Herein, we report the synthesis of a γ-Al 2 O 3 -supported NiCo catalyst for dry methane reforming (DMR) and study the catalyst using in situ scanning transmission X-ray microscopy (STXM) during the reduction (activation step) and under reaction conditions. During the reduction process, the NiCo alloy particles undergo elemental segregation with Co migrating toward the center of the catalyst particles and Ni migrating to the outer surfaces. Under DMR conditions, the segregated structure is maintained, thus hinting at the importance of this structure to optimal catalytic functions. Finally, the formation of Ni-rich branches on the surface of the particles is observed during DMR, suggesting that the loss of Ni from the outer shell may play a role in the reduced stability and hence catalyst deactivation. These findings provide insights into the morphological and electronic structural changes that occur in a NiCo-based catalyst during DMR. Further, this study emphasizes the need to study catalysts under operating conditions in order to elucidate material dynamics during the reaction.
Herein, we report
the synthesis and electrochemical oxygen evolution experiments for
a graphene-supported Ni3MnO4 catalyst. The changes
that occur at the Ni active sites during the electrocatalyic oxygen
evolution reaction (OER) were elucidated by a combination of operando
Ni L-edge X-ray absorption spectroscopy (XAS) and Ni 2p3d resonant
inelastic X-ray scattering (RIXS). These data are compared to reference
measurements on NiO, β-Ni(OH)2, β-NiOOH, and
γ-NiOOH. Through this comparative analysis, we are able to show
that under alkaline conditions (0.1 M KOH), the oxides of the Ni3MnO4 catalyst are converted to hydroxides. At the
onset of catalysis (1.47 V), the β-Ni(OH)2-like phase
is oxidized and converted to a dominantly γ-NiOOH phase. The
present study thus challenges the notion that the β-NiOOH phase
is the active phase in OER and provides further evidence that the
γ-NiOOH phase is catalytically active. The ability to use Ni
L-edge XAS and 2p3d RIXS to provide a rational basis for structure–activity
correlations is highlighted.
Ligand field spectra provide direct information about the electronic structure of transition metal complexes. However, these spectra are difficult to measure by conventional optical techniques due to small cross sections for d-to-d transitions and instrumental limitations below 4000 cm. 2p3d resonant inelastic X-ray scattering (RIXS) is a second order process that utilizes dipole allowed 2p to 3d transitions to access d-d excited states. The measurement of ligand field excitation spectra by RIXS is demonstrated for a series of tetrahedral and octahedral Fe(II) and Fe(III) chlorides, which are denoted Fe(III)-T, Fe(II)-T, Fe(III)-O, and Fe(II)-O. The strong 2p spin-orbit coupling allows the measurement of spin forbidden transitions in RIXS spectroscopy. The Fe(III) spectra are dominated by transitions from the sextet ground state to quartet excited states, and the Fe(II) spectra contain transitions to triplet states in addition to the spin allowed Γ →Γ transition. Each experimental spectrum is simulated using a ligand field multiplet model to extract the ligand field splitting parameter 10Dq and the Racah parameters B and C. The 10Dq values for Fe(III)-T, Fe(II)-T, and Fe(III)-O are found to be -0.7, -0.32, and 1.47 eV, respectively. In the case of Fe(II)-O, a single 10Dq parameter cannot be assigned because Fe(II)-O is a coordination polymer exhibiting axially compressed Fe(II)Cl units. TheT → E transition is split by the axial compression resulting in features at 0.51 and 0.88 eV. The present study forms the foundation for future applications of 2p3d RIXS to molecular iron sites in more complex systems, including iron-based catalysts and enzymes.
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