X-ray Absorption Spectroscopy Study Research Articles

Steering the Reaction Pathway of CO2 Electroreduction by Tuning the Coordination Number of Copper Catalysts.

Cu-based catalysts are optimal for the electroreduction of CO2 to generate hydrocarbon products. However, controlling product distribution remains a challenging topic. The theoretical investigations have revealed that the coordination number (CN) of Cu considerably influences the adsorption energy of *CO intermediates, thereby affecting the reaction pathway. Cu catalysts with different CNs were fabricated by reducing CuO precursors via cyclic voltammetry (Cyc-Cu), potentiostatic electrolysis (Pot-Cu), and pulsed electrolysis (Pul-Cu), respectively. High-CN Cu catalysts predominantly generate C2+ products, while low-CN Cu favors CH4 production. For instance, over the high-CN Pot-Cu, C2+ is the main product, with the Faradaic efficiency (FE) reaching 82.5% and a partial current density (j) of 514.3 mA cm-2. Conversely, the low-CN Pul(3)-Cu favors the production of CH4, achieving the highest FECH4 value of 56.7% with a jCH4 value of 234.4 mA cm-2. In situ X-ray absorption spectroscopy and Raman spectroscopy studies further confirm the different *CO adsorptions over Cu catalysts with different CN, thereby directing the reaction pathway of the CO2RR.

Ni-rich LiNi0.905Co0.043Al0.052O2 cathode material for high-energy density Li-ion cells: Tuning lithium content, structural evolution, and full-cell performance

Ni-rich LiNi0.905Co0.043Al0.052O2 oxides with the Li excess (x) up to 7 mol.% used in the synthesis are prepared by a facile dry-mixing method. It is shown that the Li/Ni mixing level and crystallite size are dependent on the Li amount, while Al from the precursor acts as a scavenger of the excessive Li. Operando X-ray diffraction (XRD) studies enable explaining differences in the structural evolution of materials exhibiting high and low Li/Ni mixing, especially in the H2↔H3 transition region. Soft X-ray absorption spectroscopy (XAS) studies show differences in the charge state evolution of the surface and bulk Ni. The optimized oxide with the Li excess x = 2 mol.% delivers excellent electrochemical performance, with an initial discharge capacity of 205.5 mAh g−1 at 0.1C, and 91.4% capacity retention after 100 cycles at 1C. The unmodified in any other way cathode material allows achieving the discharge capacity of 178.5 mAh g−1 at the high rate of 5C, and works well in the full-cells.

Novel high-pressure/high-temperature reactor cell for in situ and operando x-ray absorption spectroscopy studies of heterogeneous catalysts at synchrotron facilities.

This paper presents the development of a novel high-pressure/high-temperature reactor cell dedicated to the characterization of catalysts using synchrotron x-ray absorption spectroscopy under operando conditions. The design of the vitreous carbon reactor allows its use as a plug-flow reactor, monitoring catalyst samples in a powder form with a continuous gas flow at high-temperature (up to 1000 °C) and under high pressure (up to 1000bar) conditions, depending on the gas environment. The high-pressure/high-temperature reactor cell incorporates an automated gas distribution system and offers the capability to operate in both transmission and fluorescence detection modes. The operando x-ray absorption spectroscopy results obtained on a bimetallic InCo catalyst during CO2 hydrogenation reaction at 300 °C and 50bar are presented, replicating the conditions of a conventional microreactor. The complete setup is available for users and permanently installed on the Collaborating Research Groups French Absorption spectroscopy beamline in Material and Environmental (CRG-FAME) sciences and French Absorption spectroscopy beamline in Material and Environmental sciences at ultra-high dilution (FAME-UHD) beamlines (BM30 and BM16) at the European Synchrotron Radiation Facility in Grenoble, France.

Aluminium, Nitrogen-Dual-Doped Reduced Graphene Oxide Co-Existing with Cobalt-Encapsulated Graphitic Carbon Nanotube as an Activity Modulated Electrocatalyst for Oxygen Electrocatalyst for Oxygen Electrochemistry Applications.

