A Local Proton Source Enhances CO2 Electroreduction to CO by a Molecular Fe Catalyst
A Local Proton Source Enhances CO2 Electroreduction to CO by a Molecular Fe Catalyst
复制标题
DOI：
10.1126/science.1224581
复制
发表时间：
2012-10-05
期刊：
影响因子：
56.9
通讯作者：
Saveant, Jean-Michel
中科院分区：
文献类型：
--
作者：
Costentin, Cyrille;Drouet, Samuel;Saveant, Jean-Michel
二氧化碳（CO2）到一氧化碳（CO）的电化学转化是温室气体到燃料和商品化学品的期望转化中的潜在有用步骤。我们已经发现，通过在苯基的所有邻位和“邻”位引入酚基来修饰四苯基铁卟啉，显著地加速了电生铁（0）络合物对该反应的催化。该催化剂使用地球上最丰富的金属之一，在低过电位（0.465伏）下电解4小时，通过5000万次周转，显示出CO法拉第产率超过90%，没有观察到降解。增强活性的基础似乎是与酚羟基取代基相关的质子的高局部浓度。
Electrochemical conversion of carbon dioxide (CO2) to carbon monoxide (CO) is a potentially useful step in the desirable transformation of the greenhouse gas to fuels and commodity chemicals. We have found that modification of iron tetraphenylporphyrin through the introduction of phenolic groups in all ortho and ortho' positions of the phenyl groups considerably speeds up catalysis of this reaction by the electrogenerated iron(0) complex. The catalyst, which uses one of the most earth-abundant metals, manifests a CO faradaic yield above 90% through 50 million turnovers over 4 hours of electrolysis at low overpotential (0.465 volt), with no observed degradation. The basis for the enhanced activity appears to be the high local concentration of protons associated with the phenolic hydroxyl substituents.