Boosting water oxidation through in situ electroconversion of manganese gallide: an intermetallic precursor approach

For the first time, the manganese gallide (MnGa4) served as an intermetallic precursor, which upon in situ electroconversion in alkaline media produced high‐performance and long‐term‐stable MnOx‐based electrocatalysts for water oxidation. Unexpectedly, its electrocorrosion (with the concomitant loss of Ga) leads simultaneously to three crystalline types of MnOx minerals with distinct structures and induced defects: birnessite δ‐MnO2, feitknechtite β‐MnOOH, and hausmannite α‐Mn3O4. The abundance and intrinsic stabilization of MnIII/MnIV active sites in the three MnOx phases explains the superior efficiency and durability of the system for electrocatalytic water oxidation. After electrophoretic deposition of the MnGa4 precursor on conductive nickel foam (NF), a low overpotential of 291 mV, comparable to that of precious‐metal‐based catalysts, could be achieved at a current density of 10 mA cm−2 with a durability of more than five days.DFG, 390540038, EXC 2008: UniSysCatTU Berlin, Open-Access-Mittel - 201

Recent progress in the performance of HAPG based laboratory EXAFS and XANES spectrometers

New developments in the description and modeling of Highly Annealed Pyrolytic Graphite (HAPG) mosaic crystals have led to the possibility of designing optimized optical solutions for X-ray absorption fine structure (XAFS) spectroscopy. XAFS is a very versatile method that is usually divided into two sub methods: extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopies, which need different experimental conditions concerning spectral resolving power, energetic bandwidth and number of detected photons. For facilitating XANES and EXAFS spectroscopies with laboratory- and von Hamos-based spectrometers, tailored optics were designed as well as optimized spectrometer components, i.e. an adequate microfocus X-ray source and a pixelated detector, were chosen. This is shown with a demonstration experiment on pure copper foil. In the XANES case a spectral resolving power of E/ΔE ≈ 4000 and an energy bandpass of around 300 eV were achieved with a measurement time of t = 7 min. For EXAFS, the tailored optic has an increased solid angle at moderate spectral resolving power in combination with a large energy bandpass of over 1 keV and a measurement time of t = 250 s for the given copper foil. These optimized solutions pave the way to perform XANES and EXAFS in the laboratory even for diluted samples with analyte concentrations of only a few weight percent or even less in a reasonable time frame of minutes to hours. Spectrometers, that already had an impact on research, especially catalysis research, therefore, made a huge leap in efficiency that prepares them to meet new challenges, not only as a standalone method, but also in combination with high-end synchrotron radiation facility-based XAFS experiments.TU Berlin, Open-Access-Mittel - 202

In situ / operando plug-flow fixed-bed cell for synchrotron PXRD and XAFS investigations at high temperature, pressure, controlled gas atmosphere and ultra-fast heating

A plug-flow fixed-bed cell for synchrotron powder X-ray diffraction (PXRD) and X-ray absorption fine structure (XAFS) idoneous for the study of heterogeneous catalysts at high temperature, pressure and under gas flow is designed, constructed and demonstrated. The operating conditions up to 1000°C and 50 bar are ensured by a set of mass flow controllers, pressure regulators and two infra-red lamps that constitute a robust and ultra-fast heating and cooling method. The performance of the system and cell for carbon dioxide hydrogenation reactions under specified temperatures, gas flows and pressures is demonstrated both for PXRD and XAFS at the P02.1 (PXRD) and the P64 (XAFS) beamlines of the Deutsches Elektronen-Synchrotron (DESY)

One-pot synthesis of iron-doped ceria catalysts for tandem carbon dioxide hydrogenation

We report on the one-pot synthesis of inexpensive and abundant CeO2 and 1.5, 4.5, and 9 mol% Fe-doped ceria (Ce1−xFexO2−δ) systems and their catalytic activity for tandem CO2 hydrogenation. XAFS and XRD demonstrate that oxygen vacancies are generated via two mechanisms: firstly, by the substitution of Ce4+ by Fe3+ in the lattice and the subsequent loss of oxygen anions. Secondly, by the partial reduction of Ce4+ to Ce3+, which is enhanced by the presence of Fe. All the samples tested show high activity for CO2 hydrogenation and the production of CO, CH4, and light (C2–C4) alkanes and alkenes, with the 9 mol% Fe-doped CeO2 showing the best performance in terms of CO2 reaction rate and product selectivity. During reaction, Fe exsolves/seggregates from the ceria, resulting in particles decorating the surface of the catalyst and increasing the reaction rates of CO2. This system is composed of two functionalities, the oxygen vacancy and the Fe, whose close vicinity results in a high selectivity toward CO and CH4 detrimental to the more valuable hydrocarbons. A rather complex interplay between the two functionalities, their interface, and the particle size of the catalysts exists for this tandem reaction network on this catalytic system and deserves further studies

Elucidating the role of earth alkaline doping in perovskite-based methane dry reforming catalysts.

