The fundamental principles derived from model studies on metallic gold single crystals for oxygen-assisted reactions provides a framework for understanding nanoporous gold-silver alloy catalysts under working catalytic conditions (ambient pressure, moderate temperature). The mechanistic principles for reactivity obtained from fundamental studies guide the understanding of reactivity and selectivity for oxygen-assisted self-coupling and cross-coupling reactions of alcohols on the catalytic materials. Furthermore, current results coupled with recent reports regarding the activation of nanoporous gold provide insight into the activation/deactivation of these catalysts and the challenge of maintaining sustainable reactivity. Finally, new fabrication methods and developments for gold-based nanoporous alloys with Cu, Pd, and Pt show that complementary reactivity and new properties are possible through these materials.' (C) 2013 Elsevier Inc. All rights reserved.