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Akaline EO TiO2 active sites preprint.pdf (5.47 MB)

Alkaline Earth Metal Oxide Nanocluster Modification of Rutile TiO2 (110) Promotes Water Activation and CO2 Chemisorption

submitted on 21.02.2018, 15:50 and posted on 22.02.2018, 14:50 by Michael Nolan
Metal oxide photocatalysts are widely studied for applications in solar driven environmental remediation, antimicrobial activity, hydrogen production and CO2 reduction to fuels. Common requirements for each technology include absorption of visible light, reduced charge carrier recombination and the ability to activate the initial molecule be it a pollutant, water or CO2. The leading photocatalyst is some form of TiO2. A significant amount of work has been undertaken to modifying TiO2 to induce visible light absorption. The structure and composition of the catalyst should facilitate separation of electrons and holes and having active sites on the catalyst is important to promote the initial adsorption and activation of molecules of interest. In this paper we present a first principles density functional theory (DFT) study of the modification of rutile TiO2 (110) with nanoclusters of the alkaline earth metal oxides (MgO, Ca, BaO) and we focus on the effect of surface modification on the key catalyst properties. The modification of rutile TiO2 with CaO and BaO induces a predicted red shift in light absorption. In all cases, photoexcited electrons and holes localise on oxygen in the nanocluster and surface Ti sites, thus enhancing charge separation. The presence of these non-bulk alkaline earth oxide nanoclusters provides highly active sites for water and CO2 adsorption. On MgO-rutile, water adsorbs molecularly and overcomes a barrier of only 0.36 eV for dissociation whereby hydroxyls are stabilised. On CaO- and BaO-modified rutile water adsorbs dissociatively. We attribute this to the high lying O 2p states in the alkaline earth oxide modifiers which are available to interact with water, as well as the non-bulk like geometry around the active site. Upon adsorption of CO2 the preferred binding mode is as a tridentate carbonate-like species, as characterised by geometry and vibrational modes. The carbonate is bound by up to 4 eV. Thus these heterostructures can be interesting for CO2 capture, helping alleviate the problem of CO2 emissions.


SFI 14/US/E2915, H2020 Grant Number 685451 and SFI Grant Number 16/M-ERA/3418, PRACE DECI RI-312763 and 653838, COST CM1104


Email Address of Submitting Author


Tyndall National Institute, UCC



ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest