Theory-guided design of hydrogen-bonded cobaltoporphyrin frameworks for highly selective electrochemical H2O2 production in acid

Abstract The pursuit of selective two-electron oxygen reduction reaction to H 2 O 2 in acids is demanding and largely hampered by the lack of efficient non-precious-metal-based electrocatalysts. Metal macrocycles hold promise, but have been relatively underexplored. Efforts are called for to promote their inherent catalytic activities and/or increase the surface exposure of active sites. In this contribution, we perform the high-throughput computational screening of thirty-two different metalloporphyrins by comparing their adsorption free energies towards key reaction intermediates. Cobalt porphyrin is revealed to be the optimal candidate with a theoretical overpotential as small as 40 mV. Guided by the computational predictions, we prepare hydrogen-bonded cobaltoporphyrin frameworks in order to promote the solution accessibility of catalytically active sites for H 2 O 2 production in acids. The product features an onset potential at ~0.68 V, H 2 O 2 selectivity of >90%, turnover frequency of 10.9 s −1 at 0.55 V and stability of ~30 h, the combination of which clearly renders it stand out from existing competitors for this challenging reaction.