Carrier dynamics and the role of surface defects: Designing a photocatalyst for gas-phase CO2 reduction.

In2O3-x(OH)y nanoparticles have been shown to function as an effective gas-phase photocatalyst for the reduction of CO2 to CO via the reverse water-gas shift reaction. Their photocatalytic activity is strongly correlated to the number of oxygen vacancy and hydroxide defects present in the system. To better understand how such defects interact with photogenerated electrons and holes in these materials, we have studied the relaxation dynamics of In2O3-x(OH)y nanoparticles with varying concentration of defects using two different excitation energies corresponding to above-band-gap (318-nm) and near-band-gap (405-nm) excitations. Our results demonstrate that defects play a significant role in the excited-state, charge relaxation pathways. Higher defect concentrations result in longer excited-state lifetimes, which are attributed to improved charge separation. This correlates well with the observed trends in the photocatalytic activity. These results are further supported by density-functional theory calculations, which confirm the positions of oxygen vacancy and hydroxide defect states within the optical band gap of indium oxide. This enhanced understanding of the role these defects play in determining the optoelectronic properties and charge carrier dynamics can provide valuable insight toward the rational development of more efficient photocatalytic materials for CO2 reduction.

Colloidal synthesis of 1T-WS2 and 2H-WS2 nanosheets: applications for photocatalytic hydrogen evolution.

In recent years, a lot of attention has been devoted to monolayer materials, in particular to transition-metal dichalcogenides (TMDCs). While their growth on a substrate and their exfoliation are well developed, the colloidal synthesis of monolayers in solution remains challenging. This paper describes the development of synthetic protocols for producing colloidal WS2 monolayers, presenting not only the usual semiconducting prismatic 2H-WS2 structure but also the less common distorted octahedral 1T-WS2 structure, which exhibits metallic behavior. Modifications of the synthesis method allow for control over the crystal phase, enabling the formation of either 1T-WS2 or 2H-WS2 nanostructures. We study the factors influencing the formation of the two WS2 nanostructures, using X-ray diffraction, microscopy, and spectroscopy analytical tools to characterize them. Finally, we investigate the integration of these two WS2 nanostructured polymorphs into an efficient photocatalytic hydrogen evolution system to compare their behavior.

Non-wettable, oxidation-stable, brightly luminescent, perfluorodecyl-capped silicon nanocrystal film.

Here we describe for the first time the synthesis of colloidally stable, brightly luminescent perfluorodecyl-capped silicon nanocrystals and compare the properties of solutions and films made from them with those of their perhydrodecyl-capped relatives. The perfluorodecyl capping group compared to the perhydrodecyl capping group yields superior hydrophobicity and much greater resistance to air oxidation, the enhanced electron-withdrawing character induces blue shifts in the wavelength of photoluminescence, and the lower-frequency carbon-fluorine stretching modes disfavor non-radiative relaxation pathways and boost the absolute photoluminescence quantum yield. Together these attributes bode well for advanced materials and biomedical applications founded upon perfluorodecyl-protected silicon nanocrystals.

Single-crystal adsorption calorimetry and density functional theory of CO chemisorption on fcc Co{110}.

Using single-crystal adsorption calorimetry (SCAC) and density functional theory (DFT), the interaction of carbon monoxide on fcc Co{110} is reported for the first time. The results indicate that adsorption is consistent with molecular chemisorption at all coverages. The initial heat of adsorption of 140 kJ mol(-1) is found in the range of heat values calorimetrically measured on other ferromagnetic metal surfaces, such as nickel and iron. DFT adsorption energies are in good agreement with the experimental results, and comparison between SCAC and DFT for CO on other ferromagnetic surfaces is made. The calculated dissociation barrier of 2.03 eV implies that dissociation at 300 K is unlikely even at the lowest coverage. At high coverages during the adsorption-desorption steady state regime, a pre-exponential factor for CO desorption of 1.2 × 10(17) s(-1) is found, implying a localised molecular adsorbed state prior to desorption in contrast to what we found with Ni surfaces. This result highlights the importance of the choice of the pre-exponential factor in evaluating the activation energy for desorption.

Microcalorimetry of oxygen adsorption on fcc Co{110}.

