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低电负性阴离子掺杂调控钴酸锌的电子结构以提高析氧反应活性 被引量:1
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作者 熊兵 葛良兵 +7 位作者 雷雪颜 汪扬凯 杨吉文 李威威 李晓宁 程振祥 傅正平 陆亚林 《Science China Materials》 SCIE EI CAS CSCD 2023年第5期1793-1800,共8页
电子结构和电导率是析氧反应活性的重要描述符,它们可以通过掺杂来调节.鉴于金属掺杂通常会减少电催化剂的活性位点数量,本工作探究了阴离子掺杂对尖晶石钴酸锌(ZCO)电子结构及其析氧活性的影响.与三价钴为主的ZCO相比,用电负性较低的... 电子结构和电导率是析氧反应活性的重要描述符,它们可以通过掺杂来调节.鉴于金属掺杂通常会减少电催化剂的活性位点数量,本工作探究了阴离子掺杂对尖晶石钴酸锌(ZCO)电子结构及其析氧活性的影响.与三价钴为主的ZCO相比,用电负性较低的硫取代氧会提高低自旋态(t_(2g)-^(6)e_(g)^(1))二价钴的占比,其析氧活性要高于低自旋态的三价钴(t_(2g)-^(6)e_(g)^(0)).掺硫钴酸锌(ZCO-S)中钴离子和阴离子之间的电子密度的再分布导致了二价钴的增多,而且钴和硫离子间的强共价作用也会加速电荷迁移.ZCO-S在1.65伏(相对于可逆氢电极)下的比活性比原始ZCO高11倍.相反,掺入具有较高电负性和价态的氟(F)并不能有效地改善电子结构,最终导致材料析氧活性的降低.本工作建立了所掺阴离子的电负性与钴酸锌本征析氧活性之间的联系,并提供了一种通过掺杂不同电负性的阴离子来调控尖晶石氧化物的电子结构的简单有效的方法,这为合理设计高性能尖晶石电催化剂提供了新途径. 展开更多
关键词 oxygen evolution reaction anion doping ELECTRONEGATIVITY electronic structure SPINEL
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Strong and tough graphene papers constructed with pyrene-containing small molecules via π-π/Hbonding synergistic interactions 被引量:1
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作者 Hong Yuan liangbing ge +11 位作者 Kun Ni Xiukai Kan Si-Ming Chen Mengting Gao Fei Pan Jianglin Ye Fang Xu Na Shu Jieyun Li Tao Suo Shu-Hong Yu Yanwu Zhu 《Science China Materials》 SCIE EI CAS CSCD 2021年第5期1206-1218,共13页
Lightweight yet strong paper with high toughness is desirable especially for impact protection. Herein we demonstrated electrically conductive and mechanically robust paper(AP/PB-GP) made of reduced graphene oxide via... Lightweight yet strong paper with high toughness is desirable especially for impact protection. Herein we demonstrated electrically conductive and mechanically robust paper(AP/PB-GP) made of reduced graphene oxide via interfacial crosslinking with 1-aminopyrene(AP) and 1-pyrenebutyrat(PB) small molecules. The AP/PB-GP with thickness of over ten micrometer delivers a record-high toughness(~69.67 ± 15.3 MJ m^(-3) in average), simultaneously with superior strength(close to 1 GPa), allowing an impressive specific penetration energy absorption(~0.17 MJ kg^(-1)) at high impact velocities when used for ballistic impact protection. Detailed interfacial and structural analysis reveals that the reinforcement is synergistically determined by π-π interaction and H-bonding linkage between adjacent graphene lamellae. Especially, the defective pores within the graphene platelets benefit the favorable adsorption of the pyrene-containing molecules, which imperatively maximizes the interfacial binding, facilitating deflecting crack and plastic deformation under loading. Density functional theory simulation suggests that the coupling between the polar functional groups, e.g., –COOH, at the edges of graphene platelets and –NH_(2) and –COOH of AP/PB are critical to the formation of hydrogen bonding network. 展开更多
关键词 graphene paper π-πinteraction H-BONDING synergistic reinforcement mechanical properties
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