Chemical looping air separation (CLAS) is a promising technology for oxygen generation with high efficiency. The key challenge for CLAS is to design robust oxygen sorbents with suitable redox properties and fast redox kinetics. In this work, perovskite-structured Sr1-xCaxFe1-yCoyO3oxygen sorbents were investigated and demonstrated for oxygen production with tunable redox properties, high redox rate, and excellent thermal/steam stability. Cobalt doping at B site was found to be highly effective, 33% improvement in oxygen productivity was observed at 500 °C. Moreover, it stabilizes the perovskite structure and prevents phase segregation under pressure swing conditions in the presence of steam. Scalable synthesis of Sr0.8Ca0.2Fe0.4Co0.6O3oxygen sorbents was carried out through solid state reaction, co-precipitation, and sol-gel methods. Both co-precipitation and sol-gel methods are capable of producing Sr0.8Ca0.2Fe0.4Co0.6O3sorbents with satisfactory phase purity, high oxygen capacity, and fast redox kinetics. Large scale evaluation of Sr0.8Ca0.2Fe0.4Co0.6O3, using an automated CLAS testbed with over 300 g sorbent loading, further demonstrated the effectiveness of the oxygen sorbent to produce 95% pure O2with a satisfactory productivity of 0.04 gO2gsorbent−1h−1at 600 °C.
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.
- Publication Date:
- NSF-PAR ID:
- 10381932
- Journal Name:
- Nature Communications
- Volume:
- 13
- Issue:
- 1
- ISSN:
- 2041-1723
- Publisher:
- Nature Publishing Group
- Sponsoring Org:
- National Science Foundation
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