High Energy Resolution Fluorescence Detected X-ray Absorption Near Edge Structure Research Articles

(Invited) Evolution of Single Atom Catalysts during CO2 Electrocatalytic Reduction

The re-utilization of CO2 via its electrocatalytic reduction (CO2RR) into value-added chemicals and fuels is a promising avenue to minimize the impact of existing technologies on the climate change. This requires the development of low cost, efficient, selective and durable electrocatalysts based of their rational understanding. Moreover, it should be considered that even morphologically and chemically well-defined pre-catalysts can be susceptible to drastic modifications under operation, especially when the reaction conditions themselves change dynamically.This talk will address the transformations that Metal-N-C catalysts (M=Cu, Ni, Co, Fe, Sn, Zn) experience during static and pulsed CO2RR using operando quick X-ray absorption spectroscopy (XAS) and Raman spectroscopy. In particular, I will illustrate the astonishing behaviordisplayed by Cu-N-C catalystsduring CO2RR, featuring reversible transformations from single atom sites towards Cu nanoparticles. The switchable nature of these species that can be achieved by applying different potential pulses holds the key for the on-demand control of the distribution of the CO2RR products and thus, a wide-spread adoption of this process.Moreover, I will elucidate the nature of the ligands forming under CO2RR at singly dispersed Ni sites in Ni-N-C catalysts, which are currently drawing great attention for their high performances in the CO formation. This will be achieved by a synergistic combination of conventional XAS, high energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy, and X-ray emission spectroscopy (XES) coupled with unsupervised and supervised machine learning methodologies and density functional theory.Overall, my lecture will feature the importance of operando characterization of electrocatalysts in order to unveil structure/composition-reactivity correlations during CO2RR.

Versatile Spectroscopic Cell for Operando Studies in Heterogeneous Catalysis Using Tender X‐ray Spectroscopy in Fluorescence Mode

AbstractThe design and commissioning of a cell suitable for operando studies using high‐energy‐resolution fluorescence‐detected X‐ray absorption near‐edge structure (HERFD‐XANES) spectroscopy in the tender X‐ray regime is reported. The cell is optimized for measurements within the energy range of 1.5 keV to 4.5 keV. It has a plug‐flow geometry and can be used for sieved powder samples, analogous to reactors employed for laboratory tests. The functionality of the spectroscopic cell is demonstrated in the area of emission control using CO oxidation as target reaction over 1 wt.% Rh/γ‐Al2O3 as catalyst. We show how HERFD‐XANES at the Rh L3‐edge captures variations in the noble metal structure resulting from the interaction with the support material and reactant molecules. Moreover, distinct structural changes were identified along the catalyst bed as a function of temperature and local gas mixture.

Unraveling the Molecular Details of the “Gate Opening” Phenomenon in ZIF-8 with X-ray Absorption Spectroscopy

The local structural changes associated with the ZIF-8 framework flexibility upon nitrogen gas adsorption have been studied by in situ X-ray absorption spectroscopy (XAS) and high-energy-resolution fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopy. Different thermodynamic conditions (isobar and isotherm) have been used to explore the so-called “gate opening” transition in which the hexagonal pore windows of the sodalite cage open, increasing the accessible volume for gas adsorption. To elucidate the source of the spectral changes in the XANES region of the absorption spectra observed along the gas adsorption and through the transition from the closed to the open pore configuration, ab initio calculations have been performed. Our results demonstrate that the transition from the closed to the open pore configurations involves not only the rotation of the MeIM ligand but also a further bend of the Me group away from the plane defined by the IM ring. Additionally, the contribution of the N2 molecules adsorbed in the center of the 4-ring window has been included in the scattering model to fully reproduce the main features of the X-ray absorption spectra in the open pore configuration.

HERFD-XANES and RIXS Study on the Electronic Structure of Trivalent Lanthanides across a Series of Isostructural Compounds.

