Pd掺杂量对有机无机杂化SiO2膜H2/CO2分离性能和水热稳定性能的影响

doi:10.15541/jim20180189

摘要/Abstract

摘要：

以1,2-二(三乙氧基硅基)乙烷(BTESE)为前驱体、PdCl₂为钯源, 制备Pd掺杂有机无机杂化SiO₂(POS)溶胶, 涂膜后在水蒸气氛围中煅烧, 制备得到POS膜。采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、N₂吸附-脱附和透射电子显微镜(TEM)对POS粉体的微观结构进行表征。考察了钯/硅摩尔比(n(Pd/Si)=0.1、0.5和1)对POS膜的气体分离性能与水热稳定性能的影响。结果表明: 随着Pd掺杂量的增加, POS膜的H₂渗透率逐渐增大, H₂/CO₂的理想选择性逐渐下降。经100 kPa水蒸气处理180 h后, 采用n (Pd/Si)=1制备的POS膜的H₂渗透率达到1.62× 10^-7 mol·m^-2·s^-1·Pa^-1, H₂/CO₂理想分离因子达到13.6, 表明该膜具有较好的H₂渗透性能、H₂/CO₂分离性能和水热稳定性能。

关键词: 有机无机杂化SiO₂膜, Pd掺杂, 气体分离, 水热稳定性

Abstract:

Pd-doped organic-inorganic hybrid SiO₂ (POS) sols were synthesized by using 1,2-bis(triethoxysilyl) ethane (BTESE) and palladium chloride as precursors. POS membranes were fabricated via dip-coating process followed by calcination in the water vapor environment. The microstructure of POS powders was characterized by X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), N₂ adsorption-desorption, and transmission electron microscope (TEM). Effect of the molar ratio of Pd to Si (n (Pd/Si)=0.1, 0.5 and 1) on separation performance and hydrothermal stability of POS membranes was investigated. Results showed that with the increase of Pd doping amount, H₂ permeance of POS membranes increased while the permselectivity of H₂/CO₂decreased. After exposing to 100 kPa steam atmosphere for 180 h, H₂ permeance and H₂/CO₂ permselectivity of the POS membrane prepared with n (Pd/Si) of 1 reached 1.62×10^-7 mol·m^-2·s^-1·Pa^-1 and 13.6, respectively. This result indicated that as-prepared POS membrane exhibited good H₂ permeance, H₂/CO₂ permselectivity and hydrothermal stability.

Key words: organic-inorganic hybrid SiO₂ membranes, Pd-doping, gas separation, hydrothermal stability

中图分类号:

TQ174

张恒飞, 刘为, 雷姣姣, 宋华庭, 漆虹. Pd掺杂量对有机无机杂化SiO₂膜H₂/CO₂分离性能和水热稳定性能的影响[J]. 无机材料学报, 2018, 33(12): 1316-1322.

ZHANG Heng-Fei, LIU Wei, LEI Jiao-Jiao, SONG Hua-Ting, QI Hong. Pd Doping on H₂/CO₂ Separation Performance and Hydrothermal Stability of Organic-inorganic Hybrid SiO₂ Membranes[J]. Journal of Inorganic Materials, 2018, 33(12): 1316-1322.

图/表 10

图1 POS粉体的XRD图谱

Fig. 1 XRD patterns of POS powders

图2 POS粉体的FT-IR谱图

Fig. 2 FT-IR spectra of POS powders

图3 POS粉体的N2吸附-脱附曲线(a)和NLDFT孔径分布图(b)

Fig. 3 N2 adsorption-desorption isotherms (a) and NLDFT pore size distributions (b) of POS powders

表1 POS粉体的孔结构数据

Table 1 Pore structure data of POS powders

n(Pd/Si)	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	(V_micro/V_total)/%
0.1	490	0.29	66
0.5	471	0.33	53
1	333	0.31	39

表2 SiO2基膜的气体渗透率和H2/CO2理想分离因子

Table 2 Gas permeance and H2/CO2 permselectivity of silica-based membranes

Membranes	Gas permeance/(×10^-8, mol· m^-2·s^-1·Pa^-1)					Permselectivity
Membranes	H₂(d_k=0.289 nm)	CO₂(d_k=0.33 nm)	N₂(d_k=0.364 nm)	CH₄(d_k=0.382 nm)	SF₆(d_k=0.55 nm)	H₂/CO₂ (Knudsen factor: 4.7)
POS-0.1	2.41	0.21	0.13	0.14	0.08	11.50
POS-0.5	13.00	2.18	0.65	0.30	0.06	5.97
POS-1	20.70	4.58	2.48	2.99	0.93	4.52
SiO₂^[25]	63.00	1.30	0.42	0.11	≤0.01	46.00
BTESE^[26]	46.20	12.40	4.40	4.00	-	3.70
Nb-BTESE^[16]	6.280	0.06	-	-	-	108.00

图4 POS膜的H2、CO2渗透性能、H2/CO2分离性能随水蒸气处理时间的变化(测试条件: 200℃、300 kPa)

Fig. 4 Variations of H2, CO2 permeance and H2/CO2 permselectivity of POS membranes during hydrothermal treatment (measured at 200℃ and 300 kPa)

表3 POS粉体中Pd晶粒尺寸

Table 3 Grain size of Pd in POS powders

n(Pd/Si)	Grain size/nm		Increase ratio/%
n(Pd/Si)	Before HT	After HT	Increase ratio/%
0.1	12.7	14.0	10
0.5	20.6	28.1	36
1	26.1	30.1	15

图5 POS粉体水热处理前后的TEM照片

Fig. 5 TEM images of POS powders before and after hydrothermal treatment(a-c) as-prepared POS-0.1, POS-0.5 and POS-1 powders; (d-f) POS-0.1, POS-0.5 and POS-1 powders after hydrothermal treatment

图6 有机无机杂化SiO2网络的孔结构示意图

Fig. 6 Schematic diagram of pore structure of organic-inorganic hybrid SiO2 network

图7 水蒸气处理前后POS膜结构示意图

Fig. 7 Schematic structure of POS membranes before and after hydrothermal treatment

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Pd掺杂量对有机无机杂化SiO₂膜H₂/CO₂分离性能和水热稳定性能的影响

Pd Doping on H₂/CO₂ Separation Performance and Hydrothermal Stability of Organic-inorganic Hybrid SiO₂ Membranes

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