Tailoring Cu Nanoparticles Motif Into Atomic-Level Sites for Efficient H₂O₂ Electrosynthesis

TY - JOUR

T1 - Tailoring Cu Nanoparticles Motif Into Atomic-Level Sites for Efficient H2O2 Electrosynthesis

AU - Hou, Mengyun

AU - Liu, Jing

AU - Zheng, Lirong

AU - Feng, Wuyi

AU - Hussain, Irshad

AU - Zhang, Jiatao

AU - Zhao, Di

N1 - Publisher Copyright: © 2026 Wiley-VCH GmbH.

PY - 2026/6/15

Y1 - 2026/6/15

N2 - The engineering of active motifs via ensemble effects has emerged as a powerful strategy for modulating oxygen reduction reaction (ORR) selectivity. While Cu-based materials have demonstrated promising potential as ORR electrocatalysts, the correlation between ensemble effects in Cu active motifs and the selectivity toward hydrogen peroxide (H2O2) production via the 2e− ORR pathway remains insufficiently investigated. Herein, we systematically demonstrate that structural evolution of carbon-supported Cu electrocatalysts from nanoparticles to atomic-level single Cu─C2 sites and nanoclusters (denoted as CuSA─Cuclu/C) effectively eliminates accessible ensemble sites characteristic of nanoparticles and induces preferential end-on adsorption of O2 on atomic-level sites, thereby significantly enhancing both the selectivity and activity for H2O2 generation. Comprehensive evaluations through rotating ring-disk electrodes, H-cell testing, and flow cell amplification consistently verify their superior performance. Integrating experiments and theoretical modeling, we confirm that the 2e− ORR selectivity and activity exhibit progressive enhancement as the active motif dimension decreases from nanoparticles (multi-atom ensembles) to nanoclusters (sub-nm aggregates) and ultimately to single-atom sites. This study provides the first experimental confirmation of the size-dependent activity/selectivity trends in H2O2 generation over Cu-based electrocatalysts, establishing a generalizable framework that could be extended to other transition metal systems for precise regulation of ORR activity and selectivity.

AB - The engineering of active motifs via ensemble effects has emerged as a powerful strategy for modulating oxygen reduction reaction (ORR) selectivity. While Cu-based materials have demonstrated promising potential as ORR electrocatalysts, the correlation between ensemble effects in Cu active motifs and the selectivity toward hydrogen peroxide (H2O2) production via the 2e− ORR pathway remains insufficiently investigated. Herein, we systematically demonstrate that structural evolution of carbon-supported Cu electrocatalysts from nanoparticles to atomic-level single Cu─C2 sites and nanoclusters (denoted as CuSA─Cuclu/C) effectively eliminates accessible ensemble sites characteristic of nanoparticles and induces preferential end-on adsorption of O2 on atomic-level sites, thereby significantly enhancing both the selectivity and activity for H2O2 generation. Comprehensive evaluations through rotating ring-disk electrodes, H-cell testing, and flow cell amplification consistently verify their superior performance. Integrating experiments and theoretical modeling, we confirm that the 2e− ORR selectivity and activity exhibit progressive enhancement as the active motif dimension decreases from nanoparticles (multi-atom ensembles) to nanoclusters (sub-nm aggregates) and ultimately to single-atom sites. This study provides the first experimental confirmation of the size-dependent activity/selectivity trends in H2O2 generation over Cu-based electrocatalysts, establishing a generalizable framework that could be extended to other transition metal systems for precise regulation of ORR activity and selectivity.

KW - HO production

KW - active motifs

KW - electrocatalysis

KW - reaction pathway

UR - https://www.scopus.com/pages/publications/105038535801

U2 - 10.1002/adfm.75746

DO - 10.1002/adfm.75746

M3 - Article

AN - SCOPUS:105038535801

SN - 1616-301X

VL - 36

JO - Advanced Functional Materials

JF - Advanced Functional Materials

IS - 48

M1 - e75746

ER -