Operando X-ray Absorption Spectroscopy Research Articles

Understanding the Correlation between Electrochemical Performance and Operating Mechanism of a Co-free Layered-Spinel Composite Cathode for Na-Ion Batteries.

Compositing different crystal structures of layered transition metal oxides (LTMOs) is an emerging strategy to improve the electrochemical performance of LTMOs in sodium-ion batteries. Herein, a cobalt-free P2/P3-layered spinel composite, P2/P3-LS-Na1/2Mn2/3Ni1/6Fe1/6O2 (LS-NMNF), is synthesized, and the synergistic effects from the P2/P3 and spinel phases were investigated. The material delivers an initial discharge capacity of 143 mAh g-1 in the voltage range of 1.5-4.0 V and displays a capacity retention of 73% at the 50th cycle. The material shows a discharge capacity of 72 mAh g-1 at 5C. This superior rate performance by the material could be by virtue of the increased electronic conductivity contribution of the incorporated spinel phase. The charge compensation mechanism of the material is investigated by in operando X-ray absorption spectroscopy (in a voltage range of 1.5-4.5 V vs Na+/Na), which revealed the contribution of all transition metals toward the generated capacity. The crystal structure evolution of each phase during electrochemical cycling was analyzed by in operando X-ray diffraction. Unlike in the case of many reported P2/P3 composite cathode materials and spinel-incorporated cobalt-containing P2/P3 composites, the formation of a P'2 phase at the end of discharge is absent here.

Redox-driven surface generation of highly active Pd/PdO interface boosting low-temperature methane combustion

The supported Pd catalyst has been a benchmark for methane elimination. However, the active structures have been long under debate. Here, by the aberration-corrected high angle annular dark field scanning transmission electron microscopy, operando X-ray absorption spectroscopy and quasi in situ X-ray photoelectron spectroscopy, we revealed the two-dimensional metallic Pd bumps on the PdO surface (litchi-like structure) generated by the redox atmosphere under the lean condition as a highly active structure of the Pd/Al2O3 catalyst. The substantially increased Pd/PdO interfaces boost the methane combustion activity higher than the similar catalysts reported previously, and remarkably enhance the reaction rate by 15.5 and 10.7 times that of pure PdO or metallic Pd counterpart under lean condition at 300 °C, respectively. Density-functional theory calculations confirm the synergistic C–C bond activation of methane on the Pd/PdO interfaces. Our work provides new insight into the traditional understanding of the chemical state and particle size effects of the industrial Pd catalysts for methane oxidation.

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.

A Versatile Electrochemical Cell for Operando XAS

AbstractIn situ and operando X‐ray absorption spectroscopy (XAS) provides fundamental insight into the working principles of electrocatalysts and is an important tool for future catalyst development. However, the design of an operando XAS electrocatalytic cell is not facile, and researchers designing cells, whether new cells or modifications to previous cells, often spend many hours on cell design before obtaining high‐quality XAS data. Here, we describe the design, with engineering drawings, and operation of a versatile XAS cell with options for gas flow, electrolyte flow, pH monitoring, temperature monitoring, and the ability to handle many catalyst forms (any catalyst that can be deposited onto a conductive X‐ray transparent substrate). We benchmarked XAS spectra collected using the new experimental cell to a previous cell design showing its ability to produce quality XAS data. We demonstrate the viability of this cell by providing insight into electrocatalysts by studying cation effects and show the tetrabutylammonium cation prevents bulk oxidation of copper. We hope the availability of this cell allows researchers to convert time typically spent on cell design to time spent on breakthroughs in electrocatalysis.

Atomically Dispersed Ru-doped Ti4O7 Electrocatalysts for Chlorine Evolution Reaction with a Universal Activity.

