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Defect-Rich CoNi Prussian Blue Analogues Enable Highly Selective Electrochemical Hydrogen Peroxide Production
Kai Sun1, Yu Mao1, Yongfang Zhou1
1School of Chemical Sciences, The University of Auckland, Auckland, New Zealand.
Angewandte Chemie (International Ed. in English)
|August 5, 2026
Summary
Researchers developed a defect-engineered cobalt-nickel catalyst for efficient decentralized hydrogen peroxide (H2O2) electrosynthesis. This novel catalyst shows high selectivity and durability, offering a sustainable alternative to traditional methods.
Area of Science:
- Electrochemistry
- Materials Science
- Catalysis
Background:
- Decentralized electrosynthesis of hydrogen peroxide (H2O2) is a sustainable alternative to the anthraquinone process.
- Developing non-precious metal electrocatalysts with high activity, selectivity, and durability for the two-electron oxygen reduction reaction (2e- ORR) is crucial but challenging.
Purpose of the Study:
- To engineer CoNi Prussian blue analogues (PBAs) with tunable defect concentrations for enhanced H2O2 electrosynthesis.
- To investigate the structural and electronic effects of defects on the ORR pathway and catalytic performance.
- To establish a robust and durable electrocatalyst for decentralized H2O2 production.
Main Methods:
- Synthesized CoNi PBAs using a defect-engineering strategy with kinetic trapping to control vacancy concentrations.
- Characterized catalyst structure and coordination environment using synchrotron X-ray diffraction and absorption spectroscopy (EXAFS).
- Evaluated electrocatalytic performance for H2O2 production in a flow-cell device and assessed durability via a 120-h stability test.
- Employed density functional theory (DFT) calculations to identify active sites and understand reaction mechanisms.
Main Results:
- Achieved over 97% H2O2 selectivity and a production rate of 6.2 mol g_cat.-1 h-1.
- Demonstrated exceptional durability over a 120-hour stability test.
- Identified coordinatively unsaturated Ni-N4 motifs, induced by vacancies, as key active sites.
- DFT calculations confirmed optimized *OOH intermediate binding and suppression of the 4e- ORR pathway.
Conclusions:
- Defect engineering in CoNi PBAs creates unsaturated Ni-N4 sites, significantly enhancing H2O2 electrosynthesis.
- The developed catalyst offers high activity, selectivity, and durability for decentralized H2O2 production.
- This work provides a validated protocol for defect engineering in coordination frameworks for catalysis.
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