As a single atom Pd outperforms Pt as the most active co-catalyst for photocatalytic H2 evolution
Gihoon Cha,
Imgon Hwang,
Seyedsina Hejazi,
Ana S. Dobrota,
Igor A. Pašti,
Benedict Osuagwu,
Hyesung Kim,
Johannes Will,
Tadahiro Yokosawa,
Zdeněk Badura,
Štěpán Kment,
Shiva Mohajernia,
Anca Mazare,
Natalia V. Skorodumova,
Erdmann Spiecker,
Patrik Schmuki
Affiliations
Gihoon Cha
Institute for Surface Science and Corrosion WW4-LKO, Department of Materials Science, University of Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, Germany
Imgon Hwang
Institute for Surface Science and Corrosion WW4-LKO, Department of Materials Science, University of Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, Germany
Seyedsina Hejazi
Institute for Surface Science and Corrosion WW4-LKO, Department of Materials Science, University of Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, Germany
Ana S. Dobrota
Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, 11000 Serbia
Igor A. Pašti
Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, Belgrade, 11000 Serbia; Department of Materials Science and Engineering, School of Industrial Engineering and Management, KTH-Royal Institute of Technology, Brinellvägen 23, 100 44 Stockholm, Sweden
Benedict Osuagwu
Institute for Surface Science and Corrosion WW4-LKO, Department of Materials Science, University of Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, Germany
Hyesung Kim
Institute for Surface Science and Corrosion WW4-LKO, Department of Materials Science, University of Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, Germany
Johannes Will
Institute of Micro- and Nanostructure Research & Center for Nanoanalysis and Electron Microscopy (CENEM), University of Erlangen-Nuremberg, IZNF, Cauerstraße 3, 91058 Erlangen, Germany
Tadahiro Yokosawa
Institute of Micro- and Nanostructure Research & Center for Nanoanalysis and Electron Microscopy (CENEM), University of Erlangen-Nuremberg, IZNF, Cauerstraße 3, 91058 Erlangen, Germany
Zdeněk Badura
Regional Centre of Advanced Technologies and Materials, Šlechtitelů 27, Olomouc, 78371 Czech Republic
Štěpán Kment
Regional Centre of Advanced Technologies and Materials, Šlechtitelů 27, Olomouc, 78371 Czech Republic
Shiva Mohajernia
Institute for Surface Science and Corrosion WW4-LKO, Department of Materials Science, University of Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, Germany
Anca Mazare
Institute for Surface Science and Corrosion WW4-LKO, Department of Materials Science, University of Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, Germany
Natalia V. Skorodumova
Department of Materials Science and Engineering, School of Industrial Engineering and Management, KTH-Royal Institute of Technology, Brinellvägen 23, 100 44 Stockholm, Sweden; Department of Physics and Astronomy, Uppsala University, Box 516, 751 20 Uppsala, Sweden
Erdmann Spiecker
Institute of Micro- and Nanostructure Research & Center for Nanoanalysis and Electron Microscopy (CENEM), University of Erlangen-Nuremberg, IZNF, Cauerstraße 3, 91058 Erlangen, Germany
Patrik Schmuki
Institute for Surface Science and Corrosion WW4-LKO, Department of Materials Science, University of Erlangen-Nuremberg, Martensstraße 7, 91058 Erlangen, Germany; Regional Centre of Advanced Technologies and Materials, Šlechtitelů 27, Olomouc, 78371 Czech Republic; Department of Chemistry, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah, 21569 Saudi Arabia; Corresponding author
Summary: Here, we evaluate three different noble metal co-catalysts (Pd, Pt, and Au) that are present as single atoms (SAs) on the classic benchmark photocatalyst, TiO2. To trap the single atoms on the surface, we introduced controlled surface vacancies (Ti3+-Ov) on anatase TiO2 nanosheets by a thermal reduction treatment. After anchoring identical loadings of single atoms of Pd, Pt, and Au, we measure the photocatalytic H2 generation rate and compare it to the classic nanoparticle co-catalysts on the nanosheets. While nanoparticles yield the well-established the hydrogen evolution reaction activity sequence (Pt > Pd > Au), for the single atom form, Pd radically outperforms Pt and Au. Based on density functional theory (DFT), we ascribe this unusual photocatalytic co-catalyst sequence to the nature of the charge localization on the noble metal SAs embedded in the TiO2 surface.
