工程科学学报，第41卷，第2期：230-237,2019年2月 Chinese Joural of Engineering,Vol.41,No.2:230-237,February 2019 DOI:10.13374/j.issn2095-9389.2019.02.010;http://journals.ustb.edu.cn 钯掺杂a-MnO,无溶剂下催化氧化苯甲醇的性能 黄秀兵12)，王静静2)，郑海燕12)，路桂隆12)，王鹏2) 1)北京科技大学材料科学与工程学院，北京1000832)北京材料基因工程高精尖创新中心，北京100083 区通信作者，E-mail:xiubinghuang@usth.cdu.cn 摘要通过共沉淀和原位煅烧转化方法，将Pd掺杂δ-MnO,前驱体煅烧后制备得到Pd掺杂-MO,纳米棒催化材料.通 过氮气物理吸附、X射线衍射、透射电子显微镜、扫描电子显微镜、热重分析、X射线光电子能谱等技术对催化材料进行了表 征.扫描电镜和透射电镜结果显示，a-MnO,纳米棒表面没有明显的Pd纳米颗粒，表明Pd可能参杂到a-MO,品格中.纯~ -Mn0,的还原温度在390℃左右，但Pd参杂可以极大地促进c-Mn0,还原，还原温度可低至约200℃左右.研究了所制备催 化剂在无溶剂条件下对于以分子氧为氧化剂选择性催化氧化苯甲醇为苯甲醛的催化性能.结果表明：在无溶剂及用纯氧气为 氧化剂条件下，Pd参杂-MO,纳米棒对苯甲醇氧化显示出增强的催化活性：所掺杂的氧化态Pd物质可增强催化材料中的 氧迁移率；在这些P掺杂a-Mn02催化材料中，当以Pd(3%,质量分数)-MnO2为催化剂时，在110℃反应4h后，苯甲醇的转 化率为39%，远高于同条件下以纯a-M0,为催化剂时18.3%的苯甲醇转化率. 关键词纳米棒：c-MO2;钯掺杂；无溶剂氧化：溶胶-凝胶制备 分类号TB332 Catalytic performance of Pd-doped o-MnO,for oxidation of benzyl alcohol under solvent-free conditions HUANG Xiu-bing),WANG Jing-jing'2),ZHENG Hai-yan'2),LU Gui-long'),WANG Peng'2) 1)School of Materials Science and Engineering,University of Science and Technology Beijing,Beijing 100083,China 2)Beijing Advanced Innovation Center for Materials Genome Engineering,Beijing 100083.China Corresponding author,E-mail:xiubinghuang@ustb.edu.cn ABSTRACT Liquid-phase selective oxidation of benzyl alcohol to benzaldehyde is one of the most important processes in both labora- tory and chemical industry processes due to the remarkable values of benzaldehyde in the production of flavours,fragrances,and bio- logically active compounds.In the traditional processes for selective oxidation of benzyl alcohol using a stoichiometric or excessive amount of toxic and expensive inorganic oxidants,such as ammonium permanganate in aqueous acidic medium,a large amount of toxic waste is produced.A few studies on the benzyl alcohol-to-benzaldehyde oxidation by environmentally clean oxidants (0,or H,0,in the presence of organic solvents (e.g.,toluene,p-xylene,and trifuorotoluene)have been reported;however,the usage of organic sol- vent is neither economical nor environmental friendly.Even though the solvent-free oxidation of benzyl alcohol to benzaldehyde using tert-butylhydroperoxide (TBHP)as oxidant has been reported,the co-product of tert-butanol from the consumption of TBHP will be left in the reaction solution,necessitating further separation.Therefore,various heterogeneous catalysts have been developed for solvent- free selective oxidation of benzyl alcohol using flowing air or oxygen;however,in most of these systems,the reaction temperature is still high (130 C)and/or conversion/selectivity is still low.Thus,the development of efficient heterogeneous catalysts for the solvent- 收稿日期：2018-09-10 基金项目：国家自然科学基金资助项目(51802015)：中央高校基本科研业务费资助项目(FRF-TP-16-028A1):北京市青年骨干个人项目资助 项目(2017000020124G090)工程科学学报,第 41 卷,第 2 期:230鄄鄄237,2019 年 2 月 Chinese Journal of Engineering, Vol. 41, No. 2: 230鄄鄄237, February 2019 DOI: 10. 