The nature of interfaces and charge trapping sites in photocatalytic mixed-phase TiO2 from first principles modeling

Mixed phase rutile/anatase catalysts show increased reactivity compared with the pure phases alone. However, the mechanism causing this effect is not fully understood. The electronic properties of the interface and the relative energy of the electron in each phase play a key role in lowering the rate of recombination of electron hole pairs. Using density functional theory and the +U correction, we calculated the bands offsets between the phases taking into account the effect of the interface. Our model included several thousands atoms, and thus is a good representation of an interface between actual nanoparticles. We found rutile to have both higher conduction and valence band offsets than rutile, leading to an accumulation of electrons in the anatase phase accompanied by hole accumulation in the rutile phase. We also probed the electronic structure of our heterostructure and found a gap state caused by electrons localized in undercoordinated Ti atoms which were present within the interfacial region. Interfaces between bulk materials and between exposed surfaces both showed electron trapping at undercoordinated sites. These undercoordinated (typically four) atoms present localized electrons that could enable reduction reactions in the interfacial region, and could explain the increased reactivity of mixed-phase TiO2 photocatalyst materials

Local interfacial structure influences charge localization in titania composites: Beyond the band alignment paradigm

The phase junction of nanocomposite materials is key to enhanced performance but is largely ignored in recent theoretical examinations of photocatalytic interactions in titania-based composites. Computational advances now allow more precise modeling of the electronic and optical properties of composites, and focusing on mixed-phase TiO2 as a model, we use density functional theory (DFT) to interrogate the essential structural feature, namely, the rutile anatase interface, and its relationship to photogenerated charge localization, bulk band alignments, and defect formation. The interfacial region is disordered and distinct from rutile and anatase and contains low coordinated Ti sites and oxygen vacancies, both drivers of charge localization. The relaxations of the interface upon formation of excited electrons and holes determine the final location of charges which cannot always be predicted from bulk band alignments. A detailed understanding of the interfacial phase junction lays the foundation for directed synthesis of highly active and efficient composite photocatalysts

The nature of interfaces and charge trapping sites in photocatalytic mixed-phase TiO2 from first principles modeling

Mixed phase rutile/anatase catalysts show increased reactivity compared with the pure phases alone. However, the mechanism causing this effect is not fully understood. The electronic properties of the interface and the relative energy of the electron in each phase play a key role in lowering the rate of recombination of electron hole pairs. Using density functional theory and the +U correction, we calculated the bands offsets between the phases taking into account the effect of the interface. Our model included several thousands atoms, and thus is a good representation of an interface between actual nanoparticles. We found rutile to have both higher conduction and valence band offsets than rutile, leading to an accumulation of electrons in the anatase phase accompanied by hole accumulation in the rutile phase. We also probed the electronic structure of our heterostructure and found a gap state caused by electrons localized in undercoordinated Ti atoms which were present within the interfacial region. Interfaces between bulk materials and between exposed surfaces both showed electron trapping at undercoordinated sites. These undercoordinated (typically four) atoms present localized electrons that could enable reduction reactions in the interfacial region, and could explain the increased reactivity of mixed-phase TiO2 photocatalyst materials

Lifting the Pt{100} Surface Reconstruction Through Oxygen Adsorption: A DFT Analysis

