The occurrence of quantum dipoles at layered materials semiconductor heterointerfaces was investigated by photoemission spectroscopy (PES). Due to the unique properties of layered compounds the prepared interfaces are essentially free of the structural problems known from the usually investigated heterosystems composed of III–V, IV or II–VI materials allowing the detailed investigation of electronic phenomena at the interfaces. We investigated heterostructures composed of epitaxial layers of SnS2 and SnSe2 on different single crystalline layered chalcogenide substrates (WSe2, MoS2, MoTe2, and GaSe). The epilayers were grown by van der Waals epitaxy (vdWe) on the (0001) plane of the substrate crystals. For every system the valence band offset was determined by careful evaluation of the PES data as a function of the film thickness. Using published values for the band gaps and the experimentally determined work functions and surface potentials the band lineup for each system was determined. The band offsets of all systems were found to differ from the prediction of the electron affinity rule (EAR) by a small systematic deviation which was related to the occurrence of localized quantum dipoles at the interface. This deviation can be expressed as a linear charge transfer correction term added to the original EAR. This corrected EAR is still a linear rule allowing the assignment of “characteristic energies” to each material for the calculation of the band offset. We could demonstrate that the error margin of the corrected EAR lies well within the experimental error of PES experiments, thus proving the general applicability of linear laws for the determination of the band offset in absence of structural dipoles.

No abstract

The primary challenge in materials design and synthesis is achieving the balance between performance and economy for real-world application. This issue is addressed by creating a thiol functionalized porous organic polymer (POP) using simple free radical polymerization techniques to prepare a cost-effective material with a high density of chelating sites designed for mercury capture and therefore environmental remediation. The resulting POP is able to remove aqueous and airborne mercury with uptake capacities of 1216 and 630 mg g , respectively. The material demonstrates rapid kinetics, capable of dropping the mercury concentration from 5 ppm to 1 ppb, lower than the US Environmental Protection Agency's drinking water limit (2 ppb), within 10 min. Furthermore, the material has the added benefits of recyclability, stability in a broad pH range, and selectivity for toxic metals. These results are attributed to the material's physical properties, which include hierarchical porosity, a high density of chelating sites, and the material's robustness, which improve the thiol availability to bind with mercury as determined by X-ray photoelectron spectroscopy and X-ray absorption fine structure studies. The work provides promising results for POPs as an economical material for multiple environmental remediation applications.

The offsets between the highest occupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbitals (LUMO) at the 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA)/chloroindium phthalocyanine (ClInPc) and PTCDA/zinc phthalocyanine (ZnPc) organic heterojunctions were estimated from a combination of X-ray and ultraviolet photoemission (XPS,UPS) measurements. This combined method allows an improved determination of the electronic structure of such organic/organic‘ interfaces due to the separate determination of the band bending (charge redistribution) following heterojunction formation. Both interfaces have large offsets in the onset for photoemission from their HOMO levels (PTCDA/ZnPc:  0.88 eV; PTCDA/CnlInPc:  0.93 eV). Using thin film absorbance data, the corresponding offsets in LUMO levels were estimated to be 0.66 eV (PTCDA/ZnPc) and 0.34 (PTCDA/ClInPc). The ZnPc/PTCDA interface showed a significant interface dipole (0.25 eV) while the ClInPc/PTCDA contact was essentially dipole free.

TiO 2 is one of the most promising candidate materials for clean-energy generation and environmental remediation. However, the larger-than 3.1 eV bandgap of perfectly crystalline TiO 2 confines its application to the ultraviolet (UV) range. In this study, the electronic and the optical properties of undoped mixed-phase TiO 2 nanoparticles were investigated using UV and inverse photoemission, low intensity Xray photoelectron (XP), and diffused reflectance spectroscopy methods. The facile solution-phase synthesized nanoparticles exhibited a midgap-states-induced energy gap of only ∼2.2 eV. The diffused reflectance spectrum showed sub-bandgap absorption due to the existence of a large Urbach tail at 2.2 eV. The UV photoemission spectrum evidenced the presence of midgap states. The 2.2 eV energy gap enables the nanoparticles to be photoactive in the visible energy range. The gas-phase CO 2 photoreduction test with water vapor under visible light illumination was studied in the presence of the synthesized TiO 2 nanoparticles which resulted in the production of ∼1357 ppm gr −1 (catalyst) CO and ∼360 ppm gr −1 (catalyst) CH 4 , as compared to negligible amounts using a standard TiO 2 (P25) sample. The synthesized nanoparticles possessed a Brunauer−Emmett−Teller (BET) surface area of ∼131 m 2 gr −1 , corresponding to a Langmuir surface area of ∼166 m 2 gr −1 . The determined interplanar distances of atomic planes by highresolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) methods were consistent. A detailed elemental analysis using XPS and inductively coupled plasma mass spectrometry (ICP-MS) demonstrated that the synthesized catalyst is indeed undoped. The catalytic activity of the undoped synthesized nanoparticles in the visible spectrum can be ascribed to the unique electronic structure due to the presence of oxygen vacancy related defects and the high surface area.