The chemical state of a catalyst in operando is particularly important for catalysts that target minority species, such as atmospheric CO2 which has a concentration of only 400 ppm. A reaction can be promoted by the selective binding of reactants or hindered by molecules that block active sites. We show that adsorbed CO2, a very weakly bonded species on TiO2, is unlikely to play the key role in CO2 photoreduction under ambient conditions, at least on rutile (110), as the vast majority of unsaturated Ti sites are terminated by a different, much more strongly bound carbonaceous species: adsorbed bicarbonate (HCO3). Using a combination of scanning tunneling microscopy (STM) and surface spectroscopies, we show that atmospheric CO2 readily and stably displaces adsorbed H2O on rutile (110), creating a self-assembled monolayer of HCO3 and H that is stable at room temperature even in vacuum. This reaction occurs on near-ideal, stoichiometric rutile (110) and does not require surface defects, such as O vacancies, Ti interstitials, or steps. This reaction is promoted both by the strong bidentate bonding of HCO3 as well as the nanoscale H2O film that spontaneously forms on TiO2 under ambient conditions. Density functional theory calculations show that the nanoscale water layer adsorbed to rutile (110) solvates the products and changes the reaction energetics significantly. The chemical state of the catalyst in operando will also be affected by the half-monolayer of adsorbed H produced by the reactive dissociation of H2O.
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High-quality, self-assembled benzoate monolayers were synthesized on rutile (110) using simple aqueous reactions. Sputtering and annealing cycles, which create surface and subsurface defects, were not needed. The monolayers were hydrophobic and remained largely contaminant free during exposures to laboratory air for tens of minutes. During this period, infrared spectroscopy showed that the monolayers did not spontaneously adsorb airborne hydrocarbons or other adventitious aliphatic species. Scanning tunneling microscopy (STM) images, infrared and X-ray photoemission spectra, Monte Carlo simulations, and ab initio calculations were all consistent with benzoate molecules adopting an edge-to-face ring geometry with their four nearest neighborsa tetrameric bonding geometry. This bonding is further stabilized by a pairing interaction between adjacent benzoate molecules, a pairing that has previously been interpreted as dimerization. The coexistence of paired and unpaired regions of the monolayer is consistent with the relatively small additional energy gained by pairing and the cooperative nature of the pairing interaction. Monolayer stability is driven both by the strong bidentate bonding to unsaturated Ti atoms on the surface as well as by π–π interactions between adsorbates.
Our ability to predict nanocatalyst reactivity has been hindered by our lack of atomic-scale understanding of nanocatalyst surface structure. Do nanocatalyst surfaces adopt a bulk-terminated structure or do they reconstruct to minimize their free energy, thereby lowering their reactivity as often observed in vacuum? Similarly, do nanocatalysts processed at high temperatures maintain their low reactivity, reconstructed surfaces when used at low temperatures? Using a new technique for the preparation of anatase nanocatalysts suitable for atomic-scale imaging and surface spectroscopy, we show that solution-prepared anatase is terminated by a monolayer of fluorine, which acts as an atomic-scale oleophobic coating, preventing the accumulation of adventitious carbon. We further show that the most common TiO2 functionalization chemistry, a carboxylic acid solution, causes the spontaneous reorganization of a reconstructed anatase nanocatalyst, leading to a five-fold increase in reactive sites. This reorganization is not observed when carboxylic acids are deposited from the gas phase, suggesting that model experiments in vacuum environments can lead to a nonequilibrium, kinetically trapped state that may not be catalytically relevant. Aqueous carboxylic acid solutions produce densely packed carboxylate monolayers with richer adsorption geometries than previously predicted. Ab initio simulations show that although the carboxylate termination is somewhat less effective at removing surface stress than the reconstruction, it is more effective in lowering the surface energy. This observation suggests that bulk-terminated metal-oxide nanocrystals may be common in reactive environments, even if high temperatures are used to process the nanocatalyst or if the reactant is later rinsed off. As such, the assumption of a bulk-terminated surface may be a reasonable starting point for “materials-by-design” approaches to computationally engineered nanocatalysts.
Cartesian polarization analysis transforms a set of surface infrared spectra obtained in different geometries into their Cartesian components using a mathematical transform, providing direct insight into the bonding geometry of adsorbed molecules. This technique was extended to uniaxial substrates and used to analyze solution-deposited, self-assembled benzoate and alkanoate monolayers on rutile (110). This analysis resolved a long-standing controversy regarding the existence of paired molecules in benzoate monolayers, showing that two distinct isomers exist within the monolayer: a tilted tetramer, which is paired, and a twisted monomer, which is not. The two isomers are nearly isoenergetic, as shown by analysis of STM images and complementary DFT simulations. Infrared and XPS spectra as well as STM images of heptanoate and octanoate monolayers showed the formation of complete monolayers (as opposed to sparse layers or multilayers); however, the alkyl chains in the monolayer are disordered and loosely packed with a significant density of conformational defectsa stark contrast to the near-crystalline, all-trans alkyl monolayers typically formed on Au and Si surfaces. The high disorder in the alkanoate monolayers was attributed to geometry, as the density of alkanoate binding sites on rutile (110) is 30% less than the density of alkyl monolayers on Si. The high density of gauche defects in alkanoate monolayers was attributed to the small energy difference between the all-trans and single-gauche-defect conformers in isolated alkyl chains. In contrast, strong intermolecular interactions in tight-packed alkyl monolayers on Au and Si surfaces suppress gauche defect formation.
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