Citation: FEI Huilong, DUAN Xiangfeng. Nitrogen Doped Graphdiyne Enhances Oxygen Reduction Reactions[J]. Acta Physico-Chimica Sinica, ;2019, 35(6): 559-560. doi: 10.3866/PKU.WHXB201809016 shu

Nitrogen Doped Graphdiyne Enhances Oxygen Reduction Reactions

FEI Huilong ^1,, ,
DUAN Xiangfeng ^2,,

1.
College of Chemistry and Chemical Engineering, State Key Laboratory for Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082, P. R. China
2.
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095, USA

Corresponding author: FEI Huilong, hlfei@hnu.edu.cn DUAN Xiangfeng, xduan@chem.ucla.edu

. sp-N掺杂的石墨炔合成图。(b)碱性条件下，氮掺杂的石墨炔及商业Pt/C催化剂的半波电位和动力学电流密度。(c)酸性和碱性条件下，电流密度随sp-N含量变化图。

下载: 全尺寸图片幻灯片

阴极氧还原反应(ORR)是燃料电池和金属-空气电池中的一个关键反应，在能源转化领域起着至关重要的作用^{1, 2}。由于其较高的过电位，当前氧还原反应一般都需要使用贵金属铂(Pt)基催化剂。但其高昂的成本和较差的耐久性极大地限制了燃料电池的规模化与商业化进程^{3, 4}。从长远来看，寻找高效的非金属催化剂代替Pt是降低成本的根本途径。在非金属催化剂中，氮掺杂碳材料的氧还原催化活性较高，是理想的氧还原反应催化剂之一⁵。目前，常用的氮掺杂碳材料主要基于石墨烯和碳纳米管，但限制于自身的sp²杂化结构，相应的氮构型主要有吡啶氮、吡咯氮和石墨氮等^6-8。据前人的研究，在氮掺杂碳材料催化剂中，氮原子的掺杂形式与催化性能的高低密切相关，因此开发新的氮掺杂形式有望进一步提升氮掺杂碳材料的催化活性。石墨炔，作为一种新型碳材料，其独特的sp杂化碳原子有望带来新的氮掺杂构型，为发展新的氮掺杂形式带来可能⁹。

近日，中国科学院过程工程研究所王丹研究员团队通过周环反应在薄层石墨炔中成功地引入了一种新形式的N原子，即sp杂化的N原子(见图)。值得注意的是，与以往的掺杂往往在缺陷位置和边缘位置进行不同，这种sp-N是通过化学反应在碳碳三键位置引入的，实现了位点可控的掺杂。此外，通过调控反应前驱体的比例，可以实现对sp-N含量的精确控制。作者利用X射线吸收近边结构谱(XANES)和X射线光电子能谱(XPS)验证了sp-N原子存在的位点及含量。电化学测试发现sp-N掺杂的石墨炔材料具有非常优异的ORR性能，其在碱性条件下的催化活性可以媲美Pt/C催化剂；而在酸性条件下，这一材料的催化活性虽略低于Pt/C催化剂，但相比其它非金属催化剂，其活性仍要高出很多。同时，该材料表现出比Pt/C更好的稳定性和耐甲醇中毒的特性。实验表征和理论计算表明，sp-N是提升活性的关键因素，它的存在有利于O₂的吸附和活化，使电子更易转移到催化剂表面。该研究与中国科学院化学研究所李玉良院士、北京师范大学朱嘉团队等合作完成。

该研究工作近期已在Nature Chemistry上在线发表¹⁰。该工作通过利用石墨炔独有的分子结构，应用化学反应，将一种新型的N杂化形式，即sp-N，定点定量的引入到碳材料中。这种可控的掺杂合成策略以及对合成机理的深入理解为设计其它催化剂提供了新的思路，将拓宽在其它领域的应用。

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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Nitrogen Doped Graphdiyne Enhances Oxygen Reduction Reactions

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通讯作者: 陈斌, bchen63@163.com