Ce1-xMnxO2表面性质对催化CO2和甲醇直接合成DMC反应活性的影响

doi:10.7503/cjcu20200250

摘要/Abstract

摘要：

通过共沉淀法制备了一系列Mn掺杂量不同的Ce_1-_xMn_xO₂催化剂, 并将其用于催化CO₂和甲醇直接合成碳酸二甲酯(DMC). 通过X射线衍射(XRD)、氮气吸附-脱附、透射电子显微镜(TEM)、 X射线光电子能谱(XPS)和程序升温脱附(TPD)等手段研究了Ce_1-_xMn_xO₂表面性质对催化CO₂和甲醇直接合成DMC反应活性的影响. 结果表明, Mn离子进入CeO₂晶格中形成固溶体, 随着Mn掺杂量增加, 催化剂表面弱酸碱位数量逐渐降低, 中强酸碱和强酸碱位数量增加, 催化剂表面氧空位含量呈先增加后减少的变化趋势, 当Mn掺杂量较少时, 催化剂表面Mn²⁺比例较高, 有利于Ce⁴⁺+Mn²⁺→Ce³⁺+Mn³⁺反应的进行, 促进催化剂表面氧空位生成; 进一步提高Mn掺杂量时, 催化剂表面Mn⁴⁺比例提高, 有利于Ce³⁺+Mn⁴⁺→Ce⁴⁺+Mn³⁺反应的进行, 导致催化剂表面氧空位含量减少. 研究发现Ce_1-_xMn_xO₂催化剂活性与表面氧空位含量线性相关.

关键词: 二氧化碳, 碳酸二甲酯, 催化剂, 酸碱性, 氧空位

Abstract:

A series of Ce_1-_xMn_xO₂ catalysts with different Mn doping amounts were prepared by coprecipitation method and applied to catalyze direct synthesis of dimethyl carbonate(DMC) from CO₂ and methanol. The effects of surface properties of Ce_1-_xMn_xO₂ on the direct synthesis of DMC from CO₂ and methanol were studied by means of X-ray diffraction(XRD), N₂ adsorption-desorption, transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS) and programmed temperature desorption(TPD). The results indicated that Mn ions successfully entered into the lattice of CeO₂ and formed a uniform solid solution. With the increase of Mn doping, the number of weak acid and base sites on the catalyst surface decreased gradually, while the number of medium and strong acid and base sites increased. Meanwhile, the oxygen vacancy content on the catalyst surface increased first and then decreased with the increase of Mn doping. When the doping of Mn was low, the ratio of Mn²⁺ on the catalyst surface was high, which was beneficial for the reaction of Ce⁴⁺+ Mn²⁺→Ce³⁺+ Mn³⁺ and the formation of oxygen vacancies. With further increase of Mn doping, the ratio of Mn⁴⁺ on the catalyst surface increase, which was conducive to the reaction of Ce³⁺+Mn⁴⁺→Ce⁴⁺+Mn³⁺, resulting in the decrease of oxygen vacancy. The catalytic activity of Ce_1-_xMn_xO₂ catalyst was linearly correlated with the content of oxygen vacancy on surface.

Key words: Carbon dioxide, Dimethyl carbonate(DMC), Catalyst, Acidity-basicity property, Oxygen vacancy

中图分类号:

O643

TrendMD:

张国强, 孙宇辰, 史亚波, 郑华艳, 李忠, 上官炬, 刘守军, 史鹏政. Ce_1-_xMn_xO₂表面性质对催化CO₂和甲醇直接合成DMC反应活性的影响. 高等学校化学学报, 2020, 41(9): 2061.

ZHANG Guoqiang, SUN Yuchen, SHI Yabo, ZHENG Huayan, LI Zhong, SHANGGUAN Ju, LIU Shoujun, SHI Pengzheng. Surface Properties of Ce_1-_xMn_xO₂ Catalyst on the Catalytic Activities for Direct Synthesis of DMC from CO₂ and Methanol. Chem. J. Chinese Universities, 2020, 41(9): 2061.