The coverage dependent heats of adsorption and sticking probabilities for oxygen on fcc Co{110} have been measured at 300 K using single crystal adsorption calorimetry (SCAC). Initial adsorption is consistent with dissociative chemisorption at low coverage followed by oxide formation above 0.6 ML coverage. The initial heat of adsorption of 633 kJ mol(-1) is similar to heat values calorimetrically measured on other ferromagnetic metal surfaces, such as nickel and iron. As the coverage increases, the heat of adsorption and sticking probability drop very rapidly up to the onset of oxidation. As already observed for other oxygen-metal surface systems, strong lateral adatom repulsions are responsible for the transition from the chemisorption regime to oxide film formation at higher coverage. The heat of oxide formation at the onset is 475 kJ mol(-1), which is consistent with the formation of CoO crystallites. The oxide film formation is discussed in terms of nucleation and island growth, and the Mott-Cabrera mechanisms, the latter being evidenced by the relatively constant heat of adsorption and sticking probability in contrast to the nickel and iron oxidation cases.

The effect of analyte acidity on signal suppression and the implications to peak purity determinations using atmospheric pressure ionization mass spectrometry.

The effect of a co-eluting halogenated phenol, spiked at 1% of the main analyte level, has been examined for a series of halogenated phenols using LC-MS techniques. Similarly, the effect of co-eluting anilines has been investigated. The purpose of the work presented here was to evaluate the degree of signal suppression for structurally similar halogenated phenols and for similar anilines utilizing atmospheric pressure chemical ionization (APCI) in the negative mode and electrospray (ESI) in positive mode, respectively. A correlation between the effects of analyte ionization efficiency resulting from co-eluting compounds (signal suppression) and pK(a) has been made for these compounds. It was found that minimal signal suppression occurs when the spiked impurity has a similar (Delta pK(a)<1.5) acidity when compared to the main peak it is co-eluting with. The degree of signal suppression sharply increases when the difference in pK(a)'s between the main peak and the spiked impurity was greater than 1.5 units. Thus, when the main peak is much less acidic (more than 1.5 pK(a) difference) than the co-eluting impurity, signal suppression of the latter would not occur in negative mode APCI. Similarly, when the main peak is much less basic than the co-eluting peak, signal suppression of the impurity will also not be found for aniline compounds in positive mode ESI. Furthermore, the degree of signal suppression decreases as a function of sample load such that injections of 3 microg or less show no discernible impact on the spiked impurity peak. Ultimately, these results indicate that the use of mass spectrometry (MS) in peak purity determinations requires numerous considerations prior to assessing main peak purity. The optimization of sample load during an impurities assay will maximize co-eluting impurity signal as purity determinations by mass spectrometry made at sample loads above the 3 microg (sample load) threshold increase the risk for false negative assessment of impurities.

Cationic Silicon Nanocrystals with Colloidal Stability, pH-Independent Positive Surface Charge and Size Tunable Photoluminescence in the Near-Infrared to Red Spectral Range.

In this report, the synthesis of a novel class of cationic quaternary ammonium-surface-functionalized silicon nanocrystals (ncSi) using a novel and highly versatile terminal alkyl halide-surface-functionalized ncSi synthon is described. The distinctive features of these cationic ncSi include colloidal stability, pH-independent positive surface charge, and size-tunable photoluminescence (PL) in the biologically relevant near-infrared-to-red spectral region. These cationic ncSi are characterized via a combination of high-resolution scanning transmission electron microscopy with energy-dispersive X-ray analysis, Fourier transform infrared, X-ray photoelectron, and photoluminescence spectroscopies, and zeta potential measurements.

Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5.

The reverse water gas shift (RWGS) reaction driven by Nb2O5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5 hybrid catalyst that efficiently hydrogenates CO2 to CO at an impressive rate as high as 1.8 mmol gcat-1 h-1 is developed. The mechanism of this photothermal reaction involves H2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5 nanorods whereupon adsorbed CO2 is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO2 to valuable chemicals and fuels.

Spatial Separation of Charge Carriers in In2O3-x(OH)y Nanocrystal Superstructures for Enhanced Gas-Phase Photocatalytic Activity.

