Gian Luca Chiarello

A photocatalytic water splitting device for separate hydrogen and oxygen evolution.

A two-compartment Plexiglas cell has been set up and tested for separate hydrogen and oxygen production from photocatalytic water splitting on a thin TiO2 layer deposited by magnetron sputtering on a flat Ti electrode inserted between the two cell compartments.

Revealing the dynamic structure of complex solid catalysts using modulated excitation X-ray diffraction

X-ray diffraction (XRD) is typically silent towards information on low loadings of precious metals on solid catalysts because of their finely dispersed nature. When combined with a concentration modulation approach, time-resolved high-energy XRD is able to provide the detailed redox dynamics of palladium nanoparticles with a diameter of 2 nm in 2 wt % Pd/CZ (CZ = ceria-zirconia), which is a difficult sample for extended X-ray absorption fine structure (EXAFS) measurements because of the cerium component. The temporal evolution of the Pd(111) and Ce(111) reflections together with surface information from synchronous diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements reveals that Ce maintains Pd oxidized in the CO pulse, whereas reduction is detected at the beginning of the O2 pulse. Oxygen is likely transferred from Pd to Ce(3+) before the onset of Pd re-oxidation. In this context, adsorbed carbonates appear to be the rate-limiting species for re-oxidation.

Adding diffuse reflectance infrared Fourier transform spectroscopy capability to extended x-ray-absorption fine structure in a new cell to study solid catalysts in combination with a modulation approach

We describe a novel cell used to combine in situ transmission X-ray absorption spectroscopy (XAS) with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in a single experiment. The novelty of the cell design compared to current examples is that both radiations are passed through an X-ray and IR transparent window in direct contact with the sample. This innovative geometry also offers a wide surface for IR collection. In order to avoid interference from the crystalline IR transparent materials (e.g., CaF2, MgF2, diamond) a 500 μm carbon filled hole is laser drilled in the center of a CaF2 window. The cell is designed to represent a plug flow reactor, has reduced dead volume in order to allow for fast exchange of gases and is therefore suitable for experiments under fast transients, e.g., according to the concentration modulation approach. High quality time-resolved XAS and DRIFTS data of a 2 wt.% Pt/Al2O3 catalyst are obtained in concentration modulation experiments where CO (or H2) pulses are alternated to O2 pulses at 150 °C. We show that additional information can be obtained on the Pt redox dynamic under working conditions thanks to the improved sensitivity given by the modulation approach followed by Phase Sensitive Detection (PSD) analysis. It is anticipated that the design of the novel cell is likely suitable for a number of other in situ spectroscopic and diffraction methods.

Ageing induced improvement of methane oxidation activity of Pd/YFeO3

The ageing characteristics of flame-made 2 wt% Pd supported on YFeO3 were analysed in comparison with a Pd/Al2O3–CeO2–ZrO2 three-way catalyst (TWC) with respect to structural changes and catalytic performance for methane oxidation under stoichiometric reaction conditions. Thermal treatment under lean conditions (air, 900 °C) resulted in slight decrease in the methane oxidation activity of the TWC. In marked contrast, YFeO3-supported Pd catalysts exhibit an increase in activity after such treatment. Activity enhancement is even higher when the treatment was performed under stoichiometric conditions (air–fuel equivalence ratio, λ = 1, 900 °C). To explain this observation, in-depth characterization (BET, STEM, OSCC, XAS, and CO chemisorption) of fresh and aged catalysts was performed. Both thermal and stoichiometric ageing cause a severe sintering of the support particles and the phase transformation from hexagonal to orthorhombic YFeO3. Despite the absence of a mixed Pd–YFeO3 phase, the growth of Pd particles appears to be limited under the λ = 1 atmosphere. In contrast to thermally aged catalysts where large PdO particles are formed, well-defined metallic Pd nanoparticles of 10–20 nm are present after stoichiometric ageing along with higher methane oxidation activity. Although it is tempting to conclude that metallic Pd is active for methane oxidation under the given conditions, reversible and periodic partial oxidation of the large metallic particles is observed in modulation excitation high energy X-ray diffraction (HXRD) experiments designed to simulate the oscillating redox conditions experienced during operation. These results indicate that large Pd particles exhibit improved methane oxidation activity but equally confirm that activity under stoichiometric conditions is the result of a delicate equilibrium dictated by the bulk-Pd/surface-PdO pair.