Chlorine has been supplied by the chlor-alkali process that deploys dimensionally stable anodes (DSAs) for the electrochemical chlorine evolution reaction (ClER). The paramount bottlenecks have been ascribed to an intensive usage of precious elements and inevitable competition with the oxygen evolution reaction. Herein, a unique case of Ru2+-O4 active motifs anchored on Magnéli Ti4O7 (Ru-Ti4O7) via a straightforward wet impregnation and mild annealing is reported. The Ru-Ti4O7 performs radically active ClER with minimal deployment of Ru (0.13 wt%), both in 5 m NaCl (pH 2.3) and 0.1 m NaCl (pH 6.5) electrolytes. Scanning electrochemical microscopy demonstrates superior ClER selectivity on Ru-Ti4O7 compared to the DSA. Operando X-ray absorption spectroscopy and density functional theory calculations reveal a universally active ClER (over a wide range of pH and [Cl-]), through a direct adsorption of Cl- on Ru2+-O4 sites as the most plausible pathway, together with stabilized ClO* at low [Cl-] and high pH.

Best practices for operando hard X-ray absorption spectroscopy

Best practices for operando hard X-ray absorption spectroscopy

Enhanced Carbon-Carbon Coupling at Interfaces with Abrupt Coordination Number Changes.

Cu-catalyzed electrochemical CO2 reduction reaction (CO2RR) produces multi-carbon (C2+) chemicals with considerable selectivities and activities, yet required high overpotentials impede its practical application. Here, we design interfaces with abrupt coordination number (CN) changes that greatly reduce the applied potential for achieving high C2+ Faradaic efficiency (FE). Encouraged by the mechanistic finding that the coupling between *CO and *CO(H) is the most probable C-C bond formation path, we use Cu2O- and Cu-phthalocyanine-derived Cu (OD-Cu and PD-Cu) to build the interface. Using operando X-ray absorption spectroscopy (XAS), we find that the Cu CN of OD-Cu is ~11, favoring CO* adsorption, while the PD-Cu has a COH*-favorable CN of ~4. Operando Raman spectroscopy revealed that the interfaces with abrupt CN changes promote *OCCOH formation. As a result, the designed catalyst achieves a C2+ FE of 85±2 % at 220 mA cm-2 in a zero-gap CO2 electrolyzer. An improvement of C2+ FE by 3 times is confirmed at the low potential regime where the current density is 60-140 mA cm-2, compared to bare OD-Cu. We report a 45-h stable CO2RR operation at 220 mA cm-2, producing a C2+ product FE of ~80 %.

Electrocatalytic Nitrate and Nitrite Reduction toward Ammonia Using Cu2O Nanocubes: Active Species and Reaction Mechanisms.

The electrochemical reduction of nitrate (NO3-) and nitrite (NO2-) enables sustainable, carbon-neutral, and decentralized routes to produce ammonia (NH3). Copper-based materials are promising electrocatalysts for NOx- conversion to NH3. However, the underlying reaction mechanisms and the role of different Cu species during the catalytic process are still poorly understood. Herein, by combining quasi in situ X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption spectroscopy (XAS), we unveiled that Cu is mostly in metallic form during the highly selective reduction of NO3-/NO2- to NH3. On the contrary, Cu(I) species are predominant in a potential region where the two-electron reduction of NO3- to NO2- is the major reaction. Electrokinetic analysis and in situ Raman spectroscopy was also used to propose possible steps and intermediates leading to NO2- and NH3, respectively. This work establishes a correlation between the catalytic performance and the dynamic changes of the chemical state of Cu, and provides crucial mechanistic insights into the pathways for NO3-/NO2- electrocatalytic reduction.

Monitoring Redox Processes in Lithium-Ion Batteries by Laboratory-Scale Operando X-ray Emission Spectroscopy.

Tracking changes in the chemical state of transition metals in alkali-ion batteries is crucial to understanding the redox chemistry during operation. X-ray absorption spectroscopy (XAS) is often used to follow the chemistry through observed changes in the chemical state and local atomic structure as a function of the state-of-charge (SoC) in batteries. In this study, we utilize an operando X-ray emission spectroscopy (XES) method to observe changes in the chemical state of active elements in batteries during operation. Operando XES and XAS were compared by using a laboratory-scale setup for four different battery systems: LiCoO2 (LCO), Li[Ni1/3Co1/3Mn1/3]O2 (NMC111), Li[Ni0.8Co0.1Mn0.1]O2 (NMC811), and LiFePO4 (LFP) under a constant current charging the battery in 10 h (C/10 charge rate). We show that XES, despite narrower chemical shifts in comparison to XAS, allows us to fingerprint the battery SOC in real time. We further demonstrate that XES can be used to track the change in net spin of the probed atoms by analyzing changes in the emission peak shape. As a test case, the connection between net spin and the local chemical and structural environment was investigated by using XES and XAS in the case of electrochemically delithiated LCO in the range of 2-10% lithium removal.

