Aqueous-phase electrochemical reduction of carbon dioxide requires an active, earth-abundant electrocatalyst, as well as highly efficient mass transport. Here we report the design of a porous hollow fibre copper electrode with a compact three-dimensional geometry, which provides a large area, three-phase boundary for gas–liquid reactions. The performance of the copper electrode is significantly enhanced; at overpotentials between 200 and 400 mV, faradaic efficiencies for carbon dioxide reduction up to 85% are obtained. Moreover, the carbon monoxide formation rate is at least one order of magnitude larger when compared with state-of-the-art nanocrystalline copper electrodes. Copper hollow fibre electrodes can be prepared via a facile method that is compatible with existing large-scale production processes. The results of this study may inspire the development of new types of microtubular electrodes for electrochemical processes in which at least one gas-phase reactant is involved, such as in fuel cell technology.

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a b s t r a c tHybrid silica membranes have demonstrated to possess a remarkable hydrothermal stability in pervaporation and gas separation processes allowing them to be used in industrial applications. In several publications the hydrothermal stability of pure silica or that of hybrid silica membranes are investigated. To gain deeper insight into the mechanism of hydrothermal stability of silica-based membranes we report a comparison under identical conditions of the gas permeation performance of silica (TEOS), hybrid silica (BTESE) and Zr-doped BTESE (Zr-BTESE) membranes before and after hydrothermal treatments. First, a fast and straightforward hydrothermal stability test at 100°C was applied to screen these membranes. The BTESE and Zr-BTESE membranes maintained their excellent performance after this test, though the TEOS membranes lost their selectivity. Second, hydrothermal tests under water gas shift (WGS) conditions were performed at different temperatures. No significant changes in permeance and selectivity were observed for BTESE derived membranes after a hydrothermal treatment at 300°C. Surprisingly, a large reduction in carbon dioxide permeance was observed for Zr-BTESE hybrid silica membranes after a hydrothermal treatment at 200 or 300°C, resulting in a significant increase of the H 2 /CO 2 permselectivity from 12 to 35.