There is a rising need to create high-performing, affordable electrocatalysts in the new field of oxygen electrochemistry. Here, a cost-effective, activity-modulated electrocatalyst with the capacity to trigger both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in an alkaline environment is presented. The catalyst (Al, Co/N-rGCNT) is made up of aluminium, nitrogen-dual-doped reduced graphene oxide sheets co-existing with cobalt-encapsulated carbon nanotube units. Based on X-ray Absorption Spectroscopy (XAS) studies, it is established that the superior reaction kinetics in Al, Co/N-rGCNT over their bulk counterparts can be attributed to their electronic regulation. The Al, Co/N-rGCNT performs as a versatile bifunctional electrocatalyst for zinc-air battery (ZAB), delivering an open circuit potential ≈1.35V and peak power density of 106.3mWcm-2, which are comparable to the system based on Pt/C. The Al, Co/N-rGCNT-based system showed a specific capacity of 737mAhgZn -1 compared to 696mAhgZn -1 delivered by the system based on Pt/C. The DFT calculations indicate that the adsorption of Co in the presence of Al doping in NGr improves the electronic properties favoring ORR. Thus, the Al, Co/N-rGCNT-based rechargeable ZAB (RZAB) emerges as a highly viable and affordable option for the development of RZAB for practical applications.

Operando double-edge high-resolution X-ray absorption spectroscopy study of BiVO4 photoanodes.

High energy resolution fluorescence detected X-ray absorption spectroscopy is a powerful method for probing the electronic structure of functional materials. The X-ray penetration depth and photon-in/photon-out nature of the method allow operando experiments to be performed, in particular in electrochemical cells. Here, operando high-resolution X-ray absorption measurements of a BiVO4 photoanode are reported, simultaneously probing the local electronic states of both cations. Small but significant variations of the spectral lineshapes induced by the applied potential were observed and an explanation in terms of the occupation of electronic states at or near the band edges is proposed.

Correlating Structure with Spectroscopy in Ascorbate Peroxidase Compound II.

Structural and spectroscopic investigations of compound II in ascorbate peroxidase (APX) have yielded conflicting conclusions regarding the protonation state of the crucial Fe(IV) intermediate. Neutron diffraction and crystallographic data support an iron(IV)-hydroxo formulation, whereas Mössbauer, X-ray absorption (XAS), and nuclear resonance vibrational spectroscopy (NRVS) studies appear consistent with an iron(IV)-oxo species. Here we examine APX with spectroscopy-oriented QM/MM calculations and extensive exploration of the conformational space for both possible formulations of compound II. We establish that irrespective of variations in the orientation of a vicinal arginine residue and potential reorganization of proximal water molecules and hydrogen bonding, the Fe-O distances for the oxo and hydroxo forms consistently fall within distinct, narrow, and nonoverlapping ranges. The accuracy of geometric parameters is validated by coupled-cluster calculations with the domain-based local pair natural orbital approach, DLPNO-CCSD(T). QM/MM calculations of spectroscopic properties are conducted for all structural variants, encompassing Mössbauer, optical, X-ray absorption, and X-ray emission spectroscopies and NRVS. All spectroscopic observations can be assigned uniquely to an Fe(IV)═O form. A terminal hydroxy group cannot be reconciled with the spectroscopic data. Under no conditions can the Fe(IV)═O distance be sufficiently elongated to approach the crystallographically reported Fe-O distance. The latter is consistent only with a hydroxo species, either Fe(IV) or Fe(III). Our findings strongly support the Fe(IV)═O formulation of APX-II and highlight unresolved discrepancies in the nature of samples used across different experimental studies.

Probing the Dynamic Landscape: from Static to Time-Resolved X-ray Absorption Spectroscopy to Investigate Copper Redox Chemistry in Neurodegenerative Disorders.

