Power of Aerogel Platforms to Explore Mesoscale Transport in Catalysis

We describe the opportunity to deploy aerogels-an ultraporous nanoarchitecture with co-continuous networks of meso/macropores and covalently bonded nanoparticulates-as a platform to address the nature of the electronic, ionic, and mass transport that underlies catalytic activity. As a test case, we fabricated Au||TiO₂ junctions in composite guest-host aerogels in which ∼5 nm Au nanoparticles are incorporated either directly into the anatase TiO₂ network (Au "in" TiO₂, Au_IN-TiO₂ aerogel) or deposited onto preformed TiO₂ aerogel (Au "on" TiO₂, Au_ON/TiO₂ aerogel). The metal-meets-oxide nanoscale interphase as visualized by electron tomography feature extended three-dimensional (3D) interfaces, but Au_IN-TiO₂ aerogels impose a greater degree of Au contact with TiO₂ particles than does the Au_ON/TiO₂ form. Both aerogel variants enable transport of electrons over micrometer-scale distances across the TiO₂ network to Au||TiO₂ junctions, as evidenced by electron paramagnetic resonance (EPR) and ultrafast visible pump-IR probe time-resolved absorption spectroscopy. The siting of gold nanoparticles in the TiO₂ network more effectively disperses trapped electrons. Density functional theory (DFT) calculations find that increased physical contact between Au and TiO₂, induced by oxygen vacancies, produces increased hybridization of midgap states and quenches unpaired trapped electrons. We assign the apparent differences in electron-transport capabilities to a combination of the relatively better-wired Au||TiO₂ junctions in Au_IN-TiO₂ aerogels, which have a greater capacity to dilute accumulated charge over a larger interfacial surface area, with an enhanced ability to discharge the accumulated electrons via catalytic reduction of adsorbed O₂ to O^2- at the interface. Solid-state ¹H nuclear magnetic resonance experiments show that proton spin-lattice relaxation times and possibly proton diffusion are strongly coupled to Au||TiO₂ interfacial design, likely through spin coupling of protons to unpaired electrons trapped at the TiO₂ network. Taken together, our results show that Au||TiO₂ interfacial design strongly impacts charge carrier (electron and proton) transport over mesoscale distances in catalytic aerogel architectures.