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Abstract A direct electrosynthesis of H2O2from either O2or H2O is an attractive strategy to replace the energy‐intensive industrial anthraquinone process. Two‐electron water oxidation reaction (2e‐WOR) offers several advantages over the oxygen reduction reaction such as better mass transfer due to the absence of gas‐phase reactants. However, 2e‐WOR is a more challenging and less studied process with only a handful of metal oxides exhibiting reasonable activity/selectivity properties. Herein, we employ density‐functional‐theory calculations to screen a variety of metal‐nitrogen‐graphene structures for 2e‐WOR. As a consequence of scaling between the adsorption energies of reaction intermediates, we determine a linear relation between selectivities for the first and second reaction steps of 2e‐WOR, viz. that if selectivity toward adsorbed OH is improved, then selectivity toward H2O2at the subsequent step is decreased. We also find that selectivity and activity are linearly scaled in such a way that a higher activity (i. e., a lower overpotential) leads to a lower selectivity for the H2O2formation step. Based on the obtained results several chemistries, e. g., containing NiNx−C moieties, are predicted to rival the best‐performing metal oxides such as ZnO and CaSnO3in terms of combination of their activity/selectivity characteristics for 2e‐WOR.
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Discovery of LaAlO3 as an efficient catalyst for two-electron water electrolysis towards hydrogen peroxide
Abstract Electrochemical two-electron water oxidation reaction (2e-WOR) has drawn significant attention as a promising process to achieve the continuous on-site production of hydrogen peroxide (H2O2). However, compared to the cathodic H2O2generation, the anodic 2e-WOR is more challenging to establish catalysts due to the severe oxidizing environment. In this study, we combine density functional theory (DFT) calculations with experiments to discover a stable and efficient perovskite catalyst for the anodic 2e-WOR. Our theoretical screening efforts identify LaAlO3perovskite as a stable, active, and selective candidate for catalyzing 2e-WOR. Our experimental results verify that LaAlO3achieves an overpotential of 510 mV at 10 mA cm−2in 4 M K2CO3/KHCO3, lower than those of many reported metal oxide catalysts. In addition, LaAlO3maintains a stable H2O2Faradaic efficiency with only a 3% decrease after 3 h at 2.7 V vs. RHE. This computation-experiment synergistic approach introduces another effective direction to discover promising catalysts for the harsh anodic 2e-WOR towards H2O2.
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- Award ID(s):
- 2029425
- PAR ID:
- 10381932
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 13
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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