From Layered Porous Architectures to Multicomponent Functional Materials: Evolution of Catalytic Design Concepts

Abstract This Review aims to highlight Avelino Corma’s fundamental contributions to the understanding, rational design, and modification of layered zeolitic materials and to show the evolution of the concepts emerging from this research evolved and inspired the further development of increasingly sophisticated hybrid, multifunctional, and multicomponent porous architectures. The first strategies based on the swelling, pillaring, exfoliation, and delamination of layered zeolites demonstrated that accessibility to active sites could be significantly enhanced while preserving the characteristic high stability and reactivity of pristine zeolites. These advances consolidated key concepts related to accessibility, structural organization, and controlled modification that progressively paved the way to broader design concepts that were subsequently exploited in organic–inorganic hybrid materials and, at a conceptual level, in purely organic porous frameworks, in which active sites, interfaces, and cooperative functions can be intentionally incorporated and spatially organized within rationally designed architectures. The examples recompiled throughout this review illustrate how this conceptual evolution has moved towards multisite catalysis, one-pot multistep reactions and the transition from thermocatalysis towards photocatalytic and energy-related applications. Nevertheless, important challenges remain, on the one hand to the precise control of active-site location and proximity, phase separation, stability with increasing structural complexity and interfacial cooperation; and, on the other hand, the development of advanced synthetic, operando characterization, computational, and data-driven approaches for a deeper understanding and more rational design of functional organic–inorganic hybrid materials. Overall, the evolution discussed here illustrates how concepts emerging from Avelino Corma’s work on zeolite chemistry and heterogeneous catalysis have influenced the development of increasingly integrated and cooperative catalytic materials.