Photocatalysis can be used advantageously for hydrogen production using a light source (near-UV light), a noble metal-doped semiconductor and an organic scavenger (2.0 v/v% ethanol). With this end, palladium was doped on TiO2 photocatalysts at different metal loadings (0.25 to 5.00 wt%). Photocatalysts were synthetized using a sol-gel method enhancing morphological properties with a soft template precursor. Experiments were carried out in the Photo-CREC Water II reactor system developed at CREC-UWO (Chemical Reactor Engineering Centre- The University of Western Ontario) Canada. This novel unit offers hydrogen storage and symmetrical irradiation allowing precise irradiation measurements for macroscopic energy balances. Hydrogen production rates followed in all cases a zero-order reaction, with quantum yields as high as 30.8%.

Photoreduction with visible light can enhance the photocatalytic activity of TiO2 for the production of hydrogen. In this article, we present a strategy to photoreduce a palladium-doped TiO2 photocatalyst by using near-UV light prior to its utilization. A sol-gel methodology was employed to prepare the photocatalysts with different metal loadings (0.25–5.00 wt% Pd). The structural and morphological characteristics of the synthesized Pd-TiO2 were analyzed by using X-ray Diffraction (XRD), BET Surface Area (SBET), TemperatureProgrammed Reduction (TPR), Chemisorption and X-ray Photoelectron Spectroscopy (XPS). Hydrogen was produced by water splitting under visible light irradiation using ethanol as an organic scavenger. Experiments were developed in the Photo-CREC Water-II (PCW-II) Reactor designed at the CREC-UWO (Chemical Reactor Engineering Centre). It was shown that the mesoporous 0.25 wt% Pd-TiO2 with 2.5 1eV band gap exhibits, under visible light, the best hydrogen production performance, with a 1.58% Quantum Yield being achieved.

Photocatalytic hydrogen production via water splitting using a noble metal on a TiO2 is a technology that has developed rapidly over the past few years. Specifically, palladium doped TiO2 irradiated with near-UV or alternatively with visible light has shown promising results. With this end in mind, strategically designed experiments were developed in the Photo-CREC Water-II (PCW-II) Reactor using a 0.25 wt% Pd-TiO2 under near-UV and visible light, and ethanol as an organic scavenger. Acetaldehyde, carbon monoxide, carbon dioxide, methane, ethane, ethylene, and hydrogen peroxide together with hydrogen were the main chemical species observed. A Langmuir adsorption isotherm was also established for hydrogen peroxide. On this basis, it is shown that pH variations, hydrogen peroxide formation/adsorption, and the production of various redox chemical species provide an excellent carbon element balance, as well as OH• and H• radicals balances. Under near-UV irradiation, 108 cm3 STP of H2 is produced after 6 h, reaching an 99.8% elemental carbon balance and 98.2% OH• and H• and radical balance. It is also proven that a similar reaction network can be considered adequate for the photoreduced Pd-TiO2 photocatalyst yielding 29 cm3 STP of H2 with 97.5% carbon and the 99.2% OH•–H• radical balance closures. It is shown on this basis that a proposed “series-parallel” reaction network describes the water splitting reaction using the mesoporous Pd-TiO2 and ethanol as organic scavenger.

The present study reports photochemical thermodynamic efficiency factors (PTEFs) for hydrogen production. The PTEF parameter equates the enthalpy of formation of consumed OH• and H• free radicals with their absorbed photon energy. In this case, therefore, the PTEFs provide information on the efficiency of photon energy utilization. Data from different Pt- and Pd-doped photocatalysts used for hydrogen production, obtained in a Photo-CREC Water-II reactor under near-UV and visible irradiations, were considered. The evaluated photocatalysts were characterized using X-ray diffraction (XRD), the Brunauer–Emmett–Teller (BET) method, chemisorption, and diffuse reflectance UV–visible spectroscopy. Macroscopic radiation energy balances and the rates of photoconversion of hydrogen were also determined to evaluate both PTEFs and quantum yields (φ). While PTEFs were reported previously by our research group for water and air decontamination, the PTEF is now applied, for the first time, in this research, to hydrogen production.

A palladium (Pd) doped mesoporous titanium dioxide (TiO2) photocatalyst was used to produce hydrogen (H2) via water splitting under both near-UV and visible light. Experiments were carried out in the Photo-CREC Water-II Reactor (PCW-II) using a 0.25 wt% Pd-TiO2 photocatalyst, initial pH = 4 and 2.0 v/v% ethanol, as an organic scavenger. After 6 h of near-UV irradiation, this photocatalyst yielded 113 cm3 STP of hydrogen (H2). Furthermore, after 1 h of near-UV photoreduction followed by 5 h of visible light, the 0.25 wt% Pd-TiO2 photocatalyst yielded 5.25 cm3 STP of H2. The same photocatalyst, photoreduced for 24 h under near-UV and subsequently exposed to 5 h of visible light, yielded 29 cm3 STP of H2. It was observed that the promoted redox reactions led to the production of hydrogen and by-products such as methane, ethane, ethylene, acetaldehyde, carbon monoxide, carbon dioxide and hydrogen peroxide. These redox reactions could be modeled using an “in series-parallel” reaction network and Langmuir Hinshelwood based kinetics. The proposed rate equations were validated using statistical analysis for the experimental data and calculated kinetic parameters. Furthermore, Quantum yields (QYH•%) based on the H• produced were also established at promising levels: (a) 34.8% under near-UV light and 1.00 g L−1 photocatalyst concentration; (b) 8.8% under visible light and 0.15 g L−1. photocatalyst concentration following 24 h of near-UV.