Activation of CO2 at chromia-nanocluster-modified rutile and anatase TiO2

Converting CO₂ to fuels is required to enable the production of sustainable fuels and to contribute to alleviating CO₂ emissions. In considering conversion of CO₂, the initial step of adsorption and activation by the catalyst is crucial. In addressing this difficult problem, we have examined how nanoclusters of reducible metal oxides supported on TiO₂ can promote CO₂ activation. In this paper we present density functional theory (DFT) simulations of CO₂ activation on heterostructures composed of extended rutile and anatase TiO₂ surfaces modified with chromia nanoclusters. The heterostructures show non-bulk Cr and O sites in the nanoclusters and an upshifted valence band edge that is dominated by Cr 3d- O 2p interactions. We show that the supported chromia nanoclusters can adsorb and activate CO₂and that activation of CO₂ is promoted whether the TiO₂ support is oxidised or hydroxylated. Reduced heterostructures, formed by removal of oxygen from the chromia nanocluster, also promote CO₂ activation. In the strong CO₂ adsorption modes, the molecule bends giving O-C-O angles of 127 - 132^o and elongation of C-O distances up to 1.30 Å; no carbonates are formed. The electronic properties show a strong CO₂-Cr-O interaction that drives the interaction of CO₂ with the nanocluster and induces the structural distortions. These results highlight that a metal oxide support modified with reducible metal oxide nanoclusters can activate CO₂, thus helping to overcome difficulties associated with the difficult first step in CO₂ conversion

Reactivity of metal oxide nanocluster modified rutile and anatase TiO2: Oxygen vacancy formation and CO2 interaction

The reduction of CO2 to fuels is an active research topic with much interest in using solar radiation and photocatalysts to transform CO2 into higher value chemicals. However, to date there are no photocatalysts known that can use solar radiation to efficiently reduce CO2. One particularly difficult problem is activating CO2 due to its high stability. In this paper we use density functional theory simulations to study novel surface modified TiO2 composites, based on modifying rutile and anatase TiO2 with molecular-sized metal oxide nanoclusters of SnO, ZrO2 and CeO2 and the interaction between CO2 and nanocluster-modified TiO2. We show that reduction of the supported nanocluster is favourable which then provides reduced cations and sites for CO2 adsorption. The atomic structures and energies of different adsorption configurations of CO2 on the reduced modified TiO2 composites are studied. Generally on reduced SnO and CeO2 nanoclusters, the interaction of CO2 is weak producing adsorbed carbonates. On reduced ZrO2, we find a stronger interaction with CO2 and carbonate formation. The role of the energies of oxygen vacancy formation in CO2 adsorption is important because if reduction is too favourable, the interaction with CO2 is not so favourable. We do find an adsorption configuration of CO2 at reduced CeO2 where a CO bond breaks, releasing CO and filling the oxygen vacancy site in the supported ceria nanocluster. These initial results for the interaction of CO2 at surface modified TiO2 provide important insights for future work on CO2 reduction using novel materials

Metal oxide nanocluster-modified TiO2 as solar activated photocatalyst materials

In this review we describe our work on new TiO2 based photocatalysts. The key concept in our work is to form new composite structures by the modification of rutile and anatase TiO2 with nanoclusters of metal oxides and our density functional theory (DFT) level simulations are validated by experimental work synthesizing and characterizing surface-modified TiO2. We use DFT to show that nanoclusters of different metal oxides, TiO2, SnO/SnO2, PbO/PbO2, NiO and CuO can be adsorbed at rutile and anatase surfaces and can induce red shifts in the absorption edge to enable visible light absorption which is the first key requirement for a practical photocatalyst. We furthermore determine the origin of the red shift and discuss the factors influencing this shift and the fate of excited electrons and holes. For p-block metal oxides we show how the oxidation state of Sn and Pb can be used to tune both the magnitude of the red shift and also its mechanism. Finally, aiming to make our models more realistic, we present some new results on the stability of water at rutile and anatase surfaces and the effect of water on oxygen vacancy formation and on nanocluster modification. These nanocluster-modified TiO2 structures form the basis of a new class of photocatalysts which will be useful in oxidation reactions and with the suitable choice of nanocluster modifier can be applied to CO2 reduction

Theoretical insights into the hydrophobicity of low index CeO2 surfaces

The hydrophobicity of CeO2 surfaces is examined here. Since wettability measurements are extremely sensitive to experimental conditions, we propose a general approach to obtain contact angles between water and ceria surfaces of specified orientations based on density functional calculations. In particular, we analysed the low index surfaces of this oxide to establish their interactions with water. According to our calculations, the CeO2 (111) surface was the most hydrophobic with a contact angle of {\Theta} = 112.53{\deg} followed by (100) with {\Theta} = 93.91{\deg}. The CeO2 (110) surface was, on the other hand, mildly hydrophilic with {\Theta} = 64.09{\deg}. By combining our calculations with an atomistic thermodynamic approach, we found that the O terminated (100) surface was unstable unless fully covered by molecularly adsorbed water. We also identified a strong attractive interaction between the hydrogen atoms in water molecules and surface oxygen, which gives rise to the hydrophilic behaviour of (110) surfaces. Interestingly, the adsorption of water molecules on the lower-energy (111) surface stabilises oxygen vacancies, which are expected to enhance the catalytic activity of this plane. The findings here shed light on the origin of the intrinsic wettability of rare earth oxides in general and CeO2 surfaces in particular and also explain why CeO2 (100) surface properties are so critically dependant on applied synthesis methods

Design of novel visible light active photocatalyst materials: Surface modified TiO2

Work on the design of new TiO2 based photocatalysts is described. The key concept is the formation of composite structures through the modification of anatase and rutile TiO2 with molecular-sized nanoclusters of metal oxides. Density functional theory (DFT) level simulations are compared with experimental work synthesizing and characterizing surface modified TiO2. DFT calculations are used to show that nanoclusters of metal oxides such as TiO2, SnO/SnO2, PbO/PbO2, ZnO and CuO are stable when adsorbed at rutile and anatase surfaces, and can lead to a significant red shift in the absorption edge which will induce visible light absorption; this is the first requirement for a useful photocatalyst. The origin of the red shift and the fate of excited electrons and holes are determined. For p-block metal oxides the oxidation state of Sn and Pb can be used to modify the magnitude of the red shift and its mechanism. Comparisons of recent experimental studies of surface modified TiO2 that validate our DFT simulations are described. These nanocluster-modified TiO2 structures form the basis of a new class of photocatalysts which will be useful in oxidation reactions and with a correct choice of nanocluster modified can be applied to other reactions

Length-dependent resistance model for a single-wall Carbon nanotube

The non-linear length-dependent resistance, $\mathcal{R}(l)$ observed in single-wall Carbon nanotubes (SNTs) is explained through the recently proposed ionization energy ($E_I$) based Fermi-Dirac statistics ($i$FDS). The length here corresponds to the Carbon atoms number ($\mathcal{N}$) along the SNT. It is also shown that $\mathcal{R}_y(l_y)$ $<$ $\mathcal{R}_x(l_x)$ is associated with $E_I^y$ $<$ $E_I^x$, which can be attributed to different semiconducting properties in their respective $y$ and $x$ directions.Comment: Publishe