Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid-to-Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen

A large jump of proton transfer rates across solid-to-solid interfaces by inserting an ultrathin amorphous silica layer into stacked metal oxide nanolayers is discovered using electrochemical impedance spectroscopy and Fourier-transform infrared reflection absorption spectroscopy (FT-IRRAS). The triple stacked nanolayers of Co3O4, SiO2, and TiO2 prepared by atomic layer deposition (ALD) enable a proton flux of 2400 +/- 60 s(-1) nm(-2) (pH 4, room temperature), while a single TiO2 (5 nm) layer exhibits a threefold lower flux of 830 s(-1) nm(-2). Based on FT-IRRAS measurements, this remarkable enhancement is proposed to originate from the sandwiched silica layer forming interfacial SiOTi and SiOCo linkages to TiO2 and Co3O4 nanolayers, respectively, with the O bridges providing fast H+ hopping pathways across the solid-to-solid interfaces. Together with the complete O-2 impermeability of a 2 nm ALD-grown SiO2 layer, the high flux for proton transport across multi-stack metal oxide layers opens up the integration of incompatible catalytic environments to form functional nanoscale assemblies such as artificial photosystems for CO2 reduction by H2O.