Enhanced H 2 O 2 production by selective electrochemical reduction of O 2 on fluorine-doped hierarchically porous carbon
Enhanced H 2 O 2 production by selective electrochemical reduction of O 2 on fluorine-doped hierarchically porous carbon
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DOI：
10.1016/j.jcat.2017.11.008
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发表时间：
2018
影响因子：
7.3
通讯作者：
K. Zhao;Yan Su;X. Quan;Yanming Liu;Shuo Chen;Hongtao Yu
中科院分区：
文献类型：
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作者：
K. Zhao;Yan Su;X. Quan;Yanming Liu;Shuo Chen;Hongtao Yu
通过双电子氧还原反应途径电化学合成过氧化氢（H2 O2）是目前蒽醌法的一种有前途的替代方法。O2还原生成H2 O2与O2还原生成H2O是竞争反应，其选择性与OOH中间体在电催化剂表面的吸附能有关。通常，通过改变OOH中间体的电子结构可以控制其在催化剂上的键合性质。本文通过掺杂不同种类和含量的氟来调节多孔碳材料的电子结构。H2 O2的产率取决于F的含量，当F含量为3.41at.%时，催化剂对H2 O2的电合成具有最佳的催化活性。在0.2 V ~-0.3 V vs. RHE（pH 1）的电位范围内，所得的F掺杂多孔碳（FPC）催化剂表现出良好的H2 O2选择性（97.5-83.0%）和H2 O2生成速率（112.6-792.6 mmol h−1g− 1）。密度泛函理论（DFT）计算和实验结果表明，CF2，3的引入促进了O2分子的活化和OOH中间体的脱附，这对H2 O2的合成至关重要.
Electrochemical synthesis of hydrogen peroxide (H2O2) via two-electron pathway of oxygen reduction reaction is a promising alternative to the current anthraquinone process. The H2O2production from O2is a competing reaction with four-electron O2reduction to H2O, and the selectivity is related to the adsorption energy of the OOH intermediate on electrocatalysts surface. Generally, the properties for binding of OOH intermediate on catalysts can be controlled by changing its electronic structure. Herein, the electronic structure of porous carbon materials was tuned by doping different types and contents of fluorine species. The yield of H2O2generation depended on the F content and the best catalytic activity toward H2O2electrosynthesis was obtained with F content of 3.41 at.%. The resultant F-doped porous carbon (FPC) catalysts exhibited good H2O2selectivity of 97.5–83.0% and the H2O2production rate could reach 112.6–792.6 mmol h−1g−1over the potential range of 0.2 V to −0.3 vs. RHE (pH 1). The density functional theory (DFT) calculations and experiments revealed that the incorporation of CF2, 3into carbon plane promotes the activation of O2molecule and facilitates desorption of OOH intermediate, which was crucial to H2O2synthesis.