Buserite型氧化锰催化叔丁基过氧化氢歧化分解反应动力学

doi:10.15541/jim20150295

摘要/Abstract

摘要：

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338 K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%。

关键词: Buserite型氧化锰, 叔丁基过氧化氢, 叔丁醇, 歧化分解, 反应动力学

Abstract:

The series of four buserite-type layered manganese oxides (Me-buserites) with different interlayer cations (Me, Me = Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺) were synthesized by using both MnSO₄·H₂O as Mn source and K₂S₂O₈as oxidant. The as-synthesized Me-buserites were characterized by X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and N₂ adsorption-desorption (BET), in order to determine their crystal phases, elemental compositions and specific surface areas, respectively. In a 25 mL batch glass reactor, the disproportionation decomposition of tert-butyl hydroperoxide was kinetically investigated with the above Me-buserites as catalysts. The kinetic analyses show that the rate law established herein is second order in tert-butyl hydroperoxide, first order in Me-buserites and then third order overall, and that the apparent activation energy ranges from 56 kJ/mol to 125 kJ/mol. In accordance with the kinetic fittings, the proposed mechanism comprises two elementary reaction steps: pre-equilibrium step and rate-determining step. In terms of the pseudo-second-order rate constant and the half an hour-accumulated O₂ volume (both obtained at 338 K), the activity follows the order of Cu-buserite > Mg-buserite > Ni-buserite > Co-buserite. And a 100% selectivity towards tert-butyl alcohol is achieved over all the Me-buserites under selected reaction conditions.

Key words: buserite-type layered manganese oxides, tert-butyl hydroperoxide, tert-butyl alcohol, disproportionation decomposition, chemical kinetics

中图分类号:

O643

卢书培, 冯利利, 齐麟, 王丽丽, 齐兴义. Buserite型氧化锰催化叔丁基过氧化氢歧化分解反应动力学[J]. 无机材料学报, 2016, 31(1): 14-20.

LU Shu-Pei, FENG Li-Li, QI Lin, WANG Li-Li, QI Xing-Yi. Chemical Kinetics of Disproportionation Decomposition of tert-Butyl Hydroperoxide Catalyzed by Buserite-type Manganese Oxides[J]. Journal of Inorganic Materials, 2016, 31(1): 14-20.

图/表 7

图1 Na-birnessite和Me-buserites的XRD图谱

Fig. 1 XRD patterns of Na-birnessite and Me-buserites (a) Na-birnessite; (b) Mg-buserite; (c) Co-buserite; (d) Ni-buserite; (e) Cu-buserite

表1 Me-buserites分子式和BET表面积

Table 1 Molecular formulas and BET surface areas of Me-buserites catalysts

Me-buserite	Molecular formula	S_BET / (m²·g^-1)
Mg-buserite	Na_0.03Mg_3.99Mn_14.00O_30.11·19.05H₂O	61
Co-buserite	Na_0.02Mg_3.29Co_0.54Mn_14.00O_29.54·19.56H₂O	63
Ni-buserite	Na_0.03Mg_1.32Ni_1.43Mn_14.00O_28.68·14.17H₂O	57
Cu-buserite	Na_0.03Mg_1.32Cu_3.40Mn_14.00O_31.23·16.43H₂O	56

图2 Vt和V∞数据的两种动力学拟合图

Fig. 2 Two kinetic fittings of the Vt and V∞ data (catalyst: Cu-buserite) (a) the natural log fitting of ln[1/(V∞ - Vt)] versus t; (b) the linear fitting of 1/(V∞ - Vt) versus t. The line of (b) here is that of (b) in Fig. 3 and for the reaction conditions, also see those shown in Fig.3

图3 不同[Cu-buserite]的1/(V∞ - Vt) 与t的关系曲线

Fig. 3 Plots of 1/(V∞ - Vt) versus t obtained with different [Cu-buserite]s Reaction conditions: T 338 K, TBHP (65wt% in H2O) 1.00 mL, [Cu-buserite]a 1.67 mg/mL, [Cu-buserite]b 3.33 mg/mL, [Cu- buserite]c 5.00 mg/mL, [Cu-buserite]d 8.33 mg/mL, acetonitrile 5.00 mL

图4 lnk’与ln[Cu-buserite]的线性拟合图

Fig. 4 Plot of lnk’ versus ln[Cu-buserite]

图5 lnk° ~ 1 / T的Arrhenius图

Fig. 5 Arrhenius plot of lnk° ~ 1 / T Reaction conditions: Ta=323 K, Tb=328 K, Tc=333 K, Td=338 K, TBHP (65 wt% in H2O) 1.00 mL, [Cu-buserite] 8.33 mg/mL, acetonitrile 5.00 mL

表2 Me-buserites催化TBHP分解反应动力学参数和0.5 h反应时间累积O2体积

Table 2 Kinetic parameters for disproportionation decomposition of TBHP catalyzed by Me-buserites and the O2 volume accumulated in a reaction period of 0.5 h

Me-buserite	α	β	E_a /(kJ·mol^-1)	k°/(mg^-1·mL·s^-1)^*	V_{0.5 h}/mL
Mg-buserite	2	1	89	8.19	41.7
Co-buserite	2	1	56	2.38	20.0
Ni-buserite	2	1	96	5.66	33.6
Cu-buserite	2	1	125	20.30	55.6

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