Stability and Core-Level Signature of Nitrogen Dopants in Carbonaceous Materials
Stability and Core-Level Signature of Nitrogen Dopants in Carbonaceous Materials
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DOI：
10.1021/acs.chemmater.5b02370
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发表时间：
2015-08
影响因子：
8.6
通讯作者：
Ziqi Tian;S. Dai;D. Jiang
中科院分区：
文献类型：
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作者：
Ziqi Tian;S. Dai;D. Jiang
氮掺杂是调整碳材料性能和功能的重要策略。但是sp2-碳骨架中氮基团的化学形态尚未确定。在这里，我们解决了两个重要的问题，在氮掺杂的碳质材料从计算方法：不同的氮基团的相对稳定性和它们的X射线光电子能谱（XPS）签名的核心水平（N 1 s）的电子结合能。四种类型的氮基团（石墨，吡咯，氮杂吡咯，吡啶）在69个模型化合物进行了检查。计算的形成能表明，吡咯和吡啶氮显着更稳定（约110千焦/摩尔）比石墨和氮杂吡咯氮。这种稳定性趋势可以从Clar的六重规则中得到理解。预测的N 1 s结合能显示出相对较高的一致性之间的每种掺杂剂类型，从而提供了一个指导，以确定氮基团。相对稳定…
Nitrogen doping is an important strategy in tuning the properties and functions of carbonaceous materials. But the chemical speciation of the nitrogen groups in the sp2-carbon framework has not been firmly established. Here we address two important questions in nitrogen doping of carbonaceous materials from a computational approach: the relative stability of different nitrogen groups and their X-ray photoelectron spectrum (XPS) signatures of the core-level (N 1s) electron binding energies. Four types of nitrogen groups (graphitic, pyrrolic, aza-pyrrolic, and pyridinic) in 69 model compounds have been examined. Computed formation energies indicate that pyrrolic and pyridinic nitrogens are significantly more stable (by about 110 kJ/mol) than graphitic and aza-pyrrolic nitrogens. This stability trend can be understood from the Clar’s sextet rule. Predicted N 1s binding energies show relatively high consistency among each dopant type, thereby offering a guide to identify nitrogen groups. The relative stabilit...