We performed a systematic study of the complexes of trivalent lanthanide cations with the hydridotris(1-pyrazolyl)borato (Tp) ligand (LnTp3; Ln = La, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu) using both high-energy-resolution fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) and resonant inelastic X-ray scattering (RIXS) at the lanthanide L3 absorption edge. Here, we report the results obtained and we discuss them against calculations performed using density functional theory (DFT) and atomic multiplet theory. The spectral shape and the elemental trends observed in the experimental HERFD-XANES spectra are well reproduced by DFT calculations, while the pre-edge energy interval is better described by atomic multiplet theory. The RIXS data show a generally rather complex pattern that originates from the intra-atomic electron–electron interactions in the intermediate and final states, as demonstrated by the good agreement obtained with calculations using an atomic-only model of the absorber. Guided by theoretical predictions, we discuss the possible origins of the observed spectral features and the trends in energy splitting across the series. The insight into the electronic structure of trivalent lanthanide compounds demonstrated here and obtained with advanced X-ray spectroscopies coupled with theoretical calculations can be applied to any lanthanide-bearing compound and be of great interest for all research fields involving lanthanides.

Insights into the Structural Dynamics of Pt/CeO2 Single-Site Catalysts during CO Oxidation

Despite their high atomic dispersion, single site catalysts with Pt supported on CeO2 were found to have a low activity during oxidation reactions. In this study, we report the behavior of Pt/CeO2 single site catalyst under more complex gas mixtures, including CO, C3H6 and CO/C3H6 oxidation in the absence or presence of water. Our systematic operando high-energy resolution-fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopic study combined with multivariate curve resolution with alternating least squares (MCR-ALS) analysis identified five distinct states in the Pt single site structure during CO oxidation light-off. After desorption of oxygen and autoreduction of Pt4+ to Pt2+ due to the increase of temperature, CO adsorbs and reduces Pt2+ to Ptδ+ and assists its migration with final formation of PtxΔ+ clusters. The derived structure–activity relationships indicate that partial reduction of Pt single sites is not sufficient to initiate the conversion of CO. The reaction proceeds only after the regrouping of several noble metal atoms in small clusters, as these entities are probably able to influence the mobility of the oxygen at the interface with ceria.

Enhanced Sorption of Radionuclides by Defect-Rich Graphene Oxide.

Extremely defect graphene oxide (dGO) is proposed as an advanced sorbent for treatment of radioactive waste and contaminated natural waters. dGO prepared using a modified Hummers oxidation procedure, starting from reduced graphene oxide (rGO) as a precursor, shows significantly higher sorption of U(VI), Am(III), and Eu(III) than standard graphene oxides (GOs). Earlier studies revealed the mechanism of radionuclide sorption related to defects in GO sheets. Therefore, explosive thermal exfoliation of graphite oxide was used to prepare rGO with a large number of defects and holes. Defects and holes are additionally introduced by Hummers oxidation of rGO, thus providing an extremely defect-rich material. Analysis of characterization by XPS, TGA, and FTIR shows that dGO oxygen functionalization is predominantly related to defects, such as flake edges and edge atoms of holes, whereas standard GO exhibits oxygen functional groups mostly on the planar surface. The high abundance of defects in dGO results in a 15-fold increase in sorption capacity of U(VI) compared to that in standard Hummers GO. The improved sorption capacity of dGO is related to abundant carboxylic group attached hole edge atoms of GO flakes as revealed by synchrotron-based extended X-ray absorption fine structure (EXAFS) and high-energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy.

Probing Charge Ordering in Fractional Mixed-Valence Charge Density Wave Systems with Oriented HERFD-XANES Spectroscopy

We present oriented Pt LIII edge high energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) measurements on a series of structurally tunable quasi-one-dimension...

HERFD-XANES probes of electronic structures of ironII/III carbene complexes.