Photocatalytic Hydrogen Production

The photocatalytic production of hydrogen from aqueous systems is reviewed, stressing the very promising features of the process as an environmentally friendly, perfectly renewable way to produce hydrogen, the ideal fuel for the future. Starting with a brief historical background, the most recent achievements in the field on the basis of both relevant patents and published literature, are discussed here, with particular emphasis on the development of innovative materials able to capture a larger portion of the solar spectrum with respect to traditional photocatalytic materials, and on the different setups and devices which have been developed and tested.

Fabrication of Pt/Ti/TiO2 Photoelectrodes by RF-Magnetron Sputtering for Separate Hydrogen and Oxygen Production

Evolution of pure hydrogen and oxygen by photocatalytic water splitting was attained from the opposite sides of a composite Pt/Ti/TiO2 photoelectrode. The TiO2 films were prepared by radio frequency (RF)-Magnetron Sputtering at different deposition time ranging from 1 up to 8 h and then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ultraviolet-visible-near infrared (UV-vis-NIR) diffuse reflectance spectroscopy. The photocatalytic activity was evaluated by incident photon to current efficiency (IPCE) measurements and by photocatalytic water splitting measurements in a two-compartment cell. The highest H2 production rate was attained with the photoelectrode prepared by 6 h-long TiO2 deposition thanks to its high content in the rutile polymorph, which is active under visible light. By contrast, the photoactivity dropped for longer deposition time, because of the increased probability of electron-hole recombination due to the longer electron transfer path.

Effects of Surface Modification on the Photocatalytic Activity of TiO2

Abstract The photocatalytic activity of titanium dioxide modified by surface fluorination (F-TiO2) and by differently deposited gold nanoparticles (Au/TiO2) was tested in the degradation of organic substrates, i.e. mainly formic acid and the azo dye Acid Red 1 (AR1), in comparison to that of unmodified titania. The effect of different noble metals deposition on TiO2 was also investigated in the photocatalytic production of hydrogen from water solutions. Surface fluorination increases the rate of photocatalytic oxidation proceeding through a hydroxyl radical-mediated path. These radicals accumulated in higher amount on F-TiO2, because of the shielding effect of adsorbed fluoride. By contrast, the degradation of substrates implying direct interaction with the photogenerated holes occurred at a lower rate on F-TiO2, because of their hampered absorption on the fluorinated surface. The method employed to reduce Au(III) to metallic gold in the preparation of Au/TiO2 photocatalysts was found to affect their photoactivity, also by modifying the surface properties of TiO2. The presence of gold on TiO2 facilitates both the electron transfer to O2 and the mineralization of formic acid, proceeding mainly through direct interaction with photoproduced valence band holes. For substrates undergoing mainly oxidation through a hydroxyl radical mediated mechanism, the photogenerated holes may partly oxidize gold nanoparticles, which consequently act as recombination centers of photoproduced charge carriers. Photocatalytic hydrogen production tests, either from water or from methanol reforming, performed in a special set up, closed recirculation laboratory scale photoreactor employing titanium dioxide and noble-metals-modified titanium dioxide samples prepared by different techniques, confirmed the main role of noble metals nanoparticles on TiO2 in facilitating electron transfer reactions also under anaerobic conditions. Higher hydrogen production rates were attained with the photocatalysts in contact with the vapor phase, i.e. in the absence of the liquid phase mass transfer limitations of aqueous suspensions. The activity of metal nanoparticles-containing photocatalysts prepared by one step flame spray pyrolysis was always higher than that of photocatalysts prepared by deposition on pre-formed gold nanoparticles on TiO2 , most probably because of the better noble metal dispersion on the photocatalyst surface.