Copper (Cu), capable of existing in various oxidation states, notably Cu(I) and Cu(II), plays a pivotal role in diverse biological redox reactions. This includes its involvement in pathways associated with oxidative stress in neurodegenerative disorders such as Alzheimer's disease, Parkinson's disease, and Transmissible Spongiform Encephalopathies. This paper offers an overview of X-ray Absorption Spectroscopy (XAS) studies designed to elucidate the interactions between Cu ions and proteins or peptides associated with these neurodegenerative diseases. The emphasis lies on the technique's specificity, revealing the local coordination environment, and on its sensitivity to Cu oxidation states. Furthermore, the paper focuses on XAS applications targeting the characterization of intermediate reaction states and explores the opportunities arising from recent advancements in time-resolved XAS at ultra-bright synchrotron and free electron laser radiation sources.

Interfacial engineering of high-performance Fe2P2O7-based electrocatalysts for alkaline exchange membrane fuel cells

Fuel cells promise high energy density and energy conversion efficiency but are plagued by the scarcity of platinum for facilitating the oxygen reduction reaction (ORR). Herein, a facile synthesis of a heterojunction electrocatalyst of ZIF-8 derived carbon (Z8C) supported Fe2P2O7 (Fe2P2O7@Z8C) is reported. The electrocatalyst exhibited higher half-wave potential than the state-of-the-art Pt/C catalyst by more than 33 mV and achieved a peak power density of 152.47 mW cm−2, outperforming the Pt/C-driven cell by ca. 14.5 mW cm−2 in alkaline membrane electrode assemblies under similar operating conditions. X-ray photoelectron and X-ray absorption spectroscopic studies suggested a spontaneous electron redistribution across the heterojunction interface in Fe2P2O7@Z8C. Density functional theory calculations indicated that the electron redistribution may remarkably promote the intrinsic activity of Fe2P2O7@Z8C toward the four-electron ORR pathway. These findings offer an indispensable strategy for rational design of highly efficient and durable non-noble electrocatalysts.

Modulating Lattice Oxygen Activity of Iron-Based Triple-Conducting Nanoheterostructure Air Electrode via Sc-Substitution Strategy for Protonic Ceramic Cells.

Iron-based perovskite air electrodes for protonic ceramic cells (PCCs) offer broad application prospects owing to their reasonable thermomechanical compatibility and steam tolerance. However, their insufficient electrocatalytic activity has considerably limited further development. Herein, oxygen-vacancy-rich BaFe0.6 Ce0.2 Sc0.2 O3-δ (BFCS) perovskite is rationally designed by a facile Sc-substitution strategy for BaFe0.6 Ce0.4 O3-δ (BFC) as efficient and stable air electrode for PCCs. The BFCS electrode with an optimized Fe 3d-eg orbital occupancy and more oxygen vacancies exhibits a polarization resistance of ≈ 0.175Ωcm2 at 600°C, ≈ 1/3 of the BFC electrode (≈0.64Ωcm2 ). Simultaneously, BFCS shows favorable proton uptake with a low proton defect formation enthalpy (- 81kJmol-1 ). By combining soft X-ray absorption spectroscopy and electrical conductivity relaxation studies, it is revealed that the enhancement of Fe4+ -O2- interactions in BFCS promotes the activation and mobility of lattice oxygen, triggering the activity of BFCS in both oxygen reduction and evolution reactions (ORR/OER). The single cell achieves encouraging output performance in both fuel cell (1.55 Wcm-2 ) and electrolysis cell (-2.96Acm-2 at 1.3V) modes at 700°C. These results highlight the importance of activating lattice oxygen in air electrodes of PCCs.

Synthesis, Characterization, and Catalytic Application of Colloidal and Supported Manganese Nanoparticles.

Colloidal and supported manganese nanoparticles were synthesized following an organometallic approach and applied in the catalytic transfer hydrogenation (CTH) of aldehydes and ketones. Reaction parameters for the preparation of colloidal nanoparticles (NPs) were optimized to yield small (2-2.5 nm) and well-dispersed NPs. Manganese NPs were further immobilized on an imidazolium-based supported ionic phase (SILP) and characterized to evaluate NP size, metal loading, and oxidation states. Oxidation of the Mn NPs by the support was observed resulting in an average formal oxidation state of +2.5. The MnOx@SILP material showed promising performance in the CTH of aldehydes and ketones using 2-propanol as a hydrogen donor, outperforming previously reported Mn NPs-based CTH catalysts in terms of metal loading-normalized turnover numbers. Interestingly, MnOx@SILP were found to lose activity upon air exposure, which correlates with an additional increase in the average oxidation state of Mn as revealed by X-ray absorption spectroscopic studies.

