Hydrogen Selective SiCH Inorganic−Organic Hybrid/γ-Al₂O₃ Composite Membranes

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.