Efficient and selective molecular catalyst for the CO2-to-CO electrochemical conversion in water
Efficient and selective molecular catalyst for the CO2-to-CO electrochemical conversion in water
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DOI：
10.1073/pnas.1507063112
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发表时间：
2015-06-02
影响因子：
11.1
通讯作者：
Tatin, Arnaud
中科院分区：
文献类型：
--
作者：
Costentin, Cyrille;Robert, Marc;Tatin, Arnaud
用三甲基铵基取代四苯基铁卟啉的四个对苯基氢提供了能够催化二氧化碳电化学转化为一氧化碳的水溶性分子。该反应在pH中性的水中进行，几乎不产生氢气，形成准排他性的一氧化碳，尽管CO2与碳酸-一种低pKa酸部分平衡。这种选择性分子催化剂具有良好的稳定性和高的转换频率。在此基础上，可以通过调节溶液的pH值，任选地加入电惰性缓冲液来获得CO-H-2混合物的规定组成。这些战略的制定将因在水中作业而得到极大的便利。这同样适用于通过合适的隔板将阴极隔室与产生质子的阳极相关联。
Substitution of the four paraphenyl hydrogens of iron tetraphenylporphyrin by trimethylammonio groups provides a water-soluble molecule able to catalyze the electrochemical conversion of carbon dioxide into carbon monoxide. The reaction, performed in pH-neutral water, forms quasi-exclusively carbon monoxide with very little production of hydrogen, despite partial equilibration of CO2 with carbonic acid-a low pKa acid. This selective molecular catalyst is endowed with a good stability and a high turnover frequency. On this basis, prescribed composition of CO-H-2 mixtures can be obtained by adjusting the pH of the solution, optionally adding an electroinactive buffer. The development of these strategies will be greatly facilitated by the fact that one operates in water. The same applies for the association of the cathode compartment with a proton-producing anode by means of a suitable separator.