Graphical Abstract

Porous features of mesoporous metal nanocrystals are critically important for their applications in catalysis, sorption, and biomedicine and bioimaging. However, precisely engineering porous architectures of mesoporous metals is still highly challenging. Herein, we report a facile soft-templating strategy to precisely engineer porous architectures of multicomponent PdCuBP mesoporous nanospheres (MSs) by using the surfactants with different amphiphilic features. Three kinds of MSs with distinct porous architectures, including three-dimensional (3D) opened/interconnected dendritic mesopores (dMSs), one-dimensional (1D) cylindered mesopores (cMSs), and zero-dimensional (0D) spherical mesopores (sMSs), are prepared. This surfactant-templating method is generally extended to regulate elemental compositions of multicomponent MSs. The resultant Pd-based MSs have been evaluated as the electrocatalysts for ethanol oxidation reaction (EOR). Our results show that quaternary PdCuBP dMSs display remarkably high catalytic activity and better stability for electrocatalytic EOR, compared to those of multicomponent MSs with other porous architectures and less elemental compositions. Mechanism studies reveal that PdCuBP dMSs combine multiple structural and compositional advantages, which kinetically accelerate the electron/mass transfers and also improve the tolerances to poisoning intermediates. We believe that the porous architecture engineering in mesoporous metal electrocatalysts will present a new way to design highly efficient electrocatalysts with desired porous systems and explore their relations towards (electro)catalysis.