• 关键词：脱硝  氧化石墨烯  石墨烯  密度泛函理论

• 基金项目：国家自然科学基金（No.51776071）；中央高校基本科研业务费专项（No.2016YQ07，2018MS034，2018ZD08）

• 史飞
• 华北电力大学, 能源动力与资源工程学院, 北京 102206

• 麻冰云
• 华北电力大学, 能源动力与资源工程学院, 北京 102206

• 覃吴
• 华北电力大学, 能源动力与资源工程学院, 北京 102206

• 孙保民
• 华北电力大学, 能源动力与资源工程学院, 北京 102206

• 摘要：石墨烯氧化物（GO）通常是羟基化石墨烯（HyG）和羧基化石墨烯（CyG）负载金属或金属氧化物，作为催化剂可以有效地催化烟气脱硝，对环境保护具有重要意义.本文采用密度泛函理论（DFT）计算来评估HyG与NO之间的相互作用，以揭示HyG的氧化活性.首先基于5×5×1、6×6×1、7×7×1、8×8×1和9×9×1周期性石墨烯超晶胞中的碳空位能和OH—结合能来优选HyG模型，并对优化后的HyG的电子特性（包括前沿轨道、状态密度）进行研究.进而通过NO和HyG之间的相互作用，揭示HyG氧化NO的反应机理，并利用过渡态理论估算关键步骤的速率常数，进行动力学建模以确定羟基化石墨烯氧化NO脱硝反应特性.研究结果表明，无缺陷的羟基化石墨烯氧化NO的活性高于有缺陷的羟基化石墨烯，这为GO基催化材料的设计提供了理论指导.

• Abstract：Metal or metal oxide supported on graphene oxides (GO), usually hydroxylated graphene (HyG) and carboxylated graphene (CyG), can efficiently catalyze De-NO_x in fuel gas, which is of great significance for environmental protection. This work evaluated the interaction between HyG and NO using density functional theory (DFT) calculation, to reveal the oxidation activity of HyG. The HyG model was first optimized based on comparatively calculating the carbon vacancy energy and OH-binding energy of the periodic graphene supercells of 5×5×1, 6×6×1, 7×7×1, 8×8×1, and 9×9×1. Detailed electronic properties (including frontier orbital, density of state, and nucleophilic Fukui function) of the optimized HyG systems were studied. Then the interaction between NO and HyG was investigated to reveal the reaction mechanism of NO oxidation by HyG. The rate constant for the key step was estimated using transition state theory, and kinetic modeling was carried out to identify the De-NO_x reaction characteristic by oxidizing NO using HyG. Results show that the defect-free HyG is more active than the defective HyG, which provides theoretical guidance for designing novel GO-based catalysts.

• Key words：De-NO_x  graphene oxide  graphene  density functional theory (DFT)

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