The development of strategies for increasing the lifetime of photoexcited charge carriers in nanostructured metal oxide semiconductors is important for enhancing their photocatalytic activity. Intensive efforts have been made in tailoring the properties of the nanostructured photocatalysts through different ways, mainly including band-structure engineering, doping, catalyst-support interaction, and loading cocatalysts. In liquid-phase photocatalytic dye degradation and water splitting, it was recently found that nanocrystal superstructure based semiconductors exhibited improved spatial separation of photoexcited charge carriers and enhanced photocatalytic performance. Nevertheless, it remains unknown whether this strategy is applicable in gas-phase photocatalysis. Using porous indium oxide nanorods in catalyzing the reverse water-gas shift reaction as a model system, we demonstrate here that assembling semiconductor nanocrystals into superstructures can also promote gas-phase photocatalytic processes. Transient absorption studies prove that the improved activity is a result of prolonged photoexcited charge carrier lifetimes due to the charge transfer within the nanocrystal network comprising the nanorods. Our study reveals that the spatial charge separation within the nanocrystal networks could also benefit gas-phase photocatalysis and sheds light on the design principles of efficient nanocrystal superstructure based photocatalysts.

Morphology-controlled In2O3 nanostructures enhance the performance of photoelectrochemical water oxidation.

Nanotower- and nanowall-like indium oxide structures were grown directly on fluorine-doped tin oxide (FTO)/In2O3 seeded substrates and pristine FTO substrates, respectively, by a straightforward solvothermal method. The tower-like nanostructures are proposed to form via a self-assembly process on the In2O3 seeds. The wall-like nanostructures are proposed to form via epitaxial growth from the exposed edges of SnO2 crystals of the FTO substrate. The nanotowers and nanowalls are composed of highly crystalline and ordered nanocrystals with preferred orientations in the [111] and [110] directions, respectively. The two structures display remarkably different activities when used as photoanodes in solar light-driven water splitting. X-ray photoelectron spectroscopy results suggest an increased density of hydroxyl groups in the nanowalls, which results in a decrease of the work function and a concomitant shift in the onset potential of the photocurrent in the linear sweep voltammograms, which is further confirmed by Mott-Schottky and flat-band potential measurements, indicating the importance of hydroxyl content in determining the photoelectrochemical properties of the films. Morphology-controlled, nanostructured transparent conducting oxide electrodes of the kind described in this paper are envisioned to provide valuable platforms for supporting catalysts and co-catalysts that are intentionally tailored for efficient light-assisted oxidation of water and reduction of carbon dioxide.

Activation of Ultrathin Films of Hematite for Photoelectrochemical Water Splitting via H2 Treatment.

Thermal treatment of ultrathin films of hematite (α-Fe2 O3 ) under an atmosphere of 5 % H2 in Ar is presented as a means of activating α-Fe2 O3 towards the photoelectrochemical splitting of water. Spin-coated films annealed in air exhibited no photoactivity, whereas films treated in hydrogen exhibited a photocurrent response. X-ray photoelectron spectroscopy and UV/Vis absorption spectroscopy results showed that the H2 -treated films contain oxygen vacancies, which suggests improved charge transport. However, Tafel slopes, scan-rate dependent measurements, and kinetic analyses performed by using H2 O2 as a hole scavenger suggested that surface modification may also contribute to their induced photoactivity. Electrochemical impedance spectroscopy results revealed the buildup of a surface trap capacitance at the point of photocurrent onset for the hydrogen-treated films under illumination. A decrease in charge trapping resistance was also observed, which suggests improved transport of charges away from the surface.

New hydrogen-evolution heteronanostructured photocatalysts: Pt-Nb3 O7 (OH) and Cu-Nb3 O7 (OH).

Nanorods of triniobium hydroxide heptaoxide, Nb3 O7 (OH), were synthesized by means of a hydrothermal method. Subsequently, Pt and CuO nanoparticles were introduced on the surface of Nb3 O7 (OH) nanorods by a microwave-assisted solvothermal nucleation and growth technique. The resulting Pt- and CuO-decorated Nb3 O7 (OH) nanorods demonstrated uniform particle dispersion and were fully characterized by X-ray diffraction, electron microscopy, and spectroscopic analysis. Furthermore, the solar-powered photocatalytic hydrogen production properties of these heteronanostructures were studied. The solar-driven H2 formation rate over Pt-Nb3 O7 (OH) was determined to be 710.4 ± 1.7 µmol g(-1) h(-1) with a quantum efficiency of ϕ=5.40% at λ=380 nm. Interestingly, the as-prepared CuO-Nb3 O7 (OH) heteronanostructure was found to be inactive under solar irradiation during an induction phase, whereupon it undergoes an in situ photoreduction process to form the photocatalytically active Cu-Nb3 O7 (OH). This restructuring process was monitored by an in situ measurement of the time-evolution of the optical absorption spectra. The solar-powered H2 production for the restructured compound was determined to be 290.3 ± 5.1 µmol g(-1) h(-1) .

