Eko Budiyanto obtained his M.Sc. degree in Chemistry from Jagiellonian University in Kraków in 2018. He is currently working as a Ph.D. student in the Department of Heterogeneous Catalysis of the Max-Planck-Institut für Kohlenforschung. His research focuses on the design of mesostructured cobalt-, iron-, and nickel-based electrocatalysts for water electrolysis. Harun Tüysüz gained his PhD degree in chemistry in the Department of Heterogeneous Catalysis at the Max-Planck-Institut für Kohlenforschung (MPI-KOFO) in 2008 under the supervision of Prof. Ferdi Schüth and then conducted postdoctoral research with Prof. Peidong Yang at the University of California, Berkeley. In 2012 he was appointed as the head of the independent research group "Heterogeneous Catalysis and Sustainable Energy" at the MPI-KOFO. His research group is interested in the design of nanoscale materials for sustainable energy-related catalytic applications. He has received several awards including the Jochen-Block-Prize 2016, the DECHEMA Prize 2019, and the Forcheurs Jean-Marie Lehn Prize 2020. Scheme 1. A typical water electrolysis cell under alkaline conditions.
Herein, we show that coupling boron with cobalt oxide tunes its structure and significantly boost its electrocatalytic performance for the oxygen evolution reaction (OER). Through a simple precipitation and thermal treatment process, a series of Co−B oxides with tunable morphologies and textural parameters were prepared. Detailed structural analysis supported first the formation of an disordered and partially amorphous material with nanosized Co3BO5 and/or Co2B2O6 being present on the local atomic scale. The boron modulation resulted in a superior OER reactivity by delivering a large current and an overpotential of 338 mV to reach a current density of 10 mA cm−2 in 1 M KOH electrolyte. Identical location transmission electron microscopy and in situ electrochemical Raman spectroscopy studies revealed alteration and surface re‐construction of materials, and formation of CoO2 and (oxy)hydroxide intermediate, which were found to be highly dependent on crystallinity of the samples.
The influence of iron on nanocasting of cobalt oxide nanowires and the performance of these materials for the oxygen evolution reaction (OER) are investigated. Pristine Co 3 O 4 and mixed cobalt iron oxide nanowires with a diameter of 7 nm have been synthesized via a nanocasting route by using SBA-15 silica as a template. A small amount of iron added during the synthesis results in a decrease in the nanowires' array length and induces the formation of a bimodal pore size distribution. Raman spectroscopy, X-ray emission, and high-energy resolution X-ray absorption spectroscopies further show that Fe incorporation alters the electronic structure by increasing the average distortion around the cobalt centers and the amount of Co 2+ in tetrahedral sites. These affect the OER activity significantly; the overpotential of pristine Co 3 O 4 at 10 mA/cm 2 decreases from 398 to 378 mV, and the current density at 1.7 V increases from 107 to 150 mA/cm 2 with the addition of iron at the Co/Fe atomic ratio of 32. Furthermore, post-reaction characterization confirmed that both the morphology and electronic structure of nanowires remain intact after a long-term stability test.
A series of Co1+xFe2–xO4 (0≤x≤2) spinel nanowires was synthesized by nanocasting using SBA‐15 silica as hard template, which was characterized by X‐ray powder diffraction, X‐ray photoelectron spectroscopy, and transmission electron microscopy. The Co1+xFe2–xO4 spinels were applied in the aerobic oxidation of aqueous 2‐propanol solutions to systematically study the influence of exposed Co and Fe cations on the catalytic properties. The activity of the catalysts was found to depend strongly on the Co content, showing an exponential increase of the reaction rate with increasing Co content. Ensembles of Co3+cus (coordinatively unsaturated) sites were identified as the active sites for selective 2‐propanol oxidation, which are assumed to consist of more than six Co ions. In addition, gas‐phase oxidation with and without water vapor co‐feeding was performed to achieve a comparison with liquid‐phase oxidation kinetics. An apparent activation energy of 94 kJ mol−1 was determined for 2‐propanol oxidation over Co3O4 in the liquid phase, which is in good agreement with the gas‐phase oxidation in the presence of water vapor. In contrast to gas‐phase conditions, the catalysts showed high stability and reusability in the aqueous phase with constant conversion in three consecutive runs.
Herein, we report nanosecond, single-pulse laser post-processing (PLPP) in a liquid flat jet with precise control of the applied laser intensity to tune structure, defect sites, and the oxygen evolution reaction (OER) activity of mesostructured Co 3 O 4 . High-resolution X-ray diffraction (XRD), Raman, and Xray photoelectron spectroscopy (XPS) are consistent with the formation of cobalt vacancies at tetrahedral sites and an increase in the lattice parameter of Co 3 O 4 after the laser treatment. X-ray absorption spectroscopy (XAS) and X-ray emission spectroscopy (XES) further reveal increased disorder in the structure and a slight decrease in the average oxidation state of the cobalt oxide. Molecular dynamics simulation confirms the surface restructuring upon laser post-treatment on Co 3 O 4 . Importantly, the defectinduced PLPP was shown to lower the charge transfer resistance and boost the oxygen evolution activity of Co 3 O 4 . For the optimized sample, a 2-fold increment of current density at 1.7 V vs RHE is obtained and the overpotential at 10 mA/cm 2 decreases remarkably from 405 to 357 mV compared to pristine Co 3 O 4 . Post-mortem characterization reveals that the material retains its activity, morphology, and phase structure after a prolonged stability test.
Heusler compounds have potential in electrocatalysis because of their mechanical robustness, metallic conductivity, and wide tunability in the electronic structure and element compositions. This study reports the first application of Co2YZ‐type Heusler compounds as electrocatalysts for the oxygen evolution reaction (OER). A range of Co2YZ crystals was synthesized through the arc‐melting method and the eg orbital filling of Co was precisely regulated by varying Y and Z sites of the compound. A correlation between the eg orbital filling of reactive Co sites and OER activity was found for Co2MnZ compounds (Z=Ti, Al, V, and Ga), whereby higher catalytic current was achieved for eg orbital filling approaching unity. A similar trend of eg orbital filling on the reactivity of cobalt sites was also observed for other Heusler compounds (Co2VZ, Z=Sn and Ga). This work demonstrates proof of concept in the application of Heusler compounds as a new class of OER electrocatalysts, and the influence of the manipulation of the spin orbitals on their catalytic performance.
Water electrolysis that results in green hydrogen is the key process towards a circular economy. The supply of sustainable electricity and availability of oxygen evolution reaction (OER) electrocatalysts are the main bottlenecks of the process for large‐scale production of green hydrogen. A broad range of OER electrocatalysts have been explored to decrease the overpotential and boost the kinetics of this sluggish half‐reaction. Co‐, Ni‐, and Fe‐based catalysts have been considered to be potential candidates to replace noble metals due to their tunable 3d electron configuration and spin state, versatility in terms of crystal and electronic structures, as well as abundance in nature. This Review provides some basic principles of water electrolysis, key aspects of OER, and significant criteria for the development of the catalysts. It provides also some insights on recent advances of Co‐, Ni‐, and Fe‐based oxides and a brief perspective on green hydrogen production and the challenges of water electrolysis.
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