Role of p-d hybridization in structural transition and magnetic properties of Co-substituted Mn3O4: X-ray absorption spectroscopy study

This work investigates the role of p-d orbital hybridization in the structural transition from tetragonal I41/amd to cubic Fd3̅m and enhancement in Néel temperature (TN) from 43 K to 175 K in (Mn1−xCox)3O4 (where x = 0.0, 0.1, 0.2, 0.3, 0.5, and 0.6). X-ray absorption spectra of Co-L2,3 and Mn-L2,3 edges show that the high-spin Co2+ cations initially substitute the Mn2+ at the tetrahedral-sites. When the tetrahedral-sites are fully occupied, then the high-spin Co3+ cations begin to occupy the octahedral-site. The substitution of Co cations at both the tetrahedral and octahedral-sites increases the bond angle between adjacent tetrahedral and octahedral site cations via O-2p orbitals, suppressing the orbital instability of Mn3+ cations. These effects dramatically enhance the superexchange interaction and hence the TN.

Are 4f-Orbitals Engaged in Covalent Bonding Between Lanthanides and Triphenylphosphine Oxide? An Oxygen K-Edge X-ray Absorption Spectroscopy and Density Functional Theory Study.

The bonding covalency between trivalent lanthanides (Ln = La, Pr, Nd, Eu, Gd) and triphenylphosphine oxide (TPPO) is studied by X-ray absorption spectra (XAS) and density functional theory (DFT) calculations on the LnCl3(TPPO)3 complexes. The O, P, and Cl K-edge XAS for the single crystals of LnCl3(TPPO)3 were collected, and the spectra were interpreted based on DFT calculations. The O and P K-edge XAS spectra showed no significant change across the Ln series in the LnCl3(TPPO)3 complexes, unlike the Cl K-edge XAS spectra. The experimental O K-edge XAS spectra suggest no mixing between the Ln 4f- and the O 2p-orbitals in the LnCl3(TPPO)3 complexes. DFT calculations indicate that the amount of the O 2p character per Ln-O bond is less than 0.1% in the Ln 4f-based orbitals in all of the LnCl3(TPPO)3 complexes. The experimental spectra and theoretical calculations demonstrate that Ln 4f-orbitals are not engaged in the covalent bonding of lanthanides with TPPO, which contrasts the involvement of U 5f-orbitals in covalent bonding in the UO2Cl2(TPPO)2 complex. Results in this work reinforce our previous speculation that bonding covalency is potentially responsible for the extractability of monodentate organophosphorus ligands toward metal ions.

X-ray absorption spectroscopic studies of Fe environments in borosilicate waste glasses synthesized under a variety of redox conditions

Fe K-edge X-ray absorption spectroscopy (XAS) was performed on two borosilicate waste glass series to determine Fe valence and coordination changes over a wide range of redox synthesis conditions. Data were also collected on eight Fe-silicate standards, including the rare phase, pellyite, that was used as a tetrahedral Fe2+O4 standard. X-ray absorption near-edge structure (XANES) linear combination fits of the Fe2+O4, Fe2+O5, and Fe3+O4 standards data to the glass spectra determined Fe2+/Fetotal ratios from 0.07 to 0.90 that are within 10 % of Mössbauer findings. As the glasses become reduced, XANES indicates Fe3+O4 tetrahedra are being replaced by Fe2+O4 tetrahedra, and possibly, Fe2+O5 sites, while extended X-ray absorption fine structure analyses show average Fe-O distances increase from 1.88 to 1.96 Å. The XANES-determined three Fe-site population distributions in the glasses are similar to findings reported in a recent molecular dynamics study of Fe redox effects in waste glass.