The Rational Design of a Single-Component Photocatalyst for Gas-Phase CO2 Reduction Using Both UV and Visible Light.

The solar-to-chemical energy conversion of greenhouse gas CO2 into carbon-based fuels is a very important research challenge, with implications for both climate change and energy security. Herein, the key attributes of hydroxides and oxygen vacancies are experimentally identified in non-stoichiometric indium oxide nanoparticles, In2O3-x(OH)y, that function in concert to reduce CO2 to CO under simulated solar irradiation.

Electro-oxidation of ascorbic acid by cobalt core-shell nanoparticles on a H-terminated Si(100) and by nanostructured cobalt-coated Si nanowire electrodes.

Determination of the concentration of ascorbic acid in a solution has attracted intense recent interest. Here we demonstrate the feasibility of electro-oxidation of ascorbic acid on spherical cobalt core-shell nanoparticles (10-50 nm dia.) prepared by electrochemical deposition on a H-terminated Si(100) substrate. Depth-profiling X-ray photoelectron spectroscopy reveals that these nanoparticles consist of a metallic cobalt core covered by a Co(OH)2 shell without any evidence of CoOx. Glancing-incidence X-ray diffraction studies further show that the metallic Co core consists of a mixture of hexagonal close packed and face centered cubic structures, the relative composition of which can be easily controlled by the deposition potential. We further demonstrate that when these Co nanoparticles are deposited on a high-surface-area electrode as provided by a Si nanowire template, the resulting nanostructured Co-coated Si nanowire electrode offers a promising high-performance sensor platform for ascorbic acid detection.

Rotational spectra of the van der Waals complexes of molecular hydrogen and OCS.

The a- and b-type rotational transitions of the weakly bound complexes formed by molecular hydrogen and OCS, para-H2-OCS, ortho-H2-OCS, HD-OCS, para-D2-OCS, and ortho-D2-OCS, have been measured by Fourier transform microwave spectroscopy. All five species have ground rotational states with total rotational angular momentum J=0, regardless of whether the hydrogen rotational angular momentum is j=0 as in para-H2, ortho-D2, and HD or j=1 as in ortho-H2 and para-D2. This indicates quenching of the hydrogen angular momentum for the ortho-H2 and para-D2 species by the anisotropy of the intermolecular potential. The ground states of these complexes are slightly asymmetric prolate tops, with the hydrogen center of mass located on the side of the OCS, giving a planar T-shaped molecular geometry. The hydrogen spatial distribution is spherical in the three j=0 species, while it is bilobal and oriented nearly parallel to the OCS in the ground state of the two j=1 species. The j=1 species show strong Coriolis coupling with unobserved low-lying excited states. The abundance of para-H2-OCS relative to ortho-H2-OCS increases exponentially with decreasing normal H2 component in H2He gas mixtures, making the observation of para-H2-OCS in the presence of the more strongly bound ortho-H2-OCS dependent on using lower concentrations of H2. The determined rotational constants are A=22 401.889(4) MHz, B=5993.774(2) MHz, and C=4602.038(2) MHz for para-H2-OCS; A=22 942.218(6) MHz, B=5675.156(7) MHz, and C=4542.960(7) MHz for ortho-H2-OCS; A=15 970.010(3) MHz, B=5847.595(1) MHz, and C=4177.699(1) MHz for HD-OCS; A=12 829.2875(9) MHz, B=5671.3573(7) MHz, and C=3846.7041(6) MHz for ortho-D2-OCS; and A=13 046.800(3) MHz, B=5454.612(2) MHz, and C=3834.590(2) MHz for para-D2-OCS.