甘氨酸衍生的双介孔掺氮有序介孔炭用于超级电容器和氧气还原  

Glycine-derived nitrogen-doped ordered mesoporous carbons with a bimodal mesopore size distribution for supercapacitors and oxygen reduction

作　　者：邵颖 胡泽宇 姚艳 卫翔茹 高兴敏 吴张雄 SHAO Ying;HU Ze-yu;YAO Yan;WEI Xiang-ru;GAO Xing-min;WU Zhang-xiong(Particle Engineering Laboratory,School of Chemical and Environmental Engineering,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou 215123,China)

机构地区：[1]苏州大学材料与化学化工学部化学与环境工程学院,颗粒工程实验室,江苏苏州215123

出　　处：《新型炭材料》2022年第1期259-276,共18页New Carbon Materials

基　　金：国家自然科学基金项目(21875153,21501125);江苏省自然科学基金项目(BK20150312);江苏省双创团队资助项目;江苏省高校优势学科经费(PAPD).

摘　　要：掺氮多孔炭材料在电化学能量储存和转化方面具有良好的应用前景。可控的氮原子掺杂与孔结构设计对提高其性能起着重要作用。本工作利用无溶剂纳米铸造法,以甘氨酸(Gly)为单一前驱体、以SBA-15为硬模板,制备了掺氮有序介孔炭材料(N-OMCs)。甘氨酸在SBA-15孔道内的限域热解对提高碳产率、氮掺杂量以及构筑双介孔结构非常重要。NOMCs具有高比表面积(923~1374 m^(2)·g^(−1))、大孔隙体积(1.32~2.21 cm^(3)·g^(−1))、双介孔分布(4.8和6.2~20 nm)和高氮含量(3.66%~12.23%)。通过改变Gly/SBA-15的质量比和温度,可以调节材料的结构有序性、粒径、孔隙率和氮掺量。N-OMCs作为电极材料在超级电容器中具有较高性能。最佳样品在0.5 A·g^(−1)时具有298 F·g^(−1)的比电容、高倍率性能(在30 A·g^(−1)时保留70%)与良好的循环稳定性。同时,N-OMCs在电催化氧还原反应(ORR)中也表现出良好性能。最佳样品的起始电位和半波电位分别为0.92和0.83 V,极限电流密度为5.06 mA·cm^(-2)。本工作还讨论了N-OMCs的理化性质与其性能的关系。Nitrogen-doped carbon materials are promising for electrochemical energy storage and conversion.Dopant control and pore engineering play important roles in improving their performance.We have synthesized nitrogen-doped ordered mesoporous car-bons(N-OMCs)with a bimodal mesopore size distribution using a solvent-free nanocasting method.The simplest amino acid(gly-cine,Gly)was used as the only carbon precursor and ordered mesoporous silica SBA-15 as the hard template.The confined pyrolys-is of Gly in SBA-15 leads to efficient carbonization,nitrogen doping and an interesting structure.The N-OMCs have high surface areas(923–1374 m^(2)·g^(−1)),large pore volumes(1.32–2.21 cm^(3)·g^(−1)),a bimodal distribution of mesopore sizes(4.8 and 6.2–20 nm)and high nitrogen contents(3.66%–12.23%).The effects of the Gly/SBA-15 mass ratio(1–3)and carbonization temperature(700–1000°C)on the physicochemical properties of the N-OMCs were studied.When used as electrode materials the N-OMCs have a high performance in supercapacitors.A typical sample has a large specific capacitance of 298 F·g^(−1),a good rate capability(70%re-tention at 30 A·g^(−1))and high stability.The different capacitances and rate capabilities of the N-OMCs are discussed by correlating them with their physicochemical properties.A balance of surface area,degree of graphitization,nitrogen doping,and an open meso-porous structure is essential to achieve the best performance.The N-OMCs also have a good performance in the electrocatalytic oxy-gen reduction reaction.A typical sample has a high onset of 0.92 V,a high half-wave potential of 0.83 V and a large limiting current density of 5.06 mA·cm^(-2).

关 键 词：介孔炭 纳米浇筑 氮掺杂 甘氨酸 超级电容器 氧气还原 

分 类 号：TQ127.11[化学工程—无机化工]