Superhydrophobic membranes composed of an organic-inorganic hybrid polymer, namely polycarbosilane (PCS) with Mw of 4-8.9 ×10 3 , were formed on a mesoporous γ-Al 2O3-modified α-Al2O3 porous support. Under dry condition at 50 • C, the supported PCS membranes exhibited H2 permeance of 1.1-1.6 ×10 −6 mol⋅m −2 ⋅s −1 ⋅Pa −1 and H2/N2 selectivity of 9.7-12.6 together with unique H2/He selectivity of 1.4-1.6. Even under saturated humidity at 50 • C, H2 permeance remained at 7.7 ×10 −8 mol −1 m −2 s −1 Pa −1 with improved H2/N2 selectivity of 26. Moreover, when the measurements were performed using a H2-N2 (2:1) mixed feed gas as a simulated syngas produced by novel solar hydrogen production systems, the H2 permeance almost unchanged, while the N2 permeance was below the limit of detection. These results revealed a great potential of PCSs to develop novel H 2selective membranes for purifying solar hydrogen under high-humidity conditions around 50 • C. Further study on the gas permeation behaviors of He, H2 and N2 suggested that the enhanced H2/N2 selectivity under the highhumidity conditions could be explained by the synergistic effect of preferential H 2 permeation through the dense PCS network governed by the solid state diffusion mechanism and blockage of N 2 permeation through micropore channels within the PCS network by the permeate H2O-induced plugging at around the hetero interface between the superhydrophobic PCS and highly hydrophilic γ-Al 2O3.
Solar hydrogen production via the photoelectrochemical water-splitting reaction is attractive as one of the environmental-friendly approaches for producing H2. Since the reaction simultaneously generates H2 and O2, this method requires immediate H2 recovery from the syngas including O2 under high-humidity conditions around 50 °C. In this study, a supported mesoporous γ-Al2O3 membrane was modified with allyl-hydrido-polycarbosilane as a preceramic polymer and subsequently heat-treated in Ar to deliver a ternary SiCH organic–inorganic hybrid/γ-Al2O3 composite membrane. Relations between the polymer/hybrid conversion temperature, hydrophobicity, and H2 affinity of the polymer-derived SiCH hybrids were studied to functionalize the composite membranes as H2-selective under saturated water vapor partial pressure at 50 °C. As a result, the composite membranes synthesized at temperatures as low as 300–500 °C showed a H2 permeance of 1.0–4.3 × 10−7 mol m−2 s−1 Pa−1 with a H2/N2 selectivity of 6.0–11.3 under a mixed H2-N2 (2:1) feed gas flow. Further modification by the 120 °C-melt impregnation of low molecular weight polycarbosilane successfully improved the H2-permselectivity of the 500 °C-synthesized composite membrane by maintaining the H2 permeance combined with improved H2/N2 selectivity as 3.5 × 10−7 mol m−2 s−1 Pa−1 with 36. These results revealed a great potential of the polymer-derived SiCH hybrids as novel hydrophobic membranes for purification of solar hydrogen.
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