In-situ and operando Grazing Incidence XAS: a novel set-up and its application to model Pd electrodes for alcohols oxidation

Abstract In this article, we present an in-situ and operando time-resolved X-ray Absorption Spectroscopy (XAS) technique which exploits a combination of Grazing Incidence XAS (GIXAS) and Fixed Energy X-ray Absorption Voltammetry (FEXRAV), the Grazing Incidence FEXRAV (GI-FEXRAV). A case-study is also outlined. Palladium ultra-low loadings were deposited above Au polycrystalline iso-oriented substrates adopting three different deposition methods: surface-controlled electrochemical methods, direct electrodeposition, and physical vapour deposition (PVD). These catalytical surfaces were prepared for the investigation by GI-FEXRAV of the Pd oxidation/dissolution phenomenon that could occur when the metal is used in the anodic compartment of Direct Alcohol Fuel Cells (DAFCs) or in electrochemical reformers. Moreover, we report a robust, low cost and versatile procedure to obtain wide and flat iso-oriented gold substrates that can mimic monocrystalline gold (1 1 1) in the electrochemical response. The use of GI-FEXRAV for the operando characterization of the catalysts, in conjunction with the designed experimental cell and our flexible Au-based electrochemical substrates show an invaluable potential in the operando study of fundamental phenomena in heterogeneous electrocatalysis model systems and, due to its versatility, paves the way to further studies on a wide selection of electrochemical systems.

Nanofeather ruthenium nitride electrodes for electrochemical capacitors.

Fast charging is a critical concern for the next generation of electrochemical energy storage devices, driving extensive research on new electrode materials for electrochemical capacitors and micro-supercapacitors. Here we introduce a significant advance in producing thick ruthenium nitride pseudocapacitive films fabricated using a sputter deposition method. These films deliver over 0.8 F cm-2 (~500 F cm-3) with a time constant below 6 s. By utilizing an original electrochemical oxidation process, the volumetric capacitance doubles (1,200 F cm-3) without sacrificing cycling stability. This enables an extended operating potential window up to 0.85 V versus Hg/HgO, resulting in a boost to 3.2 F cm-2 (3,200 F cm-3). Operando X-ray absorption spectroscopy and transmission electron microscopy analyses reveal novel insights into the electrochemical oxidation process. The charge storage mechanism takes advantage of the high electrical conductivity and the morphology of cubic ruthenium nitride and Ru phases in the feather-like core, leading to high electrical conductivity in combination with high capacity. Accordingly, we have developed an analysis that relates capacity to time constant as a means of identifying materials capable of retaining high capacity at high charge/discharge rates.

Multiple Metal-Nitrogen Bonds Synergistically Boosting the Activity and Durability of High-Entropy Alloy Electrocatalysts.

The development of Pt-based catalysts for use in fuel cells that meet performance targets of high activity, maximized stability, and low cost remains a huge challenge. Herein, we report a nitrogen (N)-doped high-entropy alloy (HEA) electrocatalyst that consists of a Pt-rich shell and a N-doped PtCoFeNiCu core on a carbon support (denoted as N-Pt/HEA/C). The N-Pt/HEA/C catalyst showed a high mass activity of 1.34 A mgPt-1 at 0.9 V for the oxygen reduction reaction (ORR) in rotating disk electrode (RDE) testing, which substantially outperformed commercial Pt/C and most of the other binary/ternary Pt-based catalysts. The N-Pt/HEA/C catalyst also demonstrated excellent stability in both RDE and membrane electrode assembly (MEA) testing. Using operando X-ray absorption spectroscopy (XAS) measurements and theoretical calculations, we revealed that the enhanced ORR activity of N-Pt/HEA/C originated from the optimized adsorption energy of intermediates, resulting in the tailored electronic structure formed upon N-doping. Furthermore, we showed that the multiple metal-nitrogen bonds formed synergistically improved the corrosion resistance of the 3d transition metals and enhanced the ORR durability.

