H2 Photogeneration Using a Phosphonate-Anchored Ni-PNP Catalyst on a Band-Edge-Modified p-Si(111)|AZO Construct.

We report the fabrication of a {semiconductor}|{metal oxide}|{molecular catalyst} construct for the photogeneration of dihydrogen (H2) under illumination, including band-edge modulation of the semiconductor electrode depending on the identity of Si(111)-R and the metal oxide. Briefly, a synergistic band-edge modulation is observed upon (i) the introduction of a p-Si|n-AZO heterojunction and (ii) introduction of an organic dimethoxyphenyl (diMeOPh) group at the heterojunction interface; the AZO also serves as a transparent and conductive conduit, which was capped with an ultrathin layer (20 Å) of amorphous TiO2 for stability. A phosphonate-appended PNP ligand and its Ni complex were then adsorbed to the p/n heterojunction for photoelectrochemical H2 generation (figures of merit: Vonset ≈ + 0.03 V vs NHE, Jmax ≈ 8 mA cm(-2) at 60 mM TsOH).

Platinum-Enhanced Electron Transfer and Surface Passivation through Ultrathin Film Aluminum Oxide (Al2O3) on Si(111)-CH3 Photoelectrodes.

We report the preparation, stability, and utility of Si(111)-CH3 photoelectrodes protected with thin films of aluminum oxide (Al2O3) prepared by atomic layer deposition (ALD). The photoelectrodes have been characterized by X-ray photoelectron spectroscopy (XPS), photoelectrochemistry (Fc in MeCN, Fc-OH in H2O), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) simulation. XPS analysis of the growing Al2O3 layer affords both the thickness, and information regarding two-dimensional versus three-dimensional mode of growth. Impedance measurements on Si(111)|CH3|Al2O3 devices reveal that the nascent films (5-30 Å) exhibit significant capacitance, which is attenuated upon surpassing the bulk threshold (∼30 Å). The Al2O3 layer provides enhanced photoelectrochemical (PEC) stability evidenced by an increase in the anodic window of operation in MeCN (up to +0.5 V vs Ag) and enhanced stability in aqueous electrolyte (up to +0.2 V vs Ag). XPS analysis before and after PEC confirms the Al2O3 layer is persistent and prevents surface corrosion (SiOx). Sweep-rate dependent CVs in MeCN at varying thicknesses exhibit a trend of increasingly broad features, characteristic of slow electron transport kinetics. Simulations were modeled as slow electron transfer through a partially resistive and electroactive Al2O3 layer. Lastly, we find that the Al2O3 ultrathin film serves as a support for the ALD deposition of Pt nanoparticles (d ≈ 8 nm) that enhance electron transfer through the Al2O3 layer. Surface recombination velocity (SRV) measurements on the assembled Si(111)|CH3|Al2O3-15 device affords an S value of 4170 cm s(-1) (τ = 4.2 µs) comparable to the bare Si(111)-CH3 surface (3950 cm s(-1); τ = 4.4 µs). Overall, the results indicate that high electronic quality and low surface defect densities can be retained throughout a multistep assembly of an integrated and passivated semiconductor|thin-film|metal device.

Hybrid organic/inorganic band-edge modulation of p-Si(111) photoelectrodes: effects of R, metal oxide, and Pt on H2 generation.

The efficient generation of dihydrogen on molecularly modified p-Si(111) has remained a challenge due to the low barrier heights observed on such surfaces. The band-edge and barrier height challenge is a primary obstruction to progress in the area of integration of molecular H2 electrocatalysts with silicon photoelectrodes. In this work, we demonstrate that an optimal combination of organic passivating agent and inorganic metal oxide leads to H2 evolution at photovoltages positive of RHE. Modulation of the passivating R group [CH3 → Ph → Naph → Anth → Ph(OMe)2] improves both the band-edge position and ΔV (Vonset - VJmax). Subsequent atomic layer deposition (ALD) of Al2O3 or TiO2 along with ALD-Pt deposition results in to our knowledge the first example of a positive H2 operating potential on molecularly modified Si(111). Mott-Schottky analyses reveal that the flat-band potential of the stable Ph(OMe)2 surface approaches that of the native (but unstable) hydride-terminated surface. The series resistance is diminished by the methoxy functional groups on the phenyl unit, due to its chemical and electronic connectivity with the TiO2 layer. Overall, judicious choice of the R group in conjunction with TiO2|Pt effects H2 generation on p-Si(111) photoelectrodes (Voc = 207 ± 5.2 mV; Jsc = -21.7 mA/cm(2); ff = 0.22; ηH2 = 0.99%). These results provide a viable hybrid strategy toward the operation of catalysts on molecularly modified p-Si(111).

Novel coupled structures of FeWO4/TiO2 and FeWO4/TiO2/CdS designed for highly efficient visible-light photocatalysis.

