Precursor‐Mediated Direct Growth of Defect‐Rich Hierarchical Nanocarbons for Electrocatalytic Hydrogen Peroxide Production

Comprehensive Summary Carbon‐based nanomaterials show great potential in selective electrochemical oxygen reduction reaction (ORR) through two‐electron (2e−) pathway for H2O2 production, which provides an eco‐friendly alternative to industrial energy‐intensive anthraquinone process. However, it still remains challenging to directly construct topological defects, which makes it difficult to study the working mechanism on 2e– ORR. Herein, we propose a precursor‐mediated chemical vapor deposition (CVD) approach for direct growth of topological defect‐rich hierarchical nanocarbons. Boric acid (H3BO3) is introduced into the precursor for disturbing the nucleation and growth through decomposing B‐containing species, which can in situ induce the formation of pentagon defects. The topological defect is found to be capable of introducing lattice strain, which can modify the electronic structure of nanocarbons and promote the key intermediate (*OOH) formation, thus greatly enhancing the 2e– ORR performance. Experimentally, the 2e– ORR selectivity shows a positive correlation to the topological defect density, where the average H2O2 selectivity reaches above 90% over a wide potential range with optimized concentration of H3BO3 as mediator. Moreover, in a flow cell, the hierarchical nanocarbons achieve a high H2O2 production rate of 998 mmol·gcatalyst−1·h−1 over 20 h of continuous electrocatalysis with stable current density (>100 mA·cm–2) and Faradaic efficiency (> 90%). This work provides a straightforward method for the synthesis of active metal‐free carbon‐based catalyst for sustainable H2O2 production. The boric acid (H3BO3) in the precursor decomposes into B‐containing species and interferes with the nucleation and growth of sp2‐bonded carbon, thus enabling to directly produce topological defects during carbon growth. Impressively, the H3BO3‐mediated defect‐rich hierarchical nanocarbons achieve a high H2O2 production rate over 20 h of continuous electrocatalysis with a stable current density (> 100 mA·cm–2) and Faradaic efficiency (> 90%).