To elucidate the role of earth alkaline doping in perovskite-based dry reforming of methane (DRM) catalysts, we embarked on a comparative and exemplary study of a Ni-based Sm perovskite with and without Sr doping. While the Sr-doped material appears as a structure-pure Sm1.5Sr0.5NiO4 Ruddlesden Popper structure, the undoped material is a NiO/monoclinic Sm2O3 composite. Hydrogen pre-reduction or direct activation in the DRM mixture in all cases yields either active Ni/Sm2O3 or Ni/Sm2O3/SrCO3 materials, with albeit different short-term stability and deactivation behavior. The much smaller Ni particle size after hydrogen reduction of Sm1.5Sr0.5NiO4, and of generally all undoped materials stabilizes the short and long-term DRM activity. Carbon dioxide reactivity manifests itself in the direct formation of SrCO3 in the case of Sm1.5Sr0.5NiO4, which is dominant at high temperatures. For Sm1.5Sr0.5NiO4, the CO : H2 ratio exceeds 1 at these temperatures, which is attributed to faster direct carbon dioxide conversion to SrCO3 without catalytic DRM reactivity. As no Sm2O2CO3 surface or bulk phase as a result of carbon dioxide activation was observed for any material - in contrast to La2O2CO3 - we suggest that oxy-carbonate formation plays only a minor role for DRM reactivity. Rather, we identify surface graphitic carbon as the potentially reactive intermediate. Graphitic carbon has already been shown as a crucial reaction intermediate in metal-oxide DRM catalysts and appears both for Sm1.5Sr0.5NiO4 and NiO/monoclinic Sm2O3 after reaction as crystalline structure. It is significantly more pronounced for the latter due to the higher amount of oxygen-deficient monoclinic Sm2O3 facilitating carbon dioxide activation. Despite the often reported beneficial role of earth alkaline dopants in DRM catalysis, we show that the situation is more complex. In our studies, the detrimental role of earth alkaline doping manifests itself in the exclusive formation of the sole stable carbonated species and a general destabilization of the Ni/monoclinic Sm2O3 interface by favoring Ni particle sintering

Steering the Methane Dry Reforming Reactivity of Ni/La 2 O 3 Catalysts by Controlled In Situ Decomposition of Doped La 2 NiO 4 Precursor Structures

The influence of A- and/or B-site doping of Ruddlesden-Popper perovskite materials on the crystal structure, stability, and dry reforming of methane (DRM) reactivity of specific A2BO4 phases (A = La, Ba; B = Cu, Ni) has been evaluated by a combination of catalytic experiments, in situ X-ray diffraction, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and aberration-corrected electron microscopy. At room temperature, B-site doping of La2NiO4 with Cu stabilizes the orthorhombic structure (Fmmm) of the perovskite, while A-site doping with Ba yields a tetragonal space group (I4/mmm). We observed the orthorhombic-to-tetragonal transformation above 170 °C for La2Ni0.9Cu0.1O4 and La2Ni0.8Cu0.2O4, slightly higher than for undoped La2NiO4. Loss of oxygen in interstitial sites of the tetragonal structure causes further structure transformations for all samples before decomposition in the temperature range of 400 °C-600 °C. Controlled in situ decomposition of the parent or A/B-site doped perovskite structures in a DRM mixture (CH4:CO2 = 1:1) in all cases yields an active phase consisting of exsolved nanocrystalline metallic Ni particles in contact with hexagonal La2O3 and a mixture of (oxy)carbonate phases (hexagonal and monoclinic La2O2CO3, BaCO3). Differences in the catalytic activity evolve because of (i) the in situ formation of Ni-Cu alloy phases (in a composition of >7:1 = Ni:Cu) for La2Ni0.9Cu0.1O4, La2Ni0.8Cu0.2O4, and La1.8Ba0.2Ni0.9Cu0.1O4, (ii) the resulting Ni particle size and amount of exsolved Ni, and (iii) the inherently different reactivity of the present (oxy)carbonate species. Based on the onset temperature of catalytic DRM activity, the latter decreases in the order of La2Ni0.9Cu0.1O4 ∼ La2Ni0.8Cu0.2O4 ≥ La1.8Ba0.2Ni0.9Cu0.1O4 > La2NiO4 > La1.8Ba0.2NiO4. Simple A-site doped La1.8Ba0.2NiO4 is essentially DRM inactive. The Ni particle size can be efficiently influenced by introducing Ba into the A site of the respective Ruddlesden-Popper structures, allowing us to control the Ni particle size between 10 nm and 30 nm both for simple B-site and A-site doped structures. Hence, it is possible to steer both the extent of the metal-oxide-(oxy)carbonate interface and its chemical composition and reactivity. Counteracting the limitation of the larger Ni particle size, the activity can, however, be improved by additional Cu-doping on the B-site, enhancing the carbon reactivity. Exemplified for the La2NiO4 based systems, we show how the delicate antagonistic balance of doping with Cu (rendering the La2NiO4 structure less stable and suppressing coking by efficiently removing surface carbon) and Ba (rendering the La2NiO4 structure more stable and forming unreactive surface or interfacial carbonates) can be used to tailor prospective DRM-active catalysts