摘要：过渡金属氧化物催化剂(如Co3O4基催化剂等)对水汽很灵敏，在含水条件下非常容易失去活性。在低温CO氧化的实际应用过程中，催化剂的活性不可避免地会受到水汽和CO2等多种因素的影响，因此，研究含水条件下CO氧化反应催化剂的活性和稳定性具有重要的学术价值和实际意义。

本文着重研究了催化剂的组成和制备条件对Fe-Co-O催化剂物化性质和催化性能的影响。采用低温N2吸附、XRD、XPS、FT-IR、H2-TPR、CO/O2-TPD、NMR、TG和TEM等方法对催化剂的物理化学性质进行表征，采用in situ DRIFTS技术研究了催化剂表面的吸附和表面反应，研究了催化剂表面高分子层的含量及组成对催化剂抗水性的影响，取得了以下主要的研究成果。

（1）研究了催化剂组成、制备方法及条件对Fe-Co-O催化性能的影响。结果表明，无论是在常规条件(3-10 ppm H2O)还是在潮湿条件(0.6% H2O)下，草酸乙二醇辅助固相法制得的催化剂均比共沉淀法所得的催化剂具有更好的催化CO氧化的活性。同时，在Co3O4中掺杂Fe、在制备过程中添加草酸(OA)和乙二醇(EG)均能够显著提高Co3O4基催化剂在常规条件以及潮湿条件下对CO氧化的催化活性。当Fe/Co=3/16时，Fe3Co16Ox具有最好的对CO低温氧化反应的催化性能。

（2）研究了焙烧温度对Fe-Co-O催化性能的影响。结果表明，经250 ℃焙烧的催化剂具有高的比表面积、Co3+/Co2+ 比和氧空穴含量，并表现出优异的催化CO氧化反应的性能。Fe3Co16Ox-250催化剂可分别在-101 ℃ (在含有3-10ppm H2O时)和70 ℃(0.6vol.% H2O)将CO完全氧化，在含3.1%H2O的条件下，在90 ℃能使CO完全氧化，并保持1个月以上活性不降低。

（3）研究了在含水量和CO浓度对Fe-Co-O催化活性的影响。结果表明，22Fe-Co-O催化剂在水汽缺乏的条件(3-10ppm H2O)下比潮湿条件(0.6vol.% H2O)下对CO的浓度变化更加敏感，其原因是水的存在改变了催化反应的路径。表面吸附的OH-与CO会生成碳酸盐离子(CO* + OH* → COOH* + *, * 吸附位点)。表面高分子的存在可以抑制水在催化剂活性中心上的吸附。

（4）研究了高分子层对Fe-Co-O催化性能的影响。研究表明，高分子可能的结构为-(CH2CH2-O-COCOO-)n。不同焙烧温度会影响表面高分子层的厚度及含量，高分子层的存在可抑制纳米粒子长大，并明显提高催化剂的抗水性能，从而提高Co-Fe-O复合金属氧化物的催化性能。

(5)在原有基础上加入硝酸，硝酸腐蚀催化剂表层，产生更多的活性位点和高的氧空位，从而得到更好的催化性能。

关键词：Fe-Co复合氧化物；高分子层包覆的纳米催化剂；抗水性；CO氧化；催化剂制备

Abstract: transition metal oxide catalysts (such as Co3O4 base catalysts) are sensitive to water vapor and lose their activity easily under water containing conditions. In the practical application of low-temperature CO oxidation process, the activity of catalyst will inevitably influenced by many factors such as water vapor and CO2, therefore, the study of water cut under the condition of CO oxidation catalyst activity and stability has important academic value and practical significance.

The effect of catalyst composition and preparation conditions on the physicochemical properties and catalytic properties of fe-co-o catalyst was studied. Using N2 adsorption at low temperature, XRD, XPS, FT - IR, H2 - CO/O2 - TPD, TPR, NMR, TG and TEM methods for the chemical and physical properties of the catalysts were characterized, using the in situ DRIFTS technology to study the adsorption and surface reaction on the surface of the catalyst, the content of catalyst surface polymer layer and the study of influence on catalyst, water resistance, the following main research results were obtained.

(1) the influence of catalyst composition, preparation method and conditions on the catalytic performance of fe-co-o was studied. Results show that both in normal condition (3-10 PPM H2O) or under humid conditions (0.6% H2O), ethylene glycol oxalate auxiliary catalyst than coprecipitation of solid phase method, the catalyst has better catalytic activity of CO oxidation. At the same time, doping Fe in Co3O4, adding oxalic acid (OA) and ethylene glycol (EG) in the preparation process can significantly improve the catalytic activity of Co3O4 catalysts in CO oxidation under normal and moist conditions. When Fe/Co=3/16, Fe3Co16Ox has the best catalytic performance for Co oxidation at low temperature.