉配合物原位电催化O 2还原机理的理解的最新进展揭示了该速率O 2还原的数量，对于简单的铁卟啉，约为10 4至10 5 M –1 s –1，这受中间过氧化铁物种（Fe III –OOH）的O–O键裂解速率的限制。SERRS-RDE探测系统在操作中处于稳定状态时，使得相对于其衰变速率具有更大形成速率的任何中间物种（包括确定速率的物种）都会积累并可以被识别。该技术特别适合研究卟啉铁催化剂，因为强烈的对称配体振动可以高保真度确定结合铁的氧化和自旋态。
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