Effect of liquid-phase reduction temperature on performance of silver-silica catalysts for hydrogenation of dimethyl oxalate to methyl glycolate

doi:10.11949/0438-1157.20211097

Abstract

Abstract:

Four amino-functionalized SiO₂nanospheres supported silver catalysts (Ag/AS) were synthesized in this work by adjusting the temperature of the reduction process for the AgNO₃ precursor with using ethanol as the reductant. The catalyst characterization and the catalytic performance tests clearly show the effect of liquid-phase reduction temperature on the performance of Ag/AS catalysts for hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG). X-Ray diffraction, N₂ physical adsorption, transmission electron microscopy and X-ray photoelectron spectroscopy measurements indicate that the particle size of Ag particles increases significantly with the increasing reduction temperature, which results in increase of surface Ag coordination number. In-situ infrared spectroscopy of DMO adsorption and DMO temperature-programmed desorption experiments show that the increase in the coordination number of surface atoms caused by the increase of reduction temperature weakens the adsorption of DMO on the catalyst and thus reduces the activity of DMO hydrogenation to MG.

Key words: dimethyl oxalate, hydrogenation, methyl glycolate, catalyst, reduction temperature, reactivity

摘要：

以表面氨基功能化修饰的介孔二氧化硅纳米微球(AS)为载体，乙醇为还原剂，通过调变前体AgNO₃的还原温度，制得了四种不同银催化剂(Ag/AS)，结合催化剂表征技术和催化性能研究，探讨了液相还原温度对银硅催化剂上草酸二甲酯(DMO)加氢制乙醇酸甲酯(MG)反应性能的影响规律。X射线衍射、氮气物理吸附、透射电镜、X射线光电子能谱等研究结果表明，Ag/AS催化剂随着还原温度的升高Ag颗粒的平均粒径呈指数型增大，对应的表面Ag原子配位数也随之增大。DMO吸附的原位红外光谱和DMO程序升温脱附实验表明，还原温度升高引起的表面原子配位数的增大，减弱了DMO在催化剂上的吸附进而降低了DMO加氢制MG的活性。

关键词: 草酸二甲酯, 加氢, 乙醇酸甲酯, 催化剂, 还原温度, 活性

CLC Number:

TQ 032.4

Guilin DONG, Zuwei LUO, Yueqiang CAO, Jinghong ZHOU, Wei LI, Xinggui ZHOU. Effect of liquid-phase reduction temperature on performance of silver-silica catalysts for hydrogenation of dimethyl oxalate to methyl glycolate[J]. CIESC Journal, 2022, 73(1): 232-240.

董桂霖, 罗祖伟, 曹约强, 周静红, 李伟, 周兴贵. 液相还原温度对草酸酯加氢制乙醇酸甲酯银硅催化剂性能的影响[J]. 化工学报, 2022, 73(1): 232-240.

Figures/Tables 9

Fig.1 Typical TEM images of the Ag/AS catalysts reduced at different temperature and the corresponding histograms of the particle size distributions

Fig.2 Ag particle size as a function of reduction temperature

Table 1 Physicochemical properties of the Ag/AS catalysts

Sample	Ag content^①/%	S_BET^②/(m²·g^-1)	V_pore^③/(cm³·g^-1)	D_pore^③/nm	d_Ag·TEM^④/nm	d_Ag·XRD^⑤/nm	D^⑥/%	S_Ag^⑥/(m²·g^-1)	TOF/h^-1
Ag/AS_70	2.9	242	0.33	6.12	5.5±0.9	nd	31.7	4.46	230^⑦
Ag/AS_75	2.6	210	0.26	5.43	7.3±1.7	6.7	19.0	2.40	179^⑧
Ag/AS_80	2.3	162	0.21	5.27	11.4±2.1	11.0	13.3	1.48	123^⑨
Ag/AS_85	2.1	117	0.17	5.15	20.6±2.8	20.4	5.7	0.58	72^⑩

Fig.3 XRD patterns of Ag/AS catalysts synthesized at different reduction temperature

Fig.4 Ag 3d XPS spectra of Ag/AS catalysts synthesized at different reduction temperature

Fig.5 Typical HRTEM images of Ag/AS catalysts synthesized at different reduction temperature

Fig.6 Performance evaluation of Ag/AS catalysts in DMO hydrogenation to MG under 2.0 MPa，220℃，H2/DMO 80

Fig.7 FTIR spectra of the gas-phase DMO molecule and the adsorbed ones on the Ag/AS catalysts

Fig.8 DMO-TPD profiles for the Ag/AS catalysts

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