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

doi:10.15541/jim20180189

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 10

Fig. 1 XRD patterns of POS powders

Fig. 2 FT-IR spectra of POS powders

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

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

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

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

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

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

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

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

References 28

[1]	GEORGIS D, LIMA F V, ALMANSOORI A,et al. Thermal management of a Water-Gas-Shift membrane reactor for high-purity hydrogen production and carbon capture. Industrial & Engineering Chemistry Research, 2014, 53(18): 7461-7469.
[2]	CHAI M, MACHIDA M, EGUCHI K,et al. Promotion of hydrogen permeation on metal-dispersed alumina membranes and its application to a membrane reactor for methane steam reforming. Applied Catalysis A General, 1994, 110(2): 239-250.
[3]	SUN Y M, KHANG S J.Catalytic membrane for simultaneous chemical reaction and separation applied to a dehydrogenation reaction.Industrial & Engineering Chemistry Research, 1988, 27(7): 1136-1142.
[4]	YIN H, KIM H, CHOI J,et al. Thermal stability of ZIF-8 under oxidative and inert environments: a practical perspective on using ZIF-8 as a catalyst support. Chemical Engineering Journal, 2015, 278: 293-300.
[5]	BUDHI Y W, RIONAIDO H, PADAMA A A B,et al. Forced unsteady state operation for hydrogen separation through Pd-Ag membrane after start-up. International Journal of Hydrogen Energy, 2015, 40(32): 10081-10089.
[6]	CHEN W H, TSAI C W, LIN Y L.Numerical studies of the influences of bypass on hydrogen separation in a multichannel Pd membrane system. Renewable Energy, 2017, 104: 259-270.
[7]	NIJMEIJER A.Hydrogen-selective Silica Membranes for Use in Membrane Steam Reforming. ENSCHEDE: UT 1999, 136.
[8]	GAVALAS G R, MEGIRIS C E, NAM S W.Deposition of H2 - permselective SiO2 films.Chemical Engineering Science, 1989, 44(9): 1829-1835.
[9]	TSURU T.Nano/subnano-tuning of porous ceramic membranes for molecular separation. Journal of Sol-Gel Science and Technology, 2008, 46(3): 349-361.
[10]	IMAI H, MORIMOTO H, TOMINAGA A,et al. Structural changes in Sol-Gel derived SiO2 and TiO2 films by exposure to water vapor. Journal of Sol-Gel Science and Technology, 1997, 10(1): 45-54.
[11]	LI G, KANEZASHI M, TSURU T.Preparation of organic- inorganic hybrid silica membranes using organoalkoxysilanes: the effect of pendant groups.Journal of Membrane Science, 2011, 379(1): 287-295.
[12]	YANG J, CHEN J T. Hydrophobic modification and silver doping of silica membranes for H2/CO2 separation. Journal of CO2 Utilization, 2013, 3-4: 21-29.
[13]	KANEZASHI M, YADA K, YOSHIOKA T,et al. Design of silica networks for development of highly permeable hydrogen separation membranes with hydrothermal stability. Journal of the American Chemical Society, 2009, 131(2): 414-415.
[14]	UHLMANN D, LIU S, LADEWIG B P,et al. Cobalt-doped silica membranes for gas separation. Journal of Membrane Science, 2009, 326(2): 316-321.
[15]	KANEZASHI M, SANO M, YOSHIOKA T,et al. Extremely thin Pd-silica mixed-matrix membranes with nano-dispersion for improved hydrogen permeability. Chemical Communications, 2010, 46(33): 6171-6173.
[16]	QI H, CHEN H R,LI L,et al. Effect of Nb content on hydrothermal stability of a novel ethylene-bridged silsesquioxane molecular sieving membrane for H2/CO2 separation. Journal of Membrane Science, 2012, 421-422: 190-200.
[17]	IKUHARA Y H, MORI H, SAITO T,et al. High-temperature hydrogen adsorption properties of precursor-derived nickel nanoparticle- dispersed amorphous silica. Journal of the American Ceramic Society, 2007, 90(2): 546-552.
[18]	KANEZASHI M, FUCHIGAMI D, YOSHIOKA T,et al. Control of Pd dispersion in Sol-Gel-derived amorphous silica membranes for hydrogen separation at high temperatures. Journal of Membrane Science, 2013, 439(14): 78-86.
[19]	SONG H T, ZHAO S F, LEI J J,et al. Pd-doped organosilica membrane with enhanced gas permeability and hydrothermal stability for gas separation. Journal of Materials Science, 2016, 51(13): 6275-6286.
[20]	LEI J J, SONG H T, WEI Y B,et al. A novel strategy to enhance hydrothermal stability of Pd-doped organosilica membrane for hydrogen separation. Microporous & Mesoporous Materials, 2017, 253: 55-63.
[21]	SONG H T, ZHAO S F, CHEN J W, et al. Hydrothermally stable Zr-doped organosilica membranes for H2/CO2 separation. Microporous & Mesoporous Materials, 2016, 224: 277-284.
[22]	YAMAMOTO K, OHSHITA J, MIZUMO T,et al. Efficient synthesis of SiOC glasses from ethane, ethylene, and acetylene- bridged polysilsesquioxanes. Journal of Non-Crystalline Solids, 2015, 408: 137-141.
[23]	NGAMOU P T, OVERBEEK J, KREITER R, et al. Plasma-deposited hybrid silica membranes with a controlled retention of organic bridges. Journal of Materials Chemistry A, 2013, 1(18): 5567-5576.
[24]	AI-OWEINI R, EI-RASSY H.Synthesis and characterization by FT-IR spectroscopy of silica aerogels prepared using several Si(OR)4, and RSi(OR°)3, precursors.Journal of Molecular Structure, 2009, 919(1): 140-145.
[25]	BOFFA V, BLANK D H A, ELSHOF J E T. Hydrothermal stability of microporous silica and niobia-silica membranes.Journal of Membrane Science, 2008, 319(1/2): 256-263.
[26]	QURESHI H F, NIJMEIJER A, WINNUBST L.Influence of Sol-Gel process parameters on the micro-structure and performance of hybrid silica membranes.Journal of Membrane Science, 2013, 446: 19-25.
[27]	NAGASAW H, NIIMI T, KANEZASHI M.et al. Modified gas-translation model for prediction of gas permeation through microporous organosilica membranes. AICHE Journal, 2015, 60(12): 4199-4210.
[28]	SONG H T, WEI Y B, QI H.Tailoring pore structures to improve the permselectivity of organosilica membranes by tuning calcination parameters.Journal of Materials Chemistry A, 2017, 5(47): 24657-24666.

