Nitrogen Speciation Dictates Industrial‐Current Oxygen Reduction in Metal‐Free Macrocycles for H <sub>2</sub> O <sub>2</sub> Synthesis
Abstract
ABSTRACT Oxygen activation is a cornerstone of sustainable electrosynthesis, yet controlling reactive intermediates without metallic centers remains challenging at industrial current densities. Here we establish nitrogen speciation as a molecular descriptor for governing oxygen activation in metal‐free macrocycles. Guided by density functional theory, we designed a tetra‐aza macrocycle with nearly exclusive pyridinic nitrogen, distinct from the mixed‐nitrogen environments of conventional porphyrins and phthalocyanines. This configuration uniquely stabilizes the key *OOH intermediate while strengthening interfacial electronic coupling with carbon supports. When integrated into a flow‐cell electrolyzer, the catalyst achieves ∼95% H 2 O 2 Faradaic efficiency and stability for over 800 h at 300 mA cm −2 , continuously generating >3 wt.% H 2 O 2 . Furthermore, in situ generated reactive oxygen species enable selective ambient upgrading of furfural to oxime (>90% yield). Techno‐economic analysis supports the economic viability of the process. By linking well‐defined nitrogen coordination to scalable device performance, this work provides a blueprint for translating molecular precision into practical electrocatalytic manufacturing.
Article Details
Authors (12)
Zhen Liu
Yang Hu
Bufeng Zhang
State Key Laboratory of Chemo and Biosensing, National Graduate College for Elite Engineers and College of Chemistry and Chemical Engineering Hunan University Changsha China
Houting Xie
State Key Laboratory of Chemo and Biosensing, National Graduate College for Elite Engineers and College of Chemistry and Chemical Engineering Hunan University Changsha China
Laichun Zhao
State Key Laboratory of Chemo and Biosensing, National Graduate College for Elite Engineers and College of Chemistry and Chemical Engineering Hunan University Changsha China
Can Wu
Pengsheng Zhou
State Key Laboratory of Chemo and Biosensing, National Graduate College for Elite Engineers and College of Chemistry and Chemical Engineering Hunan University Changsha China
Qinjian Luo
State Key Laboratory of Chemo and Biosensing, National Graduate College for Elite Engineers and College of Chemistry and Chemical Engineering Hunan University Changsha China
Chuang Fu
State Key Laboratory of Chemo and Biosensing, National Graduate College for Elite Engineers and College of Chemistry and Chemical Engineering Hunan University Changsha China
Yuqin Zou
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering
Shuangyin Wang
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering
Shuaijun Pan
State Key Laboratory of Chemo and Biosensing, National Graduate College for Elite Engineers and College of Chemistry and Chemical Engineering Hunan University Changsha China