Robin Sandström

Comprehensive Study of an Earth-Abundant Bifunctional 3D Electrode for Efficient Water Electrolysis in Alkaline Medium

We report efficient electrolysis of both water-splitting half reactions in the same medium by a bifunctional 3D electrode comprising Co3O4 nanospheres nucleated on the surface of nitrogen-doped carbon nanotubes (NCNTs) that in turn are grown on conductive carbon paper (CP). The resulting electrode exhibits high stability and large electrochemical activity for both oxygen and hydrogen evolution reactions (OER and HER). We obtain a current density of 10 mA/cm(2) in 0.1 M KOH solution at overpotentials of only 0.47 and 0.38 V for OER and HER, respectively. Additionally, the experimental observations are understood and supported by analyzing the Co3O4:NCNT and NCNT:CP interfaces by ab initio calculations. Both the experimental and the theoretical studies indicate that firm and well-established interfaces along the electrode play a crucial role on the stability and electrochemical activity for both OER and HER.

Atomistic understanding of the origin of high oxygen reduction electrocatalytic activity of cuboctahedral Pt3Co–Pt core–shell nanoparticles

PtM-based core–shell nanoparticles are a new class of active and stable nanocatalysts for promoting oxygen reduction reaction (ORR); however, the understanding of their high electrocatalytic performance for ORR at the atomistic level is still a great challenge. Herein, we report the synthesis of highly ordered and homogeneous truncated cuboctahedral Pt3Co–Pt core–shell nanoparticles (cs-Pt3Co). By combining atomic resolution electron microscopy, X-ray photoelectron spectroscopy, extensive first-principles calculations, and many other characterization techniques, we conclude that the cs-Pt3Co nanoparticles are composed of a complete or nearly complete Pt monolayer skin, followed by a secondary shell containing 5–6 layers with ~78 at% of Pt, in a Pt3Co configuration, and finally a Co-rich core with 64 at% of Pt. Only this particular structure is consistent with the very high electrocatalytic activity of cs-Pt3Co nanoparticles for ORR, which is about 6 times higher than commercial 30%-Pt/Vulcan and 5 times more active than non-faceted (spherical) alloy Pt3Co nanoparticles. Our study gives an important insight into the atomistic design and understanding of advanced bimetallic nanoparticles for ORR catalysis and other important industrial catalytic applications.

Cationic Vacancy Defects in Iron Phosphide : A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting.

Abstract Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an approach to modulate the electronic structure of iron phosphide (FeP). The Fe vacancies were produced by chemical leaching of Mg that was introduced into FeP as “sacrificial dopant”. The obtained Fevacancy‐rich FeP nanoparticulate films, which were deposited on Ti foil, show excellent HER activity compared to pristine FeP and Mg‐doped FeP, achieving a current density of 10 mA cm−2 at overpotentials of 108 mV in 1 m KOH and 65 mV in 0.5 m H2SO4, with a near‐100 % Faradaic efficiency. Our theoretical and experimental analyses reveal that the improved HER activity originates from the presence of Fe vacancies, which lead to a synergistic modulation of the structural and electronic properties that result in a near‐optimal hydrogen adsorption free energy and enhanced proton trapping. The success in catalytic improvement through the introduction of cationic vacancy defects has not only demonstrated the potential of Fe‐vacancy‐rich FeP as highly efficient, earth abundant HER catalyst, but also opens up an exciting pathway for activating other promising catalysts for electrochemical water splitting.

Influence of Sb5+ as a Double Donor on Hematite (Fe3+) Photoanodes for Surface-Enhanced Photoelectrochemical Water Oxidation

To exploit the full potential of hematite (α-Fe2O3) as an efficient photoanode for water oxidation, the redox processes occurring at the Fe2O3/electrolyte interface need to be studied in greater detail. Ex situ doping is an excellent technique to introduce dopants onto the photoanode surface and to modify the photoanode/electrolyte interface. In this context, we selected antimony (Sb5+) as the ex situ dopant because it is an effective electron donor and reduces recombination effects and concurrently utilize the possibility to tuning the surface charge and wettability. In the presence of Sb5+ states in Sb-doped Fe2O3 photoanodes, as confirmed by X-ray photoelectron spectroscopy, we observed a 10-fold increase in carrier concentration (1.1 × 1020 vs 1.3 × 1019 cm-3) and decreased photoanode/electrolyte charge transfer resistance (∼990 vs ∼3700 Ω). Furthermore, a broad range of surface characterization techniques such as Fourier-transform infrared spectroscopy, ζ-potential, and contact angle measurements reveal that changes in the surface hydroxyl groups following the ex situ doping also have an effect on the water splitting capability. Theoretical calculations suggest that Sb5+ can activate multiple Fe3+ ions simultaneously, in addition to increasing the surface charge and enhancing the electron/hole transport properties. To a greater extent, the Sb5+- surface-doped determines the interfacial properties of electrochemical charge transfer, leading to an efficient water oxidation mechanism.

Robust hierarchical 3D carbon foam electrode for efficient water electrolysis

Herein we report a 3D heterostructure comprising a hierarchical macroporous carbon foam that incorporates mesoporous carbon nanotubes decorated with cobalt oxide nanoparticles as an unique and highly efficient electrode material for the oxygen evolution reaction (OER) in electrocatalytic water splitting. The best performing electrode material showed high stability after 10 h, at constant potential of 1.7 V vs. RHE (reversible hydrogen electrode) in a 0.1 M KOH solution and high electrocatalytic activity in OER with low overpotential (0.38 V vs RHE at 10 mA cm−2). The excellent electrocatalytic performance of the electrode is rationalized by the overall 3D macroporous structure and with the firmly integrated CNTs directly grown on the foam, resulting in a large specific surface area, good electrical conductivity, as well as an efficient electrolyte transport into the whole electrode matrix concurrent with an ability to quickly dispose oxygen bubbles into the electrolyte. The eminent properties of the three-dimensional structured carbon matrix, which can be synthesized through a simple, scalable and cost effective pyrolysis process show that it has potential to be implemented in large-scale water electrolysis systems.