期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2019
卷号：116
期号：48
页码：23915-23922
DOI：10.1073/pnas.1915319116
出版社：The National Academy of Sciences of the United States of America
摘要：Electrochemical reduction of CO 2 to useful chemicals has been actively pursued for closing the carbon cycle and preventing further deterioration of the environment/climate. Since CO 2 reduction reaction (CO 2 RR) at a cathode is always paired with the oxygen evolution reaction (OER) at an anode, the overall efficiency of electrical energy to chemical fuel conversion must consider the large energy barrier and sluggish kinetics of OER, especially in widely used electrolytes, such as the pH-neutral CO 2 -saturated 0.5 M KHCO 3 . OER in such electrolytes mostly relies on noble metal (Ir- and Ru-based) electrocatalysts in the anode. Here, we discover that by anodizing a metallic Ni–Fe composite foam under a harsh condition (in a low-concentration 0.1 M KHCO 3 solution at 85 °C under a high-current ∼250 mA/cm 2 ), OER on the NiFe foam is accompanied by anodic etching, and the surface layer evolves into a nickel–iron hydroxide carbonate (NiFe-HC) material composed of porous, poorly crystalline flakes of flower-like NiFe layer-double hydroxide (LDH) intercalated with carbonate anions. The resulting NiFe-HC electrode in CO 2 -saturated 0.5 M KHCO 3 exhibited OER activity superior to IrO 2 , with an overpotential of 450 and 590 mV to reach 10 and 250 mA/cm 2 , respectively, and high stability for >120 h without decay. We paired NiFe-HC with a CO 2 RR catalyst of cobalt phthalocyanine/carbon nanotube (CoPc/CNT) in a CO 2 electrolyzer, achieving selective cathodic conversion of CO 2 to CO with >97% Faradaic efficiency and simultaneous anodic water oxidation to O 2 . The device showed a low cell voltage of 2.13 V and high electricity-to-chemical fuel efficiency of 59% at a current density of 10 mA/cm 2 ..
关键词：oxygen evolution ; CO 2 reduction ; CO 2 electrolyzer ; electrocatalysis ; pH;neutral electrolyte