A quadrilateral disk-shaped FeWO4 nanocrystal (NC) with an average size of ∼35 nm was prepared via hydrothermal reaction. The obtained dark brown FeWO4 NC with a bandgap (Eg) of 1.98 eV was then coupled with TiO2 to form FeWO4/TiO2 composites. The valence band (VB) of FeWO4 (+2.8 eV vs NHE) was more positive than that of TiO2 (+2.7 eV); thus this system could be classified as a Type-B heterojunction. Under visible-light irradiation, 5/95 FeWO4/TiO2 (by wt %) exhibited remarkable photocatalytic activity: the amount of CO2 evolved from gaseous 2-propanol (IP) and the decomposition rate of aqueous salicylic acid (SA) were, respectively, 1.7 and 2.5 times greater than those of typical nitrogen-doped TiO2 (N-TiO2). This unique catalytic property was deduced to arise from the intersemiconductor hole transfer between the VBs of FeWO4 and TiO2. Herein, several experimental evidence were also provided to confirm the hole-transfer mechanism. To further enhance the catalytic efficiency, double-heterojunctioned FeWO4/TiO2/CdS composites were prepared by loading CdS quantum dots (QDs) onto the FeWO4/TiO2 surface. Surprisingly, the catalytic activity for evolving CO2 from IP was 2.6 times greater than that of bare FeWO4/TiO2 and 4.4 times greater than that of N-TiO2, suggesting that both holes and electrons were essential species in decomposing organic compounds.

Effect of layer-by-layer assembled SnO2 interfacial layers in photovoltaic properties of dye-sensitized solar cells.

Ultrathin SnO(2) layers were deposited on FTO substrate by the layer-by-layer (LbL) self-assembly technique utilizing negatively charged 2.5 nm sized SnO(2) nanoparticles (NPs) and cationic poly(allylamine hydrochloride) (PAH). For the construction of dye-sensitized solar cells (DSC), the bulk TiO(2) layer was deposited over the (PAH/SnO(2))(n) (n = 1-10) and subsequently calcined at 500 °C to remove organic components. With introducing four layers of self-assembled SnO(2) interfacial layer (IL), the short circuit current density (J(sc)) of DSCs was increased from 8.96 to 10.97 mA/cm(2), whereas the open circuit voltage (V(oc)) and fill factor (FF) were not appreciably changed. Consequently, photovoltaic conversion efficiency (η) was enhanced from 5.43 to 6.57%. Transient photoelectron spectroscopic analyses revealed that the ultrathin SnO(2) layer considerably increased the electron diffusion coefficient (D(e)) in TiO(2) layer, but the electron lifetime (τ(e)) was decreased unexpectedly. The observed unusual photovoltaic properties would be caused by the unique conduction band (CB) location of the SnO(2), inducing the cascadal energy band matching among the CBs of TiO(2), SnO(2), and FTO.

Improvement of photovoltaic efficiency of dye-sensitized solar cell by introducing highly transparent nanoporous TiO2 buffer layer.

13 nm-sized highly-dispersible TiO2 nanoparticle was synthesized by solvothermal reaction of titanium isopropoxide in a basic condition with tetrabutylammonium hydroxide (TBAH). The prepared TiO2 nanoparticle was applied to fabrication of the transparent nanoporous TiO2 layer with 1.2 microm-thickness. By introducing this buffer layer between FTO and main TiO2 layer in the dye-sensitized solar cell (DSSC), the photovoltaic conversion efficiency was improved from 5.92% to 7.13%. Due to the excellent antireflective role of nanoporous TiO2 buffer layer, the transmittance of FTO glass was increased by 9.2%, and this seemed to be one of the major factors in enhancing photovoltaic conversion efficiency. Moreover, the presence of nanoporous TiO2 buffer layer induces excellent adhesion between FTO and main TiO2 layer, as well as it suppresses the back reaction by blocking direct contact between I3- and FTO electrode.

Formation of efficient dye-sensitized solar cells by introducing an interfacial layer of long-range ordered mesoporous TiO2 thin film.

Long-range ordered cubic mesoporous TiO 2 films with 300 nm thickness were fabricated on fluorine-doped tin oxide (FTO) substrate by evaporation-induced self-assembly (EISA) process using F127 as a structure-directing agent. The prepared mesoporous TiO 2 film (Meso-TiO 2) was applied as an interfacial layer between the nanocrystalline TiO 2 film (NC-TiO 2) and the FTO electrode in the dye-sensitized solar cell (DSSC). The introduction of Meso-TiO 2 increased J sc from 12.3 to 14.5 mA/cm (2), and V oc by 55 mV, whereas there was no appreciable change in the fill factor (FF). As a result, the photovoltaic conversion efficiency ( eta) was improved by 30.0% from 5.77% to 7.48%. Notably, introduction of Meso-TiO 2 increased the transmittance of visible light through the FTO glass by 23% as a result of its excellent antireflective role. Thus the increased transmittance was a key factor in enhancing the photovoltaic conversion efficiency. In addition, the presence of interfacial Meso-TiO 2 provided excellent adhesion between the FTO and main TiO 2 layer, and suppressed the back-transport reaction by blocking direct contact between the electrolyte and FTO electrode.