Near-surface electronic structure in strained Ni-ferrite films: An x-ray absorption spectroscopy study

We report on the x-ray absorption spectra (XAS) and x-ray magnetic circular dichroism (XMCD) of a series of NiFe2O4 (Ni ferrite) films grown on symmetry matched substrates and measured in two geometries: out-of-plane and near in-plane. The Ni ferrite films, grown by pulsed laser deposition, are epitaxial and the substrates used (ZnGa2O4, CoGa2O4, MgGa2O4, and MgAl2O4) introduce a systematic variation in the lattice mismatch between the substrate and the film. Modeling of the XAS and XMCD spectra, both measured with the surface sensitive total electron yield mode, indicates that the Ni2+ cations reside on the octahedrally coordinated lattice sites in the spinel structure. Analyses of the Fe XAS and XMCD spectra are consistent with Fe3+ cations occupying a subset of the octahedral and tetrahedral sites in the spinel oxide lattice with the addition of a small amount of Fe2+ located on octahedral sites. The Ni2+ orbital to spin moment ratio (μℓ/μs), derived from the application of XMCD sum rules, is enhanced for the substrates with a small lattice mismatch relative to NiFe2O4. The results suggest a path for increasing the orbital moment in NiFe2O4 by applying thin film growth techniques that can maintain a highly strained lattice for the NiFe2O4 film.

Room-temperature-persistent magnetic interaction between coordination complexes and nanoparticles in maghemite-based nanohybrids.

Maghemite nanoparticles functionalised with Co(II) coordination complexes at their surface show a significant increase of their magnetic anisotropy, leading to a doubling of the blocking temperature and a sixfold increase of the coercive field. Magnetometric studies suggest an enhancement that is not related to surface disordering, and point to a molecular effect involving magnetic exchange interactions mediated by the oxygen atoms at the interface as its source. Field- and temperature-dependent X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) studies show that the magnetic anisotropy enhancement is not limited to surface atoms and involves the core of the nanoparticle. These studies also point to a mechanism driven by anisotropic exchange and confirm the strength of the magnetic exchange interactions. The coupling between the complex and the nanoparticle persists at room temperature. Simulations based on the XMCD data give an effective exchange field value through the oxido coordination bridge between the Co(II) complex and the nanoparticle that is comparable to the exchange field between iron ions in bulk maghemite. Further evidence of the effectiveness of the oxido coordination bridge in mediating the magnetic interaction at the interface is given with the Ni(II) analog to the Co(II) surface-functionalised nanoparticles. A substrate-induced magnetic response is observed for the Ni(II) complexes, up to room temperature.

Temperature Dependent EXAFS to Address Functional Mechanisms in Battery Materials

Increasing the contribution of renewable energy sources is necessary to meet the fast increase of global energy needs and match the CO2 reduction targets. In order to address these challenges, intensive research efforts are ongoing both in energy harvesting and storage technologies such as solar panels, fuel cells, supercapacitors and batteries. The latter are required to match the energy demand and supply; in fact, batteries are by far the most ubiquitous energy storage technology currently employed.Synchrotron x-ray spectroscopies have played a key role in the continuous development and breakthroughs in battery science, thanks to their capability to provide accurate information on electronic structure of the redox active element, local structure, and morphological information. In particular, X-ray absorption spectroscopy (XAS) is more and more employed for addressing battery materials [1]. Generally, XAS studies on battery materials are performed at a single temperature as a function of charge, to access information on the electrochemical behavior and charge transfer mechanism during the intercalation or deintercalation process. However, the fact that the charging/discharging process is expected to have direct influence on the bond length characteristics, strength and disorder, it is important to perform temperature dependence measurements to find a realistic correlation between the local structure and the battery characteristics. Indeed, temperature-dependent studies quantitatively allow to discriminate in between static and dynamic disorder, and to have direct access to the local force constant between the atom pairs. Here the interest of performing temperature dependent extended X-ray absorption fine structure (EXAFS) studies is highlighted by exploiting several examples. In Li and Mn-rich NMC cathodes temperature-dependent EXAFS investigation revealed the evolution of the lattice rigidity which directly affects the reversible anionic redox contribution [2-3]. Similar studies on Ti based MXene-type [4], NaxCoO2 [5], and V2O5 [6] electrode materials underline the importance of the local atomic correlations as limiting factor in the ion diffusion in battery materials.

