Zhang Qiqi, Cao Changsheng, Zhou Shenghua, Wei Wenbo, Chen Xin, Xu Rongjie, Wu Xin-Tao, Zhu Qi-Long
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
College of Science, Northeast Agricultural University, Harbin, 150030, China.
Adv Mater. 2024 Sep;36(39):e2408341. doi: 10.1002/adma.202408341. Epub 2024 Aug 4.
The electrosynthesis of hydrogen peroxide (HO) from O or HO via the two-electron (2e) oxygen reduction (2e ORR) or water oxidation (2e WOR) reaction provides a green and sustainable alternative to the traditional anthraquinone process. Herein, a paired-electrosynthesis tactic is reported for concerted HO production at a high rate by coupling the 2e ORR and 2e WOR, in which the bifunctional oxygen-vacancy-enriched BiO nanorods (O-BiO-EO), obtained through electrochemically oxidative reconstruction of Bi-based metal-organic framework (Bi-MOF) nanorod precursor, are used as both efficient anodic and cathodic electrocatalysts, achieving concurrent HO production at both electrodes with high Faradaic efficiencies. Specifically, the coupled 2e ORR//2e WOR electrolysis system based on such distinctive oxygen-defect Bi catalyst displays excellent performance for the paired-electrosynthesis of HO, delivering a remarkable cell Faradaic efficiency of 154.8% and an ultrahigh HO production rate of 4.3 mmol h cm. Experiments combined with theoretical analysis reveal the crucial role of oxygen vacancies in optimizing the adsorption of intermediates associated with the selective two-electron reaction pathways, thereby improving the activity and selectivity of the 2e reaction processes at both electrodes. This work establishes a new paradigm for developing advanced electrocatalysts and designing novel paired-electrolysis systems for scalable and sustainable HO electrosynthesis.
通过双电子（2e）氧还原（2e ORR）或水氧化（2e WOR）反应从O₂或H₂O₂电合成过氧化氢（H₂O₂），为传统蒽醌法提供了一种绿色且可持续的替代方法。在此，报道了一种配对电合成策略，通过耦合2e ORR和2e WOR以高产率协同生产H₂O₂，其中通过对Bi基金属有机框架（Bi-MOF）纳米棒前驱体进行电化学氧化重构获得的双功能富氧空位BiO纳米棒（O-BiO-EO），用作高效的阳极和阴极电催化剂，在两个电极上同时实现H₂O₂的高产率和法拉第效率。具体而言，基于这种独特的氧缺陷Bi催化剂的耦合2e ORR//2e WOR电解系统在H₂O₂的配对电合成中表现出优异性能，电池法拉第效率高达154.8%，H₂O₂产率高达4.3 mmol h⁻¹ cm⁻²。实验结合理论分析揭示了氧空位在优化与选择性双电子反应途径相关的中间体吸附方面的关键作用，从而提高了两个电极上2e反应过程的活性和选择性。这项工作为开发先进电催化剂和设计用于可扩展且可持续的H₂O₂电合成的新型配对电解系统建立了新范式。