Iron centered N-heterocyclic carbene (Fe-NHC) complexes have shown long-lived excited states with charge transfer character useful for light harvesting applications. Understanding the nature of the metal-ligand bond is of fundamental importance to rationally tailor the properties of transition metal complexes. The high-energy-resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) has been used to probe the valence orbitals of three carbene complexes, [FeII(bpy)(btz)2](PF6)2 (bpy = 2,2'-bipyridine, btz = 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene)), [FeIII(btz)3](PF6)3, and [FeIII(phtmeimb)2]PF6 (phtmeimb = [phenyl(tris(3-methylimidazol-2-ylidene))borate]-). The multiconfigurational restrict active space (RAS) approach has been used to simulate the metal K pre-edge X-ray absorption spectroscopy of these carbene complexes, and have reproduced the metal K pre-edge spectral features in terms of relative intensity and peak positions. The evident intensity difference between the FeII and the other two FeIII complexes has been elucidated with different intensity mechanisms in the transition. The smaller splitting between the t2g and eg character peak for [FeIII(btz)3](PF6)3 has been observed in the experimental measurements and been reproduced in the RAS calculations. The results show how the combination of experimental HERFD-XANES measurements and ab initio RAS simulations can give quantitative evaluation of the orbital interactions between metal and ligands for such large and strongly interacting systems and thus allow to understand and predict properties of novel complexes.

More than protection: the function of TiO2 interlayers in hematite functionalized Si photoanodes.

Worldwide significant efforts are ongoing to develop devices that store solar energy as fuels. In one such approach, solar energy is absorbed by semiconductors and utilized directly by catalysts at their surfaces to split water into H2 and O2. To protect the semiconductors in these photo-electrochemical cells (PEC) from corrosion, frequently thin TiO2 interlayers are applied. Employing a well-performing photoanode comprised of 1-D n-Si microwires (MWs) covered with a mesoporous (mp) TiO2 interlayer fabricated by solution processing and functionalized with α-Fe2O3 nanorods, we studied here the function of this TiO2 interlayer by high-energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) spectroscopy, along with X-ray emission spectroscopy (XES) and standard characterization techniques. Our data reveal that the TiO2 interlayer not only protects the n-Si MW surface from corrosion, but that it also acts as a template for the hydrothermal growth of α-Fe2O3 nanorods and improves the photocatalytic efficiency. We show that the latter effect correlates with the presence of stable oxygen vacancies at the interface between mp-TiO2 and α-Fe2O3, which act as electron traps and thereby substantially reduce the charge recombination rate at the hematite surface.

Unravelling the Different Reaction Pathways for Low Temperature CO Oxidation on Pt/CeO2 and Pt/Al2O3 by Spatially Resolved Structure–Activity Correlations

Spatially resolved operando HERFD-XANES (high energy resolution fluorescence detected X-ray absorption near edge structure) complemented by CO concentration gradient profiles along the catalyst bed (SpaciPro) was used to identify the dominant reaction paths for the low and high temperature CO oxidation on Pt/CeO2 and Pt/Al2O3. At low temperatures, features associated with CO adsorption on Pt were found for both catalysts. During the oxidation reaction light-off, the evolution of the spectral and catalytic profile diverged along the catalyst bed. The CO oxidation rate was high on Pt/CeO2 from the beginning of the catalyst bed with CO being adsorbed on Pt, whereas low CO conversion due to strong CO poisoning was found on Pt/Al2O3. This correlation of the CO concentration gradient with unique insight by HERFD-XANES gave direct proof of the crucial contribution of the Pt-CeO2 perimeter sites overcoming the CO self-inhibition effect at low temperatures.

Experimental and Theoretical High Energy Resolution Hard X-ray Absorption and Emission Spectroscopy on Biomimetic Cu2S2 Complexes.

High energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) and Valence-to-Core X-ray emission (VtC-XES) spectroscopy are established as hard X-ray methods to investigate complexes that might be relevant as mimics for the biologically important CuA site. By investigation of three carefully selected complexes of the type [Cu2(NGuaS)2X2], characterized by a cyclic Cu2S2 core portion and a varying adjunct ligand nature, it is proven that the HERFD-XANES and VtC-XES measurements in combination with extensive TD-DFT calculations can reveal details of the electronic states in such complexes, including HOMO and LUMO levels and spin states. By theoretical spectroscopy, the value of this methodic combination for future in situ studies is demonstrated.

Investigation of the nanoscale two-component ZnS-ZnO heterostructures by means of HR-TEM and X-ray based analysis

This article is devoted to the spectroscopic characterization of ZnS-ZnO nanoscale heterostructures synthesized by the microwave-assisted solvothermal method. The synthesized samples were investigated by means of X-ray powder diffraction (XRPD), high energy resolution fluorescence detected X-ray absorption near-edge-structure (HERFD-XANES) spectroscopy, valence-to-core X-ray emission spectroscopy (VtC-XES) and high resolution transmission electron microscopy (HR-TEM) as well as energy dispersive X-ray spectroscopy (EDX). The average crystallite size estimated by the broadening of XRPD peaks increases from 2.7 nm to 3.7 nm in the temperature range from 100 °C to 150 °C. HR-TEM images show that nanoparticles are arranged in aggregates with the 60–200 nm size. Theoretical estimation shows that the systems synthesized at higher temperatures more prone to the agglomeration. The full profile Reitveld analysis of XRPD data reveals the formation of hexagonal zinc sulfide structure, whereas electron diffraction data reveal also the formation of cubic zinc sulfide and claim the polymorphous character of the system. High energy resolution Zn K-edge XANES data unambiguously demonstrate the presence of a certain amount of the zinc oxide which is likely to have an amorphous structure and could not be detected by XRPD. Qualitative analysis of XANES data allows deriving ZnS/ZnO ratio as a function of synthesis temperature. EDX analysis depicts homogeneous distribution of ZnS and amorphous ZnO phases across the conglomerates. A complementary element-selective valence to core X-ray emission spectroscopy evidences formation of two-component system and confirms estimations of ZnS/ZnO fractions obtained by linear combination fit of XANES data.

The Connection between NHC Ligand Count and Photophysical Properties in Fe(II) Photosensitizers: An Experimental Study.

Four homo- and heteroleptic complexes bearing both polypyridyl units and N-heterocyclic carbene (NHC) donor functions are studied as potential noble metal-free photosensitizers. The complexes [FeII(L1)(terpy)][PF6]2, [FeII(L2)2][PF6]2, [FeII(L1)(L3)][PF6]2, and [FeII(L3)2][PF6]2 (terpy = 2,2':6',2″ terpyridine, L1 = 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine, L2 = 2,6-bis[3-isopropylimidazol-2-ylidene]pyridine, L3 = 1-(2,2'-bipyridyl)-3-methylimidazol-2-ylidene) contain tridentate ligands of the C^N^C and N^N^C type, respectively, resulting in a Fe-NHC number between two and four. Thorough ground state characterization by single crystal diffraction, electrochemistry, valence-to-core X-ray emission spectroscopy (VtC-XES), and high energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) in combination with ab initio calculations show a correlation between the geometric and electronic structure of these new compounds and the number of the NHC donor functions. These results serve as a basis for the investigation of the excited states by ultrafast transient absorption spectroscopy, where the lifetime of the 3MLCT states is found to increase with the NHC donor count. The results demonstrate for the first time the close interplay between the number of NHC functionalities in Fe(II) complexes and their photochemical properties, as revealed in a comparison of the activity as photosensitizers in photocatalytic proton reduction.

