Constructing Graphitic-Nitrogen-Bonded Pentagons in Interlayer-Expanded Graphene Matrix toward Carbon-Based Electrocatalysts for Acidic Oxygen Reduction Reaction
Constructing Graphitic-Nitrogen-Bonded Pentagons in Interlayer-Expanded Graphene Matrix toward Carbon-Based Electrocatalysts for Acidic Oxygen Reduction Reaction
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在层间膨胀石墨烯基体中构建石墨-氮键合五边形用于酸性氧还原反应的碳基电催化剂
DOI：
10.1002/adma.202103133
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Qianwang Chen
中科院分区：
文献类型：
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作者：
Shuai Liu;Yongchao Zhang;Binghui Ge;Fangcai Zheng;Nan Zhang;Ming Zuo;Yang Yang;Qianwang Chen
具有高电催化活性的无金属碳基材料是多种可再生能源系统中氧还原反应（ORR）的有前途的催化剂。然而，碳基材料在酸性电解质中的性能远不如铂基催化剂。在这里，报道了一种新型碳基电催化剂，其在0.1mHClO4中的ORR具有0.81 V的半波电位和比商业20 wt% Pt/C更好的耐久性（100 h反应时间）。它是通过在石墨碳中构建石墨-氮（GN）-键合的五边形来实现的，以提高碳位点的固有活性，并通过扩大层间距来增加活性位点的数量。X射线吸收光谱和像差校正电子显微镜表征证实了在这种碳材料中形成GN键合的五边形。拉曼和X射线光电子能谱表明，活性与五边形和相邻GN原子的量线性相关。密度泛函理论进一步证明，相邻的GN原子显著增加GN键合的五边形的碳原子处的电荷密度，这是ORR的活性来源。
Metal‐free carbon‐based materials with high electrocatalytic activity are promising catalysts for the oxygen reduction reaction (ORR) in several renewable energy systems. However, the performance of carbon‐based materials is far inferior to that of Pt‐based catalysts in acid electrolytes. Here, a novel carbon‐based electrocatalyst is reported toward ORR in 0.1mHClO4with half‐wave potential of 0.81 V and better durability (100 h reaction time) than commercial 20 wt% Pt/C. It is achieved by constructing graphitic‐nitrogen (GN)‐bonded pentagons in graphitic carbon to improve the intrinsic activity of the carbon sites and increasing the amount of active sites via expanding the interlayer spacing. X‐ray absorption spectroscopy and aberration‐corrected electron microscopy characterizations confirm the formation of GN‐bonded pentagons in this carbon material. Raman and X‐ray photoelectron spectroscopy reveal that the activity is linearly associated with the amounts of both pentagons and adjacent GN atoms. Density function theory further demonstrates that adjacent GN atoms significantly increase the charge density at the carbon atom of a GN‐bonded pentagon, which is the activity origin for the ORR.