Rapid-charging aluminium-sulfur batteries operated at 85 °C with a quaternary molten salt electrolyte

Molten salt aluminum-sulfur batteries are based exclusively on resourcefully sustainable materials, and are promising for large-scale energy storage owed to their high-rate capability and moderate energy density; but the operating temperature is still high, prohibiting their applications. Here we report a rapid-charging aluminium-sulfur battery operated at a sub-water-boiling temperature of 85 °C with a tamed quaternary molten salt electrolyte. The quaternary alkali chloroaluminate melt – possessing abundant electrochemically active high-order Al-Cl clusters and yet exhibiting a low melting point – facilitates fast Al3+ desolvation. A nitrogen-functionalized porous carbon further mediates the sulfur reaction, enabling the battery with rapid-charging capability and excellent cycling stability with 85.4% capacity retention over 1400 cycles at a charging rate of 1 C. Importantly, we demonstrate that the asymmetric sulfur reaction mechanism that involves formation of polysulfide intermediates, as revealed by operando X-ray absorption spectroscopy, accounts for the high reaction kinetics at such temperature wherein the thermal management can be greatly simplified by using water as the heating media.

Atomically Dispersed Zn/Co-N-C as ORR Electrocatalysts for Alkaline Fuel Cells.

Hydrogen fuel cells have drawn increasing attention as one of the most promising next-generation power sources for future automotive transportation. Developing efficient, durable, and low-cost electrocatalysts, to accelerate the sluggish oxygen reduction reaction (ORR) kinetics, is urgently needed to advance fuel cell technologies. Herein, we report on metal-organic frameworks-derived nonprecious dual metal single-atom catalysts (SACs) (Zn/Co-N-C), consisting of Co-N4 and Zn-N4 local structures. These catalysts exhibited superior ORR activity with a half-wave potential (E1/2) of 0.938 V versus RHE (reversible hydrogen electrode) and robust stability (ΔE1/2 = -8.5 mV) after 50k electrochemical cycles. Moreover, this remarkable performance was validated under realistic fuel cell working conditions, achieving a record-high peak power density of ∼1 W cm-2 among the reported SACs for alkaline fuel cells. Operando X-ray absorption spectroscopy was conducted to identify the active sites and reveal catalytic mechanistic insights. The results indicated that the Co atom in the Co-N4 structure was the main catalytically active center, where one axial oxygenated species binds to form an Oads-Co-N4 moiety during the ORR. In addition, theoretical studies, based on a potential-dependent microkinetic model and core-level shift calculations, showed good agreement with the experimental results and provided insights into the bonding of oxygen species on Co-N4 centers during the ORR. This work provides a comprehensive mechanistic understanding of the active sites in the Zn/Co-N-C catalysts and will pave the way for the future design and advancement of high-performance single-site electrocatalysts for fuel cells and other energy applications.

Correlating Structural Disorder in Metal (Oxy)hydroxides and Catalytic Activity in Electrocatalytic Oxygen Evolution.

Understanding the correlation between the structural evolution of electrocatalysts and their catalytic activity is both essential and challenging. In this study, we investigate this correlation in the context of the oxygen evolution reaction (OER) by examining the influence of structural disorder during and after dynamic structural evolution on the OER activity of Fe-Ni (oxy)hydroxide catalysts using operando X-ray absorption spectroscopy, alongside other experiments and theoretical calculations. The Debye-Waller factors obtained from extended X-ray absorption fine structure analyses reflect the degree of structural disorder and exhibit a robust correlation with the intrinsic OER activities of the electrocatalysts. The enhanced OER activity of in situ-generated metal (oxy)hydroxides derived from different pre-catalysts is linked to increased structural disorder, offering a promising approach for designing efficient OER electrocatalysts. This strategy may inspire similar investigations in related electrocatalytic energy-conversion systems.

Crystalline Dual-Porous Covalent Triazine Frameworks as a New Platform for Efficient Electrocatalysis.

Crystalline covalent triazine frameworks (CTFs) have gained considerable interest in energy and catalysis owing to their well-defined nitrogen-rich π-conjugated porosity and superior physicochemical properties, however, suffer from very limited molecular structures. Herein we report a novel solvent-free FeCl3 -catalyzed polymerization of 2