Study on performance of Ag-modified layered copper silicate catalyst for hydrogenation of dimethyl oxalate to methyl glycolate
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摘要: 本研究采用溶胶-凝胶法制备了一系列CuAg/SiO2催化剂用于草酸二甲酯(DMO)加氢合成MG,使用XRD、N2吸附-脱附、FT-IR、TEM、SEM、H2-TPR、XPS等方法对其结构进行表征,重点考察了Ag含量对催化剂结构及性能的影响。当Ag负载量为5%时,5Ag-Cu/SiO2催化剂活性最高,DMO的转化率和MG的选择性分别可达83.7%和72.2%。表征结果表明,适量Ag的引入可有效提高活性组分Cu的分散度,增加催化剂表面Cu+的含量,从而提高催化剂活性。此外,Ag与Cu之间的电子转移可以有效稳定Cu+,进而提高催化剂的稳定性。Abstract: Methyl glycolate (MG) is a high value-added chemical intermediate and widely used in the fields of medicine, chemical industry, fodder and dyes. A series of CuAg/SiO2 catalysts were prepared by sol-gel method for hydrogenation of dimethyl oxalate to MG. The structure of catalysts was characterized by XRD, N2-physical adsorption, FT-IR, TEM, H2-TPR, and XPS, and the influence of Ag loading on catalytic performance was investigated. The 5Ag-Cu/SiO2 catalyst with Ag loading of 5% exhibited the best catalytic performance with DMO conversion of 83.7% and MG selectivity of 72.2%. The characterization results showed that introducing appropriate amount of Ag not only improved the dispersion of copper species, but also increased the content of Cu+, thereby improving the catalytic activity of CuAg/SiO2 catalysts. In addition, the electron transfer between Ag and Cu could effectively stabilize Cu+, and eventually improved the stability of the catalyst.1) #: 共同第一作者
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表 1 催化剂的物理化学和织构性质
Table 1 Physicochemical and textural properties of catalysts
Catalyst Cu loading
w/%aAg loading
w/%aCu dispersion/
%bCu surface/
(m2·g−1)bSBET/
(m2·g−1)cvtotal/
(cm3·g−1)dd/nme Cu/SiO2 28.6 0 14.7 99.4 313 0.58 7.14 1Ag-Cu/SiO2 28.2 0.5 25.3 171.2 235 0.79 12.4 3Ag-Cu/SiO2 27.6 1.7 25.9 175.2 240 0.76 10.73 5Ag-Cu/SiO2 27.1 2.0 27.2 184.0 222 0.71 12.6 8Ag-Cu/SiO2 26.4 2.3 23.7 160.3 226 0.73 13.11 Ag/SiO2 − 1.8 − − − − − a: Cu loading and Ag loading conducted by ICP; b: Cu dispersion determined by N2O surface oxidation; c: BET specific surface areas;
d: Total pore volume by BET; e: Average pore diameter was calculated from adsorption branch by BJH表 2 还原后不同焙烧温度催化剂表面铜物种占比
Table 2 Percentage of copper species on the surface of catalysts at different calcination temperatures after activation
Catalyst E/eV $X_{{\rm{Cu}}}^+$%a Cu+ Cu0 Cu/SiO2 912.3 916.2 44.8 1Ag-Cu/SiO2 913.5 917.5 57.2 3Ag-Cu/SiO2 913.8 917.5 63.1 5Ag-Cu/SiO2 914.2 917.8 66.3 8Ag-Cu/SiO2 914.1 917.8 64.7 a: ratio of Cu+ to (Cu++Cu0) obtained by deconvolution of Cu LMM spectra -
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