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

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 28

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	LI Ziyi, ZHANG Jiajia, ZOU Xiaoqin, ZUO Jiayu, LI Jun, LIU Yingshu, PUI David Youhong. Synthesis and Gas Separation of Chabazite Zeolite Membranes [J]. Journal of Inorganic Materials, 2021, 36(6): 579-591.
[2]	YANG Liuxin,LUO Wenhua,WANG Changan,XU Chen. Novel Inorganic Two-dimensional Materials for Gas Separation Membranes [J]. Journal of Inorganic Materials, 2020, 35(9): 959-971.
[3]	YIN Hui-Min, YANG Jian-Hua, XIE Zhong, WANG Jin-Qu, LU Jing-Ming, ZHANG Yan. Deposition of Functional Modified Inorganic Particles on A Macroporous Tube for Synthesis ZIF-7 Membrane by Counter Diffusion Method [J]. Journal of Inorganic Materials, 2014, 29(4): 377-381.
[4]	YU Jiao-Zhu, LI Lin, JIN Xin, DING Ling-Hua, WANG Tong-Hua. Preparation of Organic/Inorganic Membrane by PDMS Low-temperature Pyrolysis [J]. Journal of Inorganic Materials, 2014, 29(2): 137-142.
[5]	SUN Mei-Yue, LI Lin, ZHANG Ping-Ping, XU Jia-Jia, YU Jiao-Zhu, WANG Tong-Hua. Preparation and Gas Separation Performance of P25 Hybrid Carbon Membranes [J]. Journal of Inorganic Materials, 2013, 28(5): 485-489.
[6]	SONG Cheng-Wen, JIANG Da-Wei, LI Lin, SUN Mei-Yue, WANG Tong-Hua. Preparation and Gas Separation Properties of Carbon/Carbon Nanotubes Hybrid Membranes Derived from PMDA-ODA Polyimide [J]. Journal of Inorganic Materials, 2012, 27(9): 923-927.
[7]	DU Shu-Hui, LIU Ya-Guang, KONG Ling-Yin, ZHANG Jian, LIU Hai-Ou, ZHANG Xiong-Fu. Seeded Secondary Growth Synthesis of ZIF-8 Membranes Supported on α-Al₂O₃ Ceramic Tubes [J]. Journal of Inorganic Materials, 2012, 27(10): 1105-1111.
[8]	PANG Jing, WANG Tong-Hua, LI Lin,QI Wen-Bo, CAO Yi-Ming. Effect of Different Drying Methods on PPESK CarbonMembrane [J]. Journal of Inorganic Materials, 2011, 26(2): 165-159.
[9]	QI Hong, HAN Jing, JIANG Xiao-Luo, XING Wei-Hong, FAN Yi-Qun. Preparation and Hydrothermal Stability of Organic-inorganic Hybrid Silica Membrane [J]. Journal of Inorganic Materials, 2010, 25(7): 758-764.
[10]	LI Lin-1, WANG Tong-Hua-1, CAO Xi-Ming-2, QIU Jie-Shan-1. Physical Design, Preparation and Functionalization of Carbon Membranes for Gas Separation [J]. Journal of Inorganic Materials, 2010, 25(5): 449-456.
[11]	ZHAO Xuan-Ying,WANG Tong-Hua,LI Lin,LIU Ying,CAO Yi-Ming. Polymide/Fe₃O₄-carbonized Membranes for Gas Separation [J]. Journal of Inorganic Materials, 2010, 25(1): 47-52.
[12]	LI Fang-Fei,JIANG Yin-Shan,XIA Mao-Sheng,SUN Meng-Meng,XUE Bing,LIU Da-Rui. Enhancement Effect of Nano-scaled White Silica on the Hydrothermal Stabilities of Mesoporous Montmorillonite [J]. Journal of Inorganic Materials, 2009, 24(5): 1025-1030.
[13]	ZHOU Zhi-Hua,LU Jin-Ming,WU Shu-Feng,ZHOU Jing-Lin,WANG Jin-Qu. Synthesis of MCM-48/ZSM-5 Composite Molecular Sieve by Two-step Crystallization [J]. Journal of Inorganic Materials, 2009, 24(2): 325-329.
[14]	WANG Mao-Gong,ZHONG Shun-He. Preparation, Characterization, and Gas Separation Properties of Polyimide/TiO₂Composite Membranes [J]. Journal of Inorganic Materials, 2007, 22(1): 148-152.
[15]	LI Yong-Xin,ZHANG Yan-Hua,XUE Bing. Synthesis and Characterization of NaY/MCM-48 Composite Molecular Sieve [J]. Journal of Inorganic Materials, 2006, 21(5): 1209-1216.