Temperature-Dependent Interplay of Chemical Versus Electrochemical Electrolyte Oxidation at Ni-Rich Cathodes

Increasing demands for high energy density Li-ion batteries as a source for power supply are demanding an optimization of cathode active materials (CAMs) and of the overall cell chemistry of batteries. Thus, the main interest of researchers has focused on nickel-rich (>80%) layered transition metal oxides such as NCMs (LiNixCoyMnzO2, with x+y+z=1) or NCAs (LiNixCoyAlzO2, with x+y+z=1) as CAMs, owing to their high capacity. However, as a result of the increase in Ni-content, the structural stability of these CAMs is significantly decreased at high upper cut-off potentials compared to those with lower Ni-content, resulting in capacity fading, which restricts their practically achievable capacity.[1] One possible culprit behind this capacity fading at high state-of-charge (SOC) is the release of reactive lattice oxygen, which is known for layered TM-oxides to occur at high SOC (i.e., starting at approx. 80% SOC).[2] The released oxygen is proposed to lead to the chemical oxidation of ethylene carbonate (EC), resulting in HF formation, which in turn is proposed to trigger the dissolution of TMs.[3] Furthermore, the electrochemical oxidation of the electrolyte is known to occur at high potentials, which as a result of its reactive reaction products, can induce further transition metal (TM) dissolution from the CAM.[4,5] The proposed chemical oxidation of the electrolyte by lattice oxygen suggests that this process should be strongly correlated to the dissolution of TMs from the CAM. However, as shown by operando X-ray absorption spectroscopy (XAS) and on-line electrochemical mass spectroscopy (OEMS) studies, the onset for the TM-dissolution, depending on the CAM under investigation, occurs at ~300 mV higher potentials compared to the onset for oxygen evolution.[2,3] This suggests that the dissolution of metals is rather induced by the electrochemical oxidation of the carbonate-based electrolyte, which was reported to initiate at potentials above 4.7 VLi at room temperature.[5] Both the electrochemical oxidation of battery electrolytes, as well as the dissolution of TMs from the CAM were reported to be strongly affected by temperature, while the onset potential for lattice oxygen loss is essentially unaffected, which further hints towards the significance of former.[5-7] Within this work we therefore conduct a detailed study on the temperature dependency of both the gas formation due to (electro)chemical electrolyte oxidation and the dissolution of TMs by means of OEMS and operando hard XAS, respectively. By applying a measurement protocol consisting of constant voltage-holds in steps of 50 mV at elevated potentials (see Figure 1), an excellent time as well as potential resolution enables the deconvolution of the onset for lattice oxygen release and the (electro)chemical oxidation of LP47 (1 M LiPF6 in EC:DEC 3:7 by weight) for a LiNi0.80Co0.15Al0.05O2 (NCA) CAM via OEMS. It will be shown that the onset for oxygen evolution coincides with a significant evolution of CO2 (see Figure 1b), indicating chemical oxidation of the electrolyte. However, the onset for POF3/PF5 evolution (marked in Figure 1b as “POF3”, since both gasses appear on the same mass channel)[8], which is a reaction product from the decomposition of LiPF6 caused by electrochemical electrolyte oxidation, is shifted to 300 – 450 mV higher potentials (depending on the temperature). It suggests a chemical oxidation mechanism of the electrolyte, which proceeds without significant H2O/H+ production. A change in temperature strongly affects this onset of “POF3” evolution, while O2 is released at the same degree of de-lithiation, regardless of temperature. To correlate this effect observed in the temperature-dependent gassing behavior to the dissolution of transition metals for this CAM, an operando hard XAS study at different temperatures will be conducted.

