Resumen: Tailoring the reaction kinetics is the central theme of designer electrocatalysts, which enables the selective conversion of abundant and inert atmospheric species into useful products. Here we show a supporting effect in tuning the electrocatalytic kinetics of oxygen reduction reaction (ORR) from four-electron to two-electron mechanism by docking metalloporphyrin-based metal-organic frameworks (MOFs) crystals on graphene support, leading to highly selective peroxide production with faradaic efficiency as high as 93.4%. A magic angle of 38.1° tilting for the co-facial alignment was uncovered by electron diffraction tomography, which is attributed to the maximization of π-π interaction for mitigating the lattice and symmetry mismatch between MOF and graphene. The facilitated electron migration and oxygen chemisorption could be ascribed to the supportive effect of graphene that disperses of the electron state of the active center, and ultimately regulates rate-determining step. Idioma: Inglés DOI: 10.1007/s12274-021-3382-3 Año: 2022 Publicado en: Nano Research 15, 1 (2022), 145-152 ISSN: 1998-0124 Factor impacto JCR: 9.9 (2022) Categ. JCR: CHEMISTRY, PHYSICAL rank: 29 / 161 = 0.18 (2022) - Q1 - T1 Categ. JCR: NANOSCIENCE & NANOTECHNOLOGY rank: 24 / 107 = 0.224 (2022) - Q1 - T1 Categ. JCR: PHYSICS, APPLIED rank: 18 / 160 = 0.112 (2022) - Q1 - T1 Categ. JCR: MATERIALS SCIENCE, MULTIDISCIPLINARY rank: 47 / 343 = 0.137 (2022) - Q1 - T1 Factor impacto CITESCORE: 13.7 - Engineering (Q1) - Physics and Astronomy (Q1) - Materials Science (Q1)