钾掺杂三维有序大孔结构Mn0.5Ce0.5Oδ催化剂合成及其催化燃烧炭烟性能

催化学报 , 2015, (11): 1957-1967. doi: 10.1016/S1872-2067(15)60949-4

钾掺杂三维有序大孔结构Mn0.5Ce0.5Oδ催化剂合成及其催化燃烧炭烟性能

于学华 ^1, , 赵震 ^2, , 韦岳长 ^3, , 刘坚 ^4, , 李建梅 ^5, , 段爱军 ^6, , 姜桂元 ^7,

1.中国石油大学北京重质油国家重点实验，北京102249; 沈阳师范大学能源与环境催化研究所，辽宁沈阳110034

2.中国石油大学北京重质油国家重点实验,北京,102249

3.中国石油大学北京重质油国家重点实验,北京,102249

4.中国石油大学北京重质油国家重点实验,北京,102249

5.中国石油大学北京重质油国家重点实验,北京,102249

6.中国石油大学北京重质油国家重点实验,北京,102249

7.中国石油大学北京重质油国家重点实验,北京,102249

基金项目: Beijing Nova Program(Z141109001814072) Specialized Research Fund for the Doctoral Program of High Education of China(20130007120011) 中国石油大学(北京)科学基金(2462013YJRC13,2462013BJRC003) the Science Founda-tion of China University of Petroleum-Beijing (2462013YJRC13,2462013BJRC003).基金来源:国家自然科学基金(21177160,21303263,21477164) 高等学校博士学科点专项科研基金(20130007120011) 北京市新星计划(Z141109001814072) the National Natural Science Foundation of China(21177160,21303263,21477164)

关键词：三维有序大孔结构 , 锰铈复合氧化物催化剂 , 钾掺杂 , 炭烟燃烧

Synthesis of K-doped three-dimensionally ordered macroporous Mn0.5Ce0.5Oδcatalysts and their catalytic performance for soot oxidation

Keywords： Three-dimensionally ordered , macroporous structure , Mn0.5Ce0.5Oδcatalyst , Potassuim doping

柴油发动机是一种高效耐用的发动机,具有广阔的应用前景.但柴油车尾气中的炭烟颗粒吸附了许多有毒有害物质,也是城市PM2.5的主要来源之一,对人类生命安全造成极大威胁.因此,降低和消除柴油车尾气中的炭烟颗粒是柴油车尾气净化的重要任务.尾气后处理是炭烟颗粒进入大气环境前的最后一道程序,可有效控制柴油车尾气中炭烟颗粒排放.其中,催化净化催化剂是尾气后处理技术的核心.研究表明,炭烟颗粒催化燃烧是一个气-固-固三相深度氧化反应,因此开发新型催化剂体系,改善催化剂与炭烟颗粒的接触,提高催化剂的本征活性,对于研制高活性炭烟燃烧催化剂具有重要的实际意义. ；对于三维有序大孔(3DOM)结构催化剂,大孔有利于炭烟颗粒进入催化剂内部并与活性位点接触,而有序的孔道结构可以促进炭烟颗粒在催化剂孔道内传输.因此,将催化炭烟颗粒燃烧催化剂设计成3DOM结构,可促进炭烟颗粒催化燃烧,提高催化剂活性.研究表明,锰铈复合氧化物材料在炭烟颗粒催化燃烧中表现出比单一的锰氧化物和铈氧化物更好的性能.而将K与Ce和Mn形成复合氧化物,利用三者之间的协同作用,将可使K掺杂3DOM结构Mn0.5Ce0.5Oδ催化剂具有更高的催化活性.本文利用胶体晶体模板法成功制备了3DOM结构的Mn0.5Ce0.5Oδ复合氧化物,并采用简单的等体积浸渍方法成功制备了不同K担载量的K掺杂3DOM结构Mn0.5Ce0.5Oδ催化剂(K-MCO).表征结果表明, K-MCO催化剂具有贯通有序的大孔结构,但焙烧温度和焙烧时间会对大孔结构的规整性有一定影响；催化剂中K含量、焙烧温度和焙烧时间对K-MCO的晶型影响较大,催化剂中出现了一个新的晶相K2Mn4O8.另外, K含量、焙烧温度和焙烧时间对催化剂的氧化还原性能也有较大影响.评价结果表明,所制催化剂对炭烟催化燃烧均具有较高活性,其中20% K-MCO-4h催化剂活性最高,催化燃烧炭烟的T50(炭烟的最大燃烧峰值)为331oC, CO2选择性为95.3%.催化剂的大孔结构效应以及K, Mn和Ce三者间的协同作用有利于提高催化剂催化燃烧炭烟的活性.另外,由于柴油车尾气排气口温度范围为175–400 oC,而本文所制催化剂催化燃烧炭烟的温度低于400 oC,因此该催化剂可以在柴油车尾气排气口温度范围内进行炭烟催化燃烧.由于具有合成步骤简单、活性高以及成本低等优点,该催化剂在实际应用方面具有广阔前景.

A series of K‐doped Mn0.5Ce0.5Oδ(K‐MCO) catalysts with three‐dimensionally ordered macroporous (3DOM) structure and different K loadings were successfully synthesized using simple methods. These catalysts exhibited well‐defined 3DOM nanostructure, which consisted of extensive inter‐connecting networks of spherical voids. The effects of the calcination temperature and calcination time on the morphological characteristics and crystalline forms of the catalysts were systematically studied. The catalysts showed high catalytic activity for the combustion of soot. 3DOM 20%K‐MCO‐4h catalyst, in particular, showed the highest catalytic activity of all of the catalysts studied (e.g., T50=331 °C and SmCO2=95.3%). The occurrence of structural and synergistic effects among the K, Mn, and Ce atoms in the catalysts was favorable for enhancing their catalytic activity towards the combustion of diesel soot. Furthermore, the temperatures required for the complete combustion of the soot (<400 °C) were well within the exhaust temperature range (175–400 °C), which means that the accumulated soot can be removed under the conditions of the diesel exhaust gas. These catalysts could therefore be used in numerous practical applications because they are easy to synthesize, exhibit high catalytic activity, and can be made from low cost materials.

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