Operando and Dynamic XAS Studies of Metal-Support Interactions of Iridium-Based Catalysts for Oxygen Evolution Reaction (OER) in Proton Exchange Membrane Water Electrolysis (PEMWE)

Iridium (Ir) is an important electrocatalyst material for the oxygen evolution reaction (OER) in acidic media. However, high loadings of very costly and scarce Ir are needed to achieve sufficient performance in proton exchange membrane water electrolysis (PEMWE). [1] To establish a large-scale green hydrogen economy based on PEMWE in the near future, the Ir loading needs to be further reduced. In the last decades, promising Ir-based catalyst strategies has been developed to improve the OER activity by controlling the size of Ir nanoparticles (NPs) [2] and tuning the electronic interactions of the Ir NPs with the catalyst support material, referred to as strong metal support interaction (SMSI). The latter has frequently been observed for heterogeneous catalysts (e.g. Au NPs supported on titanium oxide [3]), while the SMSI for Ir-based OER electrocatalysts is poorly understood to date.This study focuses on operando and dynamic X-ray absorption spectroscopy (XAS) analysis of Ir NPs deposited on three support materials: graphitized carbon (C), titanium oxide (TiO2) and antimony-doped tin oxide (ATO). The surfactant-free Ir NPs with controlled size of around 1 nm were obtained by a colloidal approach in low-boiling point alcohols. [2, 4] Afterwards, the Ir NPs were homogeneously distributed on different support materials with similar loadings and particle sizes confirmed by TEM and XRD. Solute components from the aged catalyst materials (Ir and/or support material) in the electrolyte solution were determined by ICP-OES, while the solid catalyst powders were analysed by TGA and µ-XRF. Our first/initial electrochemical results by recording cyclic voltammetry (CV) profiles show that after the immobilization the Ir NPs obtained from the same batch are strongly oxidized on TiO2, while a metallic character of the Ir is still observed on the C and ATO. The OER mass activity of 120±8 A/gIr for Ir/C is 2-times higher than for Ir/TiO2 (60±6 A/gIr) and 1.2-times higher than for Ir/ATO (95±4 A/gIr) at 1.5 VRHE,iR-free and 25 °C obtained from rotating disc electrode (RDE) setup.Operando and dynamic Ir LIII edge XANES measurements during the cycling from 0.06 to different upper potentials (0.8, 1.0, 1.2, 1.4 and 1.6 VRHE) at 2 mV/s were performed in acidic media at the SuperXAS (X10DA) beamline, Switzerland. All measurements were carried out using a home-made spectro-electrochemical flow-cell. Principal component analysis (PCA) of Quick-XANES data confirmed the tendencies of the formation of irreversible Irz+ species on TiO2 even at low upper potentials, while ATO and C tend to retain the metallic character of the Ir NPs. From the PCA, two independent components were identified to describe the changes in the series of XANES data. The compositions of these components were then analyzed using linear combination fitting (LCF).For 60 wt.% Ir/C, the cycling up to 1.4 VRHE shows two components with 50:25:25 wt.% of Ir0:Ir3+:Ir4+ and 42:0:58 wt.% of Ir0:Ir3+:Ir4+ obtained from the PCA and LCF analysis. During the cycling, the ratios of these components change gradually. In spite of the strong hysteresis behavior, we observed that the ratio between both components reverses to the initial state. In other words, only the component with 42:0:58 wt.% of Ir0:Ir3+:Ir4+ is present at 1.4 VRHE, while the other component is dominant at lower anodic potential.In the same experiment, the analysis of our data for 60 wt% Ir/ATO using PCA indicates two independent components with 74:11:15 wt.% of Ir0:Ir3+:Ir4+ and 70:0:30 wt.% of Ir0:Ir3+:Ir4+. The cycling up to 1.4 VRHE shows similar behavior like 60 wt.% Ir/C.Although the same batch of colloidal Ir NPs were used for the immobilization, the PCA and LCF analysis for 60 wt.% Ir/TiO2 reveal two components with high content of Ir4+ species, more precisely 36:64 wt.% of Ir0:Ir4+ and 2:98 wt.% of Ir0:Ir4+. The cycling up to 1.4 VRHE shows mainly a reversible behavior due to high content of Ir4+ species on TiO2. With increasing anodic potential, the content of metallic Ir further decreases and the main component with almost only Ir4+ species is stable at 1.4 VRHE. In the backward direction, the reduction to metallic Ir takes place to small extent. Therefore, the component with 36:64 wt.% of Ir0:Ir4+ is mainly present at 0.06 VRHE.In summary, our PCA and LCF analysis of the operando and dynamic Quick-XANES data provide further insights into the electronic structure of Ir species and the mechanism of the complex metal-support interaction for Ir NPs immobilized on C, ATO and TiO2.