13374 / j. issn2095鄄鄄9389. 2019. 02. 010; http: / / journals. ustb. edu. cn 钯掺杂 琢鄄鄄 MnO2 无溶剂下催化氧化苯甲醇的性能 黄秀兵1,2) 苣 , 王静静1,2) , 郑海燕1,2) , 路桂隆1,2) , 王 鹏1,2) 1) 北京科技大学材料科学与工程学院, 北京 100083 2) 北京材料基因工程高精尖创新中心, 北京 100083 苣通信作者, E鄄mail: xiubinghuang@ ustb. edu. cn 摘 要 通过共沉淀和原位煅烧转化方法,将 Pd 掺杂 啄鄄鄄MnO2 前驱体煅烧后制备得到 Pd 掺杂 琢鄄鄄MnO2 纳米棒催化材料. 通 过氮气物理吸附、X 射线衍射、透射电子显微镜、扫描电子显微镜、热重分析、X 射线光电子能谱等技术对催化材料进行了表 征. 扫描电镜和透射电镜结果显示,琢鄄鄄MnO2 纳米棒表面没有明显的 Pd 纳米颗粒,表明 Pd 可能掺杂到 琢鄄鄄MnO2 晶格中. 纯 琢鄄 鄄MnO2 的还原温度在 390 益左右,但 Pd 掺杂可以极大地促进 琢鄄鄄MnO2 还原,还原温度可低至约 200 益 左右. 研究了所制备催 化剂在无溶剂条件下对于以分子氧为氧化剂选择性催化氧化苯甲醇为苯甲醛的催化性能. 结果表明:在无溶剂及用纯氧气为 氧化剂条件下,Pd 掺杂 琢鄄鄄MnO2 纳米棒对苯甲醇氧化显示出增强的催化活性;所掺杂的氧化态 Pd 物质可增强催化材料中的 氧迁移率;在这些 Pd 掺杂 琢鄄鄄MnO2 催化材料中,当以 Pd(3% ,质量分数)鄄鄄MnO2 为催化剂时,在 110 益反应 4 h 后,苯甲醇的转 化率为 39% ,远高于同条件下以纯 琢鄄鄄MnO2 为催化剂时 18郾 3% 的苯甲醇转化率. 关键词 纳米棒; 琢鄄鄄MnO2 ; 钯掺杂; 无溶剂氧化; 溶胶鄄鄄凝胶制备 分类号 TB332 收稿日期: 2018鄄鄄09鄄鄄10 基金项目: 国家自然科学基金资助项目(51802015);中央高校基本科研业务费资助项目(FRF鄄鄄TP鄄鄄16鄄鄄028A1);北京市青年骨干个人项目资助 项目(2017000020124G090) Catalytic performance of Pd鄄doped 琢鄄鄄MnO2 for oxidation of benzyl alcohol under solvent鄄free conditions HUANG Xiu鄄bing 1,2) 苣 , WANG Jing鄄jing 1,2) , ZHENG Hai鄄yan 1,2) , LU Gui鄄long 1,2) , WANG Peng 1,2) 1) School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China 2) Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing 100083, China 苣Corresponding author, E鄄mail: xiubinghuang@ ustb. edu. cn ABSTRACT Liquid鄄phase selective oxidation of benzyl alcohol to benzaldehyde is one of the most important processes in both labora鄄 tory and chemical industry processes due to the remarkable values of benzaldehyde in the production of flavours, fragrances, and bio鄄 logically active compounds. In the traditional processes for selective oxidation of benzyl alcohol using a stoichiometric or excessive amount of toxic and expensive inorganic oxidants, such as ammonium permanganate in aqueous acidic medium, a large amount of toxic waste is produced. A few studies on the benzyl alcohol鄄to鄄benzaldehyde oxidation by environmentally clean oxidants (O2 or H2O2 ) in the presence of organic solvents (e. g. , toluene, p鄄xylene, and trifuorotoluene) have been reported; however, the usage of organic sol鄄 vent is neither economical nor environmental friendly. Even though the solvent鄄free oxidation of benzyl alcohol to benzaldehyde using tert鄄butylhydroperoxide (TBHP) as oxidant has been reported, the co鄄product of tert鄄butanol from the consumption of TBHP will be left in the reaction solution, necessitating further separation. Therefore, various heterogeneous catalysts have been developed for solvent鄄 free selective oxidation of benzyl alcohol using flowing air or oxygen; however, in most of these systems, the reaction temperature is still high ( > 130 益 ) and / or conversion / selectivity is still low. Thus, the development of efficient heterogeneous catalysts for the solvent鄄