Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid‐to‐Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen
Won Jun Jo, Georgios Katsoukis, Heinz Frei
Abstract
Abstract 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 Co 3 O 4 , SiO 2 , and TiO 2 prepared by atomic layer deposition (ALD) enable a proton flux of 2400 ± 60 s −1 nm −2 (pH 4, room temperature), while a single TiO 2 (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 TiO 2 and Co 3 O 4 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 SiO 2 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 CO 2 reduction by H 2 O.