图/表 14

Fig.1 XRD patterns of Ce1-xMnxO2 catalysts

Table 1 Interplanar spacing, lattice parameters and crystallite size of Ce1-xMnxO2 catalysts

Sample	2θ/(°)	Interplanar spacing/nm	Lattice parameter/nm	Particle size^*/nm
CeO₂	28.50	0.31293	0.54201	10.106
Ce_0.983Mn_0.017O₂	28.53	0.31260	0.54145	10.326
Ce_0.956Mn_0.044O₂	28.55	0.31250	0.54126	9.570
Ce_0.91Mn_0.09O₂	28.58	0.31239	0.54108	8.782
Ce_0.864Mn_0.136O₂	28.61	0.31207	0.54052	8.987

Fig.2 N2 adsorption?desorption isotherms of Ce1-xMnxO2 catalysts

Table 2 Textural parameters of Ce1-xMnxO2 catalysts

Catalyst	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	Pore size/nm
CeO₂	145	0.60	11.6
Ce_0.983Mn_0.017O₂	145	0.62	12.2
Ce_0.956Mn_0.044O₂	147	0.58	11.1
Ce_0.910Mn_0.090O₂	145	0.63	12.0
Ce_0.864Mn_0.136O₂	147	0.68	12.8

Fig.3 TEM(A―E) images and particle size distributions(A′—E′) of Ce1-xMnxO2 catalysts(A), (A′) CeO2; (B), (B′) Ce0.983Mn0.017O2; (C), (C′) Ce0.956Mn0.044O2; (D), (D′) Ce0.910Mn0.090O2; (E), (E′) Ce0.864Mn0.136O2.

Fig.4 HRTEM images of Ce1-xMnxO2 catalysts

Fig.5 CO2?TPD(A) and NH3?TPD(B) profiles of Ce1-xMnxO2 catalysts

Table 3 Adsorption capacity of CO2 and NH3 of Ce1-xMnxO2 catalysts

Sample	CO₂ adsorption^a/(mmol·g^-1)			NH₃ adsorption^b/(mmol·g^-1)
Sample	Weak(<200 ℃)	Moderate(200―400 ℃)	Strong(>400 ℃)	Weak(<200 ℃)	Moderate(200―400 ℃)	Strong(>400 ℃)
CeO₂	0.226	0.046	0.017	0.723	0.027	0.048
Ce_0.983Mn_0.017O₂	0.156	0.072	0.020	0.549	0.057	0.036
Ce_0.956Mn_0.044O₂	0.141	0.075	0.032	0.204	0.094	0.038
Ce_0.910Mn_0.090O₂	0.121	0.110	0.036	0.186	0.140	0.056
Ce_0.864Mn_0.136O₂	0.102	0.120	0.047	0.220	0.134	0.064

Fig.6 XPS spectra of Ce3d(A) and O1s(B) of Ce1-xMnxO2 catalystsa. CeO2; b. Ce0.983Mn0.017O2; c. Ce0.956Mn0.044O2; d. Ce0.910Mn0.090O2; e. Ce0.864Mn0.136O2.

Table 4 Surface concentrations of Ce, O and Mn estimated by XPS

Catalyst	Molar fraction(%)
Catalyst	Ce³⁺	Ce⁴⁺	O_V	Mn⁴⁺	Mn³⁺	Mn²⁺
CeO₂	10.8	89.2	5.6	—	—	—
Ce_0.983Mn_0.017O₂	14.6	85.4	6.9	8.8	76.8	14.3
Ce_0.956Mn_0.044O₂	11.1	88.9	6.2	12.5	76.4	11.1
Ce_0.910Mn_0.090O₂	10.7	89.3	4.9	15.7	77.2	7.1
Ce_0.864Mn_0.136O₂	9.8	90.2	4.5	19.4	73.5	7.1

Fig.7 XPS spectra of Mn2p of Ce1-xMnxO2 catalystsa. Ce0.983Mn0.017O2; b. Ce0.956Mn0.044O2;c. Ce0.91Mn0.09O2; d. Ce0.864Mn0.136O2.

Fig.8 Catalytic activity of Ce1-xMnxO2 catalystsa. CeO2; b. Ce0.983Mn0.017O2; c. Ce0.956Mn0.044O2; d. Ce0.910Mn0.090O2; e. Ce0.864Mn0.136O2.

Fig.9 Correlation between catalytic activity and basicity(A), acidity(B) of Ce1-xMnxO2 catalystsa. CeO2; b. Ce0.983Mn0.017O2; c. Ce0.956Mn0.044O2; d. Ce0.910Mn0.090O2; e. Ce0.864Mn0.136O2.

Fig.10 Correlation between oxygen vacancies and catalytic activity of Ce1-xMnxO2 catalysts

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Ce_1-_xMn_xO₂表面性质对催化CO₂和甲醇直接合成DMC反应活性的影响

Surface Properties of Ce_1-_xMn_xO₂ Catalyst on the Catalytic Activities for Direct Synthesis of DMC from CO₂ and Methanol

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