An Electrochemical Cell for Operando Grazing-Incidence X-Ray Absorption Spectroscopic Studies of Low-Loaded Electrodes

X-ray absorption spectroscopy (XAS) is a powerful technique that can provide element specific information on the local electronic and structural properties of newly developed electrocatalysts, especially when performed under operating conditions (i.e., operando). However, the large amounts of catalyst typically needed to achieve sufficiently high spectral quality and temporal resolution can result in working electrodes of several micrometers in thickness. This can in turn lead to an inhomogeneous potential distribution across the electrode, delamination and/or incomplete utilization of the catalyst layer, severe bubble formation and accumulation due to poor mass transport properties.[1, 2] In addition, the activity and selectivity of a catalyst are often measured in a different cell geometry (e.g., using rotating disk electrodes (RDEs)), leading to uncertainties in comparison with the results inferred from spectroscopic data.[3]To tackle these problems we have developed a new spectroelectrochemical XAS flow cell that enables spectral acquisition in fluorescence mode using an X-ray beam incidence angle of ≤ 0.1° with regards to the working electrode’s substrate plane, i.e., in a so called grazing incidence (GI) configuration (see Figure 1). In this acquisition configuration we successfully tracked the formation of palladium hydride with a time resolution of 10 seconds per spectrum while using a Pd-loading as low as 50 µgPd∙cm-2. Moreover, the careful design of the working electrode flow field allows the study of faradaic processes (e.g., O2-reduction) under mass-transport controlled conditions entailing currents comparable to those attained in RDE measurements (≤ 10 mA∙cm−2). The combination of these features with an ion-conductive membrane to separate the working- and counter-electrode compartments additionally enables the detection of gaseous products (e.g., from CO2-electroreduction) by degassing them out of the electrolyte and analyzing them in time-resolved fashion by means of mass spectrometry.[4] References Diklić, N., et al., Potential Pitfalls in the Operando XAS Study of Oxygen Evolution Electrocatalysts. ACS Energy Letters, 2022. 7(5): p. 1735-1740. Diercks, J.S., et al., Spectroscopy vs. Electrochemistry: Catalyst Layer Thickness Effects on Operando/In Situ Measurements. Angew Chem Int Ed Engl, 2023: p. e202216633. Diercks, J.S., et al., Interplay between Surface-Adsorbed CO and Bulk Pd Hydride under CO2-Electroreduction Conditions. ACS Catalysis, 2022: p. 10727-10741. Khanipour, P., et al., Electrochemical Real-Time Mass Spectrometry (EC-RTMS): Monitoring Electrochemical Reaction Products in Real Time. Angew Chem Int Ed Engl, 2019. 58(22): p. 7273-7277 Figure 1

An XAS study of Hg(II) sorption to Al-based drinking water treatment residuals

Drinking water treatment residuals (DWTRs) are produced from the coagulation and flocculation processes in conventional drinking water treatment. The abundant metal oxide content of these materials resulting from the use of coagulants, like alum and ferric chloride, has driven strong research interest into the reuse of DWTRs as sorptive materials. Using a suite of aluminum-based DWTRs, we provide new insights into Hg(II) sorption mechanisms. Experiments performed at circum-neutral pH show that sorption capacities are related to the amount of organic carbon/matter present in DWTRs. We found that carbon rich samples can scavenge about 9000 mg/kg of Hg, in contrast to 2000 mg/kg for lime based DWTRs. X-ray absorption spectroscopy (XAS) at the Hg L3 edge further characterizes mercury coordination. X-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS) results point to a partial association of mercury with sulfur at low mass loadings, transitioning to a full association with oxygen/carbon at higher concentrations of sorbed Hg(II) and in DWTRs with limited sulfur content. These results suggest that sorption of Hg(II) is primarily controlled by the carbon/organic matter fraction of DWTRs, but not by the coagulants.