Photocatalytic production of hydrogen from binary mixtures of C-3 alcohols on Pt/TiO2: Influence of alcohol structure

López-Tenllado, Francisco J.; Hidalgo-Carrillo, Jesús; Montes, Vicente; Sánchez‐López, Elena; Urbano, Francisco J.; Marinas, Alberto

doi:10.1016/j.cattod.2018.10.001

Cited by 16 publications

(7 citation statements)

References 21 publications

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“…There are two main ways to retard the electron-hole recombination in TiO 2 : (i) the generation of irregularities or surface defects, or (ii) the modification of TiO 2 with a metal, creating a Shottky barrier in the junction zone between the two materials that would limit the recombination process, by flowing electrons generated from the valence band of TiO 2 to the metal [ 12 ]. Noble metals such as Pt, Pd or Au [ 10 , 13 ] have been found to be particularly effective though there is a need to use some more cost-effective transition metals such as Fe, Cu or Ni [ 14 , 15 , 16 ]. This barrier can also be created by modifying TiO 2 with carbon nanostructures, such as nanotubes or graphene [ 17 ].…”

Section: Introductionmentioning

confidence: 99%

Olive Leaves as Biotemplates for Enhanced Solar-Light Harvesting by a Titania-Based Solid

et al. 2020

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Olive leaves (by-product from olive oil production in olive mills) were used as biotemplates to synthesize a titania-based artificial olive leaf (AOL). Scanning electron microscopy (SEM) images of AOL showed the successful replication of trichomes and internal structure channels present in olive leaves. The BET surface area of AOL was 52 m2·g−1. X-ray diffraction (XRD) and Raman spectra revealed that the resulting solid was in the predominantly-anatase crystalline form (7.5 nm average particle size). Moreover, the synthesis led to a red-shift in light absorption as compared to reference anatase (gap energies of 2.98 and 3.2 eV, respectively). The presence of surface defects (as evidenced by X-ray photoelectron spectroscopy, XPS, and electron paramagnetic resonance spectroscopy, EPR) and doping elements (e.g., 1% nitrogen, observed by elemental analysis and XPS) could account for that. AOL was preliminarily tested as a catalyst for hydrogen production through glycerol photoreforming and exhibited an activity 64% higher than reference material Evonik P25 under solar irradiation and 144% greater under ultraviolet radiation (UV).

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Section: Introductionmentioning

confidence: 99%

Olive Leaves as Biotemplates for Enhanced Solar-Light Harvesting by a Titania-Based Solid

et al. 2020

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“…In the entire range of the studied temperatures, the H 2 formation rate fell in the sequence of 1-BuOH >> 2-BuOH > t-BuOH as shown in Figure 3. This trend can be explained by the increased adsorption strength of primary alcohols on the metal oxide surface as compared to secondary and tertiary isomers [20]. It is worth noting that the isomers of alcohols exhibit such tendencies with many other TiO 2 -based photocatalysts loaded with noble metals, M/TiO 2 , where M = Pt, Pd, Au, Rh [21][22][23].…”

Section: Resultsmentioning

confidence: 90%

Influence of Butanol Isomerization on Photothermal Hydrogen Production over Ti@TiO2 Core-Shell Nanoparticles

et al. 2022

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In this work, we reported for the first time the effect of butanol isomerization on the photothermal production of hydrogen in the presence of a noble, metal-free Ti@TiO2 core-shell photocatalyst. The experiments were performed in aqueous solutions of 1-BuOH, 2-BuOH, and t-BuOH under Xe lamp irradiation (vis/NIR: 8.4 W, UV: 0.6 W) at 35–69 °C. The increase in temperature significantly enhanced H2 formation, indicating a strong photothermal effect in the studied systems. However, in dark conditions, H2 emission was not observed even at elevated temperatures, which clearly points out the photonic origin of H2 photothermal formation. The rate of H2 production followed the order of 1-BuOH>>2-BuOH>t-BuOH in the entire range of studied temperatures. In the systems with 1-BuOH and 2-BuOH, hydrogen was the only gaseous product measured online in the outlet carrier argon using mass spectrometry. By contrast, a mixture of H2, CH4, and C2H6 was detected for t-BuOH, indicating a C–C bond scission with this isomer during photocatalytic degradation. The apparent activation energies, Ea, with 1-BuOH/2-BuOH isomers (20–21 kJ·mol−1) was found to be larger than for t-BuOH (13 kJ·mol−1). The significant difference in thermal response for 1-BuOH/2-BuOH and t-BuOH isomers was ascribed to the difference in the photocatalytic mechanisms of these species. The photothermal effect with 1-BuOH/2-BuOH isomers can be explained by the thermally induced transfer of photogenerated, shallowly trapped electron holes to highly reactive free holes at the surface of TiO2 and the further hole-mediated cleavage of the O-H bond. In the system with t-BuOH, another mechanism could also contribute to the overall process through hydrogen abstraction from the C–H bond by an intermediate •OH radical, leading to CH3• group ejection. Formation of •OH radicals during light irradiation of Ti@TiO2 nanoparticle suspension in water has been confirmed using terephthalate dosimetry. This analysis also revealed a positive temperature response of •OH radical formation.

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“…Hydrogen production from the alcohol-based reforming 27 , including methanol 28 and ethyl alcohol 29 , is also affected by the hydrogen solubility behavior. Moreover, the hydrogen production using the photocatalytic 30 , hydrogen-liquid-hydride slurry 31 , and aqueous and anhydrous methanol 32 reactors is also controlled by H 2 /liquid phase behavior. Reliable knowledge about hydrogen solubility in bio-based alcohols (ethanol and glycerol) is necessary for hydrogen production using dehydrogenation reactions 33 , 34 .…”

Section: Introductionmentioning

confidence: 99%

Development of a reliable empirical correlation to calculate hydrogen solubility in seventeen alcoholic media

Hosseini

2022

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This study uses the differential evolution optimization algorithm to adjust the coefficient of Arrhenius-shape correlation for calculating hydrogen (H2) solubility in alcohol-based media. The pre-exponential and exponential parts of this correlation are the functions of pressure and absolute temperature, respectively. Since this model has been validated using seventeen alcohol/hydrogen binary mixtures, it is the most generalized correlation in this regard. The proposed Arrhenius-shape correlation predicts 285 laboratory solubility measurements with the absolute average relative deviation (AARD%) of 3.28% and regression coefficient (R2) of 0.99589. The accuracy of the developed model has also been compared with two empirical correlations and three equations of state suggested in the literature. The Arrhenius-shape model has 15% and 50% smaller AARD than the most accurate empirical correlation and equation of state, respectively. Simulation findings demonstrate that all alcohol/hydrogen mixtures thermodynamically behave based on Henry’s law. Hydrogen solubility in alcohols increases by increasing either pressure or temperature. 1-octanol has the maximum ability to absorb the H2 molecules.

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Photocatalytic production of hydrogen from binary mixtures of C-3 alcohols on Pt/TiO2: Influence of alcohol structure

Cited by 16 publications

References 21 publications

Olive Leaves as Biotemplates for Enhanced Solar-Light Harvesting by a Titania-Based Solid

Olive Leaves as Biotemplates for Enhanced Solar-Light Harvesting by a Titania-Based Solid

Influence of Butanol Isomerization on Photothermal Hydrogen Production over Ti@TiO2 Core-Shell Nanoparticles

Development of a reliable empirical correlation to calculate hydrogen solubility in seventeen alcoholic media

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