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通过抑制高过电位下的HO分解实现空位激活的B掺杂以高效进行2e氧还原

Vacancy-Activated B-Doping for Efficient 2e Oxygen Reduction through Suppressing HO Decomposition at High Overpotential.

作者信息

Cui Wangyang, Zhen Zhiyuan, Sun Yuanyuan, Liu Xiaofeng, Chen Jinhui, Liu Sijia, Ren Hao, Lin Yan, Wu Mingbo, Li Zhongtao

机构信息

State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao, 266580, P. R. China.

Department of Chemistry, Tsinghua University, Beijing, 100084, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2025 Mar 24;64(13):e202423056. doi: 10.1002/anie.202423056. Epub 2025 Jan 17.

Abstract

The production of hydrogen peroxide (HO) through two-electron oxygen reduction reaction (2e ORR) has emerged as a more environmentally friendly alternative to the traditional anthraquinone method. Although oxidized carbon catalysts have intensive developed due to their high selectivity and activity, the yield and conversion rate of HO under high overpotential still limited. The produced HO was rapidly consumed by the increased intensity of HO reduction, which could ascribe to decomposition of peroxide radicals under high voltage in the carbon catalyst. To overcome this issue, a B doped carbon have been developed to catalyze 2e ORR with high efficient through suppressing HO decomposition at high potential. Thus, thermal reducing of oxygen containing groups (OCGs) on graphite could construct defects and vacancies, which in situ convert to B-C subunits on the edge of graphene sheets. The introduction of B-C effectively prevented the decomposition of the *O-O bond and provided suitable adsorption capacity for *OOH, achieving excellent selectivity for the 2e ORR across a wide voltage range. Finally, a remarkable HO yield of 7.91 mmol cm h was delivered at an industrial current density of 600 mA cm, which could provide "green" pathway for scale-upable synthesis HO.

摘要

通过双电子氧还原反应(2e ORR)生产过氧化氢(HO)已成为一种比传统蒽醌法更环保的替代方法。尽管氧化碳催化剂因其高选择性和活性而得到了深入发展,但在高过电位下HO的产率和转化率仍然有限。产生的HO因HO还原强度增加而迅速消耗,这可能归因于碳催化剂在高电压下过氧化物自由基的分解。为克服这一问题,已开发出一种硼掺杂碳,通过在高电位下抑制HO分解来高效催化2e ORR。因此,石墨上含氧基团(OCGs)的热还原可构建缺陷和空位,这些缺陷和空位在石墨烯片边缘原位转化为B-C亚基。B-C的引入有效防止了O-O键的分解,并为OOH提供了合适的吸附能力,在很宽的电压范围内实现了对2e ORR的优异选择性。最后,在600 mA cm的工业电流密度下,HO的产率达到了7.91 mmol cm h,这可为可规模化合成HO提供“绿色”途径。

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