Contributed by Hongjie Dai, October 14, 2019 (sent for review September 4, 2019; reviewed by Dehui Deng and Dunwei Wang)
Electrochemical reduction of CO2 to useful chemicals or fuels is critical to closing the carbon cycle and preventing further deterioration of the environment/climate. This work addresses the low-energy-efficiency problem of CO2 reduction limited by sluggish oxygen evolution reaction (OER) on the anode side. The only active OER catalysts for coupling CO2 reduction in neutral conditions are based on noble metals such as Ir, Ru, and gold. Herein, we developed a nonprecious-metal-based OER anode with higher activity and stability than those based on noble-metal catalysts IrO2 and Ir/C. We integrated our anode with a selective CO2 reduction cathode to achieve >97% conversion of CO2 to CO and a record-setting high energy efficiency for CO2 conversion.
Electrochemical reduction of CO2 to useful chemicals has been actively pursued for closing the carbon cycle and preventing further deterioration of the environment/climate. Since CO2 reduction reaction (CO2RR) 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 CO2-saturated 0.5 M KHCO3. 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 KHCO3 solution at 85 °C under a high-current ∼250 mA/cm2), 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 CO2-saturated 0.5 M KHCO3 exhibited OER activity superior to IrO2, with an overpotential of 450 and 590 mV to reach 10 and 250 mA/cm2, respectively, and high stability for >120 h without decay. We paired NiFe-HC with a CO2RR catalyst of cobalt phthalocyanine/carbon nanotube (CoPc/CNT) in a CO2 electrolyzer, achieving selective cathodic conversion of CO2 to CO with >97% Faradaic efficiency and simultaneous anodic water oxidation to O2. 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/cm2.
↵1Y.M. and X. Zhang contributed equally to this work.
Author contributions: Y.M. and H.D. designed research; Y.M., X. Zhang, W.-H.H., J.H., Y.-S.T., M.J.K., J.-J.S., K.H.S., and X. Zheng performed research; Y.M., X. Zhang, W.-H.H., J.H., Y.-S.T., Y.K., J.-J.S., Y. Liu, K.H.S., X. Zheng, S.L.S., M.-C.L., Y. Liang, and H.D. contributed new reagents/analytic tools; Y.M., X. Zhang, W.-H.H., J.H., Y.-S.T., and H.D. analyzed data; and Y.M., X. Zhang, and H.D. wrote the paper.
Reviewers: D.D., Dalian Institute of Chemical Physics, Chinese Academy of Sciences; and D.W., Boston College.
The authors declare no competing interest.
This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1915319116/-/DCSupplemental.
Published under the PNAS license.
