A compact photo-cell reactor for online H2 photoproduction: revisiting the Pd, Pt, & Au/TiO2 Schottky junctions Pablo Jiménez Calvo 1,¥* , Mario J. Muñoz-Batista 2 , Mark Isaacs 3,4 , Vinavadini Ramnarain 5 , Dris Ihiawakrim 5 , Xiaoyan Li 1 , Miguel Ángel Muñoz-Márquez 4 , Gilberto Teobaldi 5,6 , Mathieu Kociak 1 , Erwan Paineau 1* *pablo.jimenez.calvo@fau.de 1 Université Paris-Saclay, CNRS, Laboratoire de Physique des Solides, 91405 Orsay, France. 2 Department of Chemical Engineering, Faculty of Sciences, University of Granada, Granada, Spain. 3 HarwellXPS, Research Complex at Harwell, Rutherford Appleton Lab, Didcot OX11 0FA, UK. 4 Department of Chemistry, University College London, 20 Gower Street, London, WC1H 0AJ, UK. 5 Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), UMR 7504 CNRS, Université de Strasbourg, 67200 Strasbourg, France . 4 School of Science and Technology - Chemistry Division, University of Camerino, Via Madonna delle Carceri, 62032 Camerino, Italy . 5 Scientific Computing Department, STFC UKRI, Rutherford Appleton Laboratory, Harwell Campus, OX11 0QX Didcot, UK. 6 School of Chemistry, University of Southampton, Highfield, SO17 1BJ Southampton, UK Solar energy is a potential avenue to mitigate the energy crisis. Harvesting and storing solar energy is regarded as a suitable solution. 1 Photocatalysis as a state-of-the-art technology has exhibited reasonable harvesting of energy, allowing chemical transformations to generate solar fuels, as hydrogen (H 2 ), a key vector for the foreseen low-carbon economy. 2 A single catalyst exhibiting an efficient solar-to-photon conversion remains as the bottleneck for technological development. 3 Benchmark semiconductors (SCs), such as Titanium dioxide (TiO 2 ) still do not surpass the needed efficient conversion. TiO 2 limitations are water oxidation overpotential, large band gap i.e., 3.2 eV, and UV light absorption. Adding a metal (M) onto a TiO 2, creates a Schottky junction, regarded as one state-of-the-art approach to enhanced energy conversions. The new interphase junction is expected to enhance the SCs photoactivities in the order of 10-100 folds than the SC alone. 4 The materials design aims at increasing the limited light absorption of TiO 2 by plasmonic effects, to create an intimate M/SC interphase contact to promote new electronic paths and increase the co-catalytic sites along its surface. 5 Pd. Pt, and Au/TiO 2 Schottky materials were used as models to validate the efficiency of a new photoreactor. The compositesvaried their M loading 0.5, 1, and 2 wt.% and were characterized by X-ray scattering, Transmission electron microscopy, Infrared, UV-vis, Ultraviolet / X-ray photoelectron spectroscopies and Inductively coupled plasma. The photocatalytic H 2 production was quantified over time, exhibiting rates of 13, 10, and 7 mmol h -1 g cat -1 for the highest loading, e.g., 2wt.% (Pd, Pt, Au)/TiO 2 . Correlations between structure, M loadings, distribution-size- coverage of M NPs, and the photocatalytic factorswill be discussed. References 1. N. S. Lewis and D. G. Nocera, PNAS , 2006 , 103, 15729-15735. 2. N. S. Lewis, Science , 2007 , 315, 798-801. 3. M. Melchiona and P. Fornasiero, ACS Cat , 2020 , 10, 10, 5493-5501. 4. Y. Dubi and Y. Sivan, Light Sci Appl , 2019 , 8, 89. 5. P. Jiménez-Calvo et al ., Nano Energy , 2020 , 75, 104888.
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