含氧功能团调控的碳材料用于选择性氧气还原制备过氧化氢及其机理研究

High value-added and clean hydrogen peroxide can be produced efficiently and steadily through modulating the selectivity of the oxygen reduction reaction. Recent studies manifest that oxygen functional group modified carbon nanomaterials possess outstanding electrocatalytic performance for H2O2 production by oxygen reduction reaction. In this project, we propose to prepare oxygen-containing functional group modified carbon nanomaterials via oxidation treatment, and test their electrocatalytic performance for H2O2 production. Using ingenious chemical titration method, the specific oxygen functional groups can be selectively deactivated. The electrocatalytic performance before and after the chemical deactivation are compared to ascertain the effect of different oxygen-containing functional groups on the H2O2 production performance. Meanwhile, combined with the modified Boehm’s titration method and other characterizations, the content of the oxygen-containing groups on the electrocatalytic performance are also studied. The oxygen-containing functional groups are then removed by reduction treatment to explore whether the defects are active sites during the H2O2 production. The identification of active sites can further feedback and guide the preparation and optimization of the carbon nanomaterials to improve their electrocatalytic H2O2 production performance. By carrying out this program, we can disclose the relationship between the structure and the performance of the catalyst, and provide the new methods for deciphering the active sites of the oxidized carbon nanomaterials, as while as uncover the mechanism of H2O2 production through oxygen reduction. In this research, the preparation cost of electrocatalysts can be reduced so that the in situ generated H2O2 by electrocatalysis can be readily used for practical water pollution treatment.

通过调节氧气还原反应的选择性可以绿色、高效、稳定地产生具有高附加值的过氧化氢。含氧功能团修饰的碳材料被证明具有优异的电催化氧气还原产生H2O2的性能。本项目拟通过氧化处理方法得到含氧功能团修饰的碳纳米材料，并对其进行电催化产生H2O2的性能测试。利用合理设计的化学滴定方法选择性屏蔽氧化碳纳米材料中不同的含氧功能团，研究含氧功能团种类对产生H2O2选择性的影响。同时，结合改进的Boehm滴定方法及其它表征手段，研究含氧功能团含量对电催化性能的影响。再将各种含氧官能团还原消除，判断活性位点与缺陷的关系。根据得出的活性位点，进一步反馈指导材料的合成及优化，提高碳纳米材料的电催化产生H2O2的性能。项目的实施，可以揭示碳基电催化剂的构-效关系，提供研究该类材料活性位点的新方法，阐明氧气还原制备H2O2的反应机理。本研究可以降低电催化剂制备成本，使电催化原位产生的H2O2用作实际水污染处理成为可能。

过氧化氢是非常重要的化学品，在医药、卫生和环境保护等领域起到非常重要的作用。传统的工业蒽醌法制过氧化氢工艺复杂、能耗较高且有安全隐患。通过合理地设计合成电催化材料，调节氧气还原反应的选择性可以绿色、高效、稳定地产生具有高附加值的过氧化氢。本项目通过独特的氧化处理方法（如热活化过硫酸盐、揉制氧化等）得到含氧功能团修饰的碳纳米材料，对材料的形貌、结构、组成等进行了充分的表征，并对该材料进行电催化产生H2O2的性能进行测试，得到了高选择性、高产率、高稳定性的氧气2电子还原电催化剂。结合适当的理论模拟和原位测试（如电化学原位红外光谱）技术，揭示了该类材料高电催化活性的来源，获取了电催化剂的结构-性能之间相互关系的规律。为氧气2电子还原产H2O2的深入研究开辟了新的研究思路，对该领域的研究具有借鉴意义。基于该项目的研究，在国际学术期刊上发表SCI论文十余篇，获批专利2项（其中一项为发明专利，一项为实用新型专利）。培养研究生4名，参加国内外学术会议并邀请相关领域专家交流访问。