Spectroscopic Identification of Active Sites of Oxygen-Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide

Longxiang Liu; Liqun Kang; Arunabhiram Chutia; Jianrui Feng; Martyna Michalska; Pilar Ferrer; David C Grinter; Georg Held; Yeshu Tan; Fangjia Zhao; Fei Guo; David G Hopkinson; Christopher S Allen; Yanbei Hou; Junwen Gu; Ioannis Papakonstantinou; Paul R Shearing; Dan J L Brett; Ivan P Parkin; Guanjie He

doi:10.1002/anie.202303525

Spectroscopic Identification of Active Sites of Oxygen-Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide

Angew Chem Int Ed Engl. 2023 May 15;62(21):e202303525. doi: 10.1002/anie.202303525. Epub 2023 Apr 18.

Authors

Longxiang Liu¹, Liqun Kang², Arunabhiram Chutia³, Jianrui Feng¹, Martyna Michalska⁴, Pilar Ferrer⁵, David C Grinter⁵, Georg Held⁵, Yeshu Tan¹, Fangjia Zhao¹, Fei Guo¹, David G Hopkinson⁶, Christopher S Allen^{6

7}, Yanbei Hou⁸, Junwen Gu¹, Ioannis Papakonstantinou⁴, Paul R Shearing⁹, Dan J L Brett⁹, Ivan P Parkin¹, Guanjie He^{1

9}

Affiliations

¹ Christopher Ingold Laboratory, Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK.
² Department of Inorganic Spectroscopy, Max-Planck-Institute for Chemical Energy Conversion, Stiftstr. 34-36, 45470, Mülheim an der Ruhr, Germany.
³ School of Chemistry, University of Lincoln, Lincolnshire, LN6 7DL, UK.
⁴ Photonic Innovations Lab, Department of Electronic & Electrical Engineering, University College London, Torrington Place, London, WC1E 7JE, UK.
⁵ Diamond Light Source, Rutherford Appleton Laboratory, Harwell, Didcot, OX11 0DE, UK.
⁶ electron Physical Science Imaging Centre, Rutherford Appleton Laboratory, Harwell, Didcot, OX11 0DE, UK.
⁷ Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK.
⁸ HP-NTU Digital Manufacturing Corporate Laboratory, School of Mechanical and Aerospace, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798, Singapore.
⁹ Electrochemical Innovation Lab, Department of Chemical Engineering, University College London, London, WC1E 7JE, UK.

Abstract

The electrochemical synthesis of hydrogen peroxide (H₂ O₂ ) via a two-electron (2 e^- ) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst for H₂ O₂ electrochemical production. The optimized PCC₉₀₀ material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H₂ O₂ selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e^- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.

Keywords: Electrocatalysis; Hydrogen Peroxide; NEXAFS; Porous Carbon; Quinone.

Grants and funding

, EP/V027433/1, EP/L015862/1, EP/R023581/1/Engineering and Physical Sciences Research Council