Detection and Characterization of Hydride Ligands in Iron Complexes by High-Resolution Hard X-ray Spectroscopy and Implications for Catalytic Processes

Two hydride catalysts [Fe(CO)(dppp)H(NO)] (dppp = 1,3-bis(diphenylphosphino)propane) and [Fe(CO)H(NO)(PPh3)2] in comparison with nonhydride analogues [Fe(dppe)(NO)2] (dppe = 1,3-bis(diphenylphosphino)ethane) and [Fe(NO)2(PPh3)2] are investigated with a combination of valence-to-core X-ray emission spectroscopy (VtC-XES) and high-energy resolution fluorescence detected X-ray absorption near-edge structure (HERFD-XANES). To fully understand the experiments and to obtain precise information about molecular levels being involved in the spectral signals, time-dependent density functional theory (TD-DFT) calculations and ground state density functional theory (DFT) calculations are necessary. An excellent agreement between experiment and theory allows the identification of particular spectral signals of the Fe-H group. Antibonding Fe-H interactions clearly contribute to pre-edge signals in HERFD-XANES spectra, while bonding Fe-H interactions cause characteristic signatures in the VtC-XES spectra. The sensitivity of both methods with respect to the Fe-H distance is demonstrated by a scanning simulation approach. The results open the way to study metal hydride complexes in situ, their formation, and their fate during catalytic reactions, using high-resolution XANES and valence-to-core X-ray emission spectroscopy.

Experimental and Theoretical High-Energy-Resolution X-ray Absorption Spectroscopy: Implications for the Investigation of the Entatic State.

High-energy-resolution-fluorescence-detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopy is shown to be a sensitive tool to investigate the electronic changes of copper complexes induced by geometric distortions caused by the ligand backbone as a model for the entatic state. To fully exploit the information contained in the spectra gained by the high-energy-resolution technique, (time-dependent) density functional theory calculations based on plane-wave and localized orbital basis sets are performed, which in combination allow the complete spectral range from the prepeak to the first resonances above the edge step to be covered. Thus, spectral changes upon oxidation and geometry distortion in the copper N-(1,3-dimethylimidazolidin-2-ylidene)quinolin-8-amine (DMEGqu) complexes [CuI(DMEGqu)2](PF6) and [CuII(DMEGqu)2](OTf)2·MeCN can be accessed.

Selective catalytic reduction of NO over Fe-ZSM-5: mechanistic insights by operando HERFD-XANES and valence-to-core X-ray emission spectroscopy.

An in-depth understanding of the active site requires advanced operando techniques and the preparation of defined catalysts. We elucidate here the mechanism of the selective catalytic reduction of NO by NH3 (NH3-SCR) over a Fe-ZSM-5 zeolite catalyst. 1.3 wt % Fe-ZSM-5 with low nuclearity Fe sites was synthesized, tested in the SCR reaction and characterized by UV-vis, X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopy. Next, this defined Fe-zeolite catalyst was studied by complementary high-energy-resolution fluorescence-detected XANES (HERFD-XANES) and valence-to-core X-ray emission spectroscopy (V2C XES) under different model in situ and realistic working (operando) conditions identical to the catalyst test bench including the presence of water vapor. HERFD-XANES uncovered that the coordination (between 4 and 5), geometry (tetrahedral, partly 5-fold), and oxidation state of the Fe centers (reduced in NH3, partly in SCR mixture, slight reduction in NO) strongly changed. V2C XES supported by DFT calculations provided important insight into the chemical nature of the species adsorbed on Fe sites. The unique combination of techniques applied under realistic reaction conditions and the corresponding catalytic data unraveled the adsorption of ammonia via oxygen on the iron site. The derived reaction model supports a mechanism where adsorbed NOx reacts with ammonia coordinated to the Fe(3+) site yielding Fe(2+) whose reoxidation is slow.

Probing the Electronic Structure of Substituted Ferrocenes with High-Resolution XANES Spectroscopy

Bridging the gap: High energy resolution fluorescence detected X-ray absorption near edge structure (HERFD-XANES) in combination with TD-DFT calculations makes it possible to probe the electronic structure of substituted ferrocene compounds and to make the influence of substituents visible. This opens the door to in situ HERFD-XANES studies of catalytic mechanisms in transition-metal chemistry (see figure). Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.