The role of surface oxygenated-species and adsorbed hydrogen in the oxygen reduction reaction (ORR) mechanism and product selectivity on Pd-based catalysts in acid media

Literature Information

Publication Date 2015-05-13
DOI 10.1039/C5CP00692A
Impact Factor 3.676
Authors

R. Rahul, R. K. Singh, B. Bera, R. Devivaraprasad, M. Neergat


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Abstract

Oxygen reduction reaction (ORR) is investigated on bulk PdO-based catalysts (oxides of Pd and Pd3Co) in oxygen-saturated 0.1 M HClO4 to establish the role of surface oxides and adsorbed hydrogen in the activity and product selectivity (H2O/H2O2). The initial voltammetric features suggest that the oxides are inactive toward ORR. The evolution of the ORR voltammograms and potential-dependent H2O2 generation features on the PdO catalyst suggest gradual and parallel in situ reduction of the bulk PdO phase below ∼0.4 V in the hydrogen underpotential deposition (Hupd) region; the reduction of the bulk PdO catalyst is confirmed from the X-ray photoelectron spectra (XPS) and X-ray diffraction (XRD) patterns. The potential-dependent H2O2 generation features originate due to the presence of surface oxides and adsorbed hydrogen; this is further confirmed using halide ions (Cl− and Br−) and peroxide as the external impurities.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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