Substrate surface modification is a key pretreatment during fabrication of composite palladium membranes for hydrogen purification in hydrogen energy applications. The suspension of a natural porous material, Nontronite-15A mineral, without any organic additives was employed in dip-coating of the porous Al2O3 substrate. The Nontronite-15A mineral was characterized by SEM, XRD, TG-DSC and granulometry analysis. The surface and cross-section of the coated porous Al2O3 tubes were observed by SEM, and their pore size distribution and nitrogen flux were also measured. Palladium membranes were fabricated over the coated Al2O3 tubes by a suction-assisted electroless plating. The optimal loading amount of the Nontronite-15A mineral is just to fill in and level up the surface cavities of the Al2O3 substrate rather than to form an extra continuous layer. A thin and selective palladium membrane was successfully obtained, and its permeation performances were tested. The kinetic analyses on the hydrogen flux indicate that the hydrogen permeation behavior exhibits typical characteristics for most of the palladium membranes. During the stability test at 450 degrees C for 192 h, no membrane damage was detected, and the hydrogen flux increased slightly. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.