以MnSO4·H2O为锰源,K2S2O8为氧化剂,制备了4种含有不同层间阳离子(Me,Me=Mg2+、Co2+、Ni2+、Cu2+)的buserite型氧化锰(Me-buserites).采用X射线衍射(XRD)、电感耦合等离子体原子发射(ICP-AES)和N2吸附-脱附(BET)对制成Me-buserites的晶相结构、元素组成和比表面积进行了表征.采用25 mL间歇式玻璃反应器,考察了Me-buserites催化叔丁基过氧化氢歧化分解反应动力学.反应动力学分析表明:反应底物叔丁基过氧化氢浓度项反应级数为2,Me-buserites形式浓度项反应级数为1,总反应级数为3;表观活化能为56～125 kJ/mol.与动力学拟合结果相一致的反应机理是由前置平衡和速控两个反应步骤组成.基于338K反应温度准二级速率常数和0.5 h反应时间累积O2体积决定的活性顺序为Cu-buserite＞Mg-buserite＞Ni-buserite＞Co-buserite;在选定反应条件下,所有Me-buserites的叔丁醇选择性均为100％.
参考文献
| [1] | Schwegman JJ;Hardwick LM;Akers MJ.Practical formulation and process development of freeze-dried products.[J].Pharmaceutical development and technology,20052(2):151-173. |
| [2] | Joseph P Salanifro.Understanding the limitations of microbial metabolism of ethers used as fuel octane enhancers[J].Current Opinion in Biotechnology,19953(3):337-340. |
| [3] | E. W. de Menezes;R. Cataluna;D. Samios.Addition of an azeotropic ETBE/ethanol mixture in eurosuper-type gasolines[J].Fuel,200617/18(17/18):2567-2577. |
| [4] | Feng Shi;Hai Xiong;Yanlong Gu;Shu Guo;Youquan Deng.The first non-acid catalytic synthesis of tert-butyl ether from tert-butyl alcohol using ionic liquid as dehydrator[J].Chemical communications,20039(9):1054-1055. |
| [5] | Riahi A.;Muzart J.;Henin F..Homogeneous chromium(VI)-catalyzed oxidations of allylic alcohols by alkyl hydroperoxides: Influence of the nature of the alkyl group on the product distribution[J].Tetrahedron letters: The International Journal for the Rapid Publication of Preliminary Communications in Organic Chemistry,199912(12):2303-2306. |
| [6] | Rothenberg G.;Sasson Y.;Wiener H..Pyridines as bifunctional co-catalysts in the CrO3-catalyzed oxygenation of olefins by t-butyl hydroperoxide[J].Journal of molecular catalysis, A. Chemical,19983(3):253-262. |
| [7] | Turrà, N.;Neuenschwander, U.;Baiker, A.;Peeters, J.;Hermans, I..Mechanism of the catalytic deperoxidation of tert-butylhydroperoxide with cobalt(II) acetylacetonate[J].Chemistry: A European journal,201044(44):13226-13235. |
| [8] | Zachary J. West;Ryan K. Adams;Steven Zabarnick.Homogeneous Catalysis of Liquid-Phase Hydroperoxide Decomposition in Hydrocarbons[J].Energy & Fuels,2011Mar./Apr.(Mar./Apr.):897-904. |
| [9] | Ganapati D. Yadav;Navinchandra S. Asthana.Selective decomposition of cumene hdyroperoxide into phenol and acetone by a novel cesium substituted heteropolyacid on clay[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,20032(2):341-357. |
| [10] | Yi Luo;Satoshi Maeda;Koichi Ohno.Decomposition of alkyl hydroperoxide by a copper(I) complex: insights from density functional theory[J].Tetrahedron letters: The International Journal for the Rapid Publication of Preliminary Communications in Organic Chemistry,200848(48):6841-6845. |
| [11] | Ryan, P.;Konstantinov, I.;Snurr, R.Q.;Broadbelt, L.J..DFT investigation of hydroperoxide decomposition over copper and cobalt sites within metal-organic frameworks[J].Journal of Catalysis,20121(1):95-102. |
| [12] | Haojie Cui;Xiangwen Liu;Wenfeng Tan;Xionghan Feng;Fan Liu;Huada Daniel Ruan.INFLUENCE OF Mn(III) AVAILABILITY ON THE PHASE TRANSFORMATION FROM LAYERED BUSERITE TO TUNNEL-STRUCTURED TODOROKITE[J].Clays and clay minerals,20084(4):397-403. |
| [13] | Ming Yang;Qiang Ling;Hongxiao Yang.Enhanced catalytic activity of K-birnessite MnO2 confined in carbon nanotubes for selective oxidation of benzyl alcohol[J].Catalysis Communications,2014:238-241. |
| [14] | Mathias Wiechen;Ivelina Zaharieva;Holger Dau.Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion[J].Chemical science,20127(7):2330-2339. |
| [15] | I. Atribak;A. Bueno-Lopez;A. Garcia-Garcia.Catalytic activity for soot combustion of birnessite and cryptomelane[J].Applied Catalysis, B. Environmental: An International Journal Devoted to Catalytic Science and Its Applications,20103/4(3/4):267-273. |
| [16] | 张宣宣;冉奋;范会利;孔令斌;康龙.互通多孔碳/二氧化锰纳米复合材料的原位水热合成及电化学性能[J].物理化学学报,2014(5):881-890. |
| [17] | Zhenjie Sun;Dong Shu;Hongyu Chen;Chun He;Shaoqing Tang;Jie Zhang.Microstructure and supercapacitive properties of buserite-type manganese oxide with a large basal spacing[J].Journal of Power Sources,2012Oct.15(Oct.15):425-433. |
| [18] | Athouel L;Moser F;Dugas R;Crosnier O;Belanger D;Brousse T.Variation of the MnO2 birnessite structure upon charge/discharge in an electrochemical supercapacitor electrode in aqueous Na2SO4 electrolyte[J].The journal of physical chemistry, C. Nanomaterials and interfaces,200818(18):7270-7277. |
| [19] | Ouassim Ghodbane;Jean-Louis Pascal;Frederic Favier.Microstructural Effects on Charge-Storage Properties in MnO2-Based Electrochemical Supercapacitors[J].ACS applied materials & interfaces,20095(5):1130-1139. |
| [20] | Kuppukkannu Ramalingam;Thiyagarajan Kamatchi;Pullarkat A. Sumod.Synthesis, spectral, thermal and CO2 absorption studies on birnessites type layered MnO6 oxide[J].Transition Metal Chemistry,20064(4):429-433. |
| [21] | Stanton Ching;Katarzyna S. Krukowska;Steven L. Suib.A new synthetic route to todorokite-type manganese oxides[J].Inorganica Chimica Acta,19992(2):123-132. |
| [22] | Liu, YM;Tsunoyama, H;Akita, T;Tsukuda, T.Efficient and selective epoxidation of styrene with TBHP catalyzed by Au-25 clusters on hydroxyapatite[J].Chemical communications,20104(4):550-552. |
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