The adsorption of atomic oxygen on unreconstructed Pt{100}-(1×1) role= presentation style= box-sizing: border-box; display: inline; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; color: rgb(51, 51, 51); font-family: Arial, sans-serif; position: relative; \u3ePt{100}-(1×1)Pt{100}-(1×1) and reconstructedPt{100}-(5×1) role= presentation style= box-sizing: border-box; display: inline; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; color: rgb(51, 51, 51); font-family: Arial, sans-serif; position: relative; \u3ePt{100}-(5×1)Pt{100}-(5×1) was modeled using density-functional theory in an attempt to understand the relative stability of the unreconstructed phase as a function of oxygen coverage. Our calculations showed that at zero temperature the (5×1) role= presentation style= box-sizing: border-box; display: inline; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; color: rgb(51, 51, 51); font-family: Arial, sans-serif; position: relative; \u3e(5×1)(5×1) is more stable than the unreconstructed (1×1) role= presentation style= box-sizing: border-box; display: inline; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; color: rgb(51, 51, 51); font-family: Arial, sans-serif; position: relative; \u3e(1×1)(1×1) phase at zero oxygen coverage. However, oxygen absorption on the Pt{100}-(5×1) role= presentation style= box-sizing: border-box; display: inline; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; color: rgb(51, 51, 51); font-family: Arial, sans-serif; position: relative; \u3ePt{100}-(5×1)Pt{100}-(5×1) phase removed the reconstruction, reversing the phase stability. Using thermochemical analysis, we show desorption of oxygen corresponding to a temperature near 730 K, consistent with experimentally observed desorption peaks for oxygen covered (1×1) role= presentation style= box-sizing: border-box; display: inline; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; color: rgb(51, 51, 51); font-family: Arial, sans-serif; position: relative; \u3e(1×1)(1×1)surfaces. These results have ramifications for understanding the full Pt{100}(1×1)→Pt{100} role= presentation style= box-sizing: border-box; display: inline; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; color: rgb(51, 51, 51); font-family: Arial, sans-serif; position: relative; \u3ePt{100}(1×1)→Pt{100}Pt{100}(1×1)→Pt{100}-hex-R0.7° surface phase transition

Immobilization Mechanisms of Deoxyribonucleic Acid (DNA) to Hafnium Dioxide (HfO₂) Surfaces for Biosensing Applications

Immobilization of biomolecular probes to the sensing substrate is a critical step for biosensor fabrication. In this work we investigated the phosphate-dependent, oriented immobilization of DNA to hafnium dioxide surfaces for biosensing applications. Phosphate-dependent immobilization was confirmed on a wide range of hafnium oxide surfaces; however, a second interaction mode was observed on monoclinic hafnium dioxide. On the basis of previous materials studies on these films, DNA immobilization studies, and density functional theory (DFT) modeling, we propose that this secondary interaction is between the exposed nucleobases of single stranded DNA and the surface. The lattice spacing of monoclinic hafnium dioxide matches the base-to-base pitch of DNA. Monoclinic hafnium dioxide is advantageous for nanoelectronic applications, yet because of this secondary DNA immobilization mechanism, it could impede DNA hybridization or cause nonspecific surface intereactions. Nonetheless, DNA immobilization on polycrystalline and amorphous hafnium dioxide is predominately mediated by the terminal phosphate in an oriented manner which is desirable for biosensing applications

Palladium–Tin Alloyed Catalysts for the Ethanol Oxidation Reaction in an Alkaline Medium

In this paper, we present a study of a series of carbon-supported Pd–Sn binary alloyed catalysts prepared through a modified Polyol method as anode electrocatalysts for direct ethanol fuel cell reactions in an alkaline medium. Transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and aberration-corrected scanning transmission electron microscopy equipped with electron energy loss spectroscopy were used to characterize the Pd–Sn/C catalysts, where homogeneous Pd–Sn alloys were determined to be present with the surface Sn being partially oxidized. Among various Pd–Sn catalysts, Pd₈₆Sn₁₄/C catalysts showed much enhanced current densities in cyclic voltammetric and chronoamperometric measurements, compared to commercial Pd/C (Johnson Matthey). The overall rate law of ethanol oxidation reaction for both Pd₈₆Sn₁₄/C and commercial Pd/C were also determined, which clearly showed that Pd₈₆Sn₁₄/C was more favorable in high ethanol concentration and/or high pH environment. Density functional theory calculations also confirmed Pd–Sn alloy structures would result in lower reaction energies for the dehydrogenation of ethanol, compared to the pure Pd crystal