Photocatalytic Production of Hydrogen

Abstract: The photocatalytic production of hydrogen represents a fascinating way to convert and store solar energy as chemical energy, in the form of renewable hydrogen, the ideal fuel for the future. Hydrogen can be produced either by direct water splitting or by photo-reforming of organics in either liquid or gas phase. Both methods are reviewed in this chapter. Starting with a brief historical background, the most recent achievements in the field of photocatalytic hydrogen production are discussed, concerning both the development of innovative materials able to exploit a larger portion of the solar spectrum compared to traditional photocatalytic materials, and the different set-ups and devices which have been developed and tested.

Enhanced photopromoted electron transfer over a bilayer WO3 n–n heterojunction prepared by RF diode sputtering

A bilayer WO3 photoelectrode was obtained by radio frequency (RF) plasma sputtering in a reactive 40%O2/Ar atmosphere by depositing two successive WO3 coatings on a tungsten foil at two different total gas pressures (3 Pa and 1.7 Pa, respectively), followed by calcination at 600 °C. Two monolayer samples deposited at each of the two pressures and a bilayer sample deposited at inverted pressures were also prepared. Their photoelectrocatalytic (PEC) activity was evaluated by both Incident Photon-to-Current Efficiency (IPCE) measurements and separate evolution of H2 and O2 by water splitting in a two-compartment PEC cell. SEM analysis revealed that the photoanodes have a nanostructured porous double layer surmounting a columnar basement (Staffa-like morphology, after the name of the Scottish island). Mott–Schottky analysis showed that the single layer deposited at 3 Pa has a conduction flat band potential 0.1 V more positive than that deposited at 1.7 Pa. The equivalent n–n heterojunction at the interface of the double-layer creates a built-in electric field that facilitates the photopromoted electron transfer toward the lower lying conduction band material, while the columnar innermost layer introduces percolation paths for efficient electron transport toward the conductive tungsten foil. Both phenomena contribute to decrease the interfacial charge transfer resistance (Rct) and lead up to a ca. 30% increase in the PEC performance compared to the monolayer and the inverted bilayer coatings and to a 93% faradaic efficiency, which is among the highest reported so far for WO3 photoanodes. Upon methanol addition an outstanding 4-fold photocurrent density increase up to 6.3 mA cm−2 was attained over the bilayer WO3 photoanode, much larger than the usually observed current doubling effect.

In situ attenuated total reflection infrared spectroscopy study of the photocatalytic steam reforming of methanol on Pt/TiO 2

Abstract The effect of Pt deposition on TiO2 and of Pt particle size on the photocatalytic steam reforming of methanol was studied by in situ attenuated total reflectance infrared spectroscopy (ATR-IR). Two 0.5 wt.% Pt/TiO2 samples were investigated, one possessing Pt nanoparticles of ca. 4 nm mean size, the other Pt clusters of ca. 1.3 nm mean size showing significantly different photoactivity in terms of both hydrogen production rate and selectivity to CO, CO2 and all other by-products. The presence of Pt nanoparticles strongly affected both the adsorption/desorption and the reactivity properties of the TiO2 surface. Moreover, the variation of the IR spectrum background upon UV–vis irradiation proved that the photopromoted electrons can be trapped by the Pt particles with the consequent increase of electron-hole separation. Reducing the Pt size from nanoparticles to clusters increased the rate of methanol and water absorption and hindered the detrimental formation of irreversibly adsorbed CO on Pt. All of these aspects contribute to increase the photocatalytic performance of Pt cluster-decorated TiO2 with respect to Pt nanoparticles containing TiO2. Finally, prolonged exposure of all samples to methanol/water vapour in the dark led to the formation of unreactive formate which persisted also under UV–vis irradiation. By contrast, this spectator species did not form when the sample was exposed to methanol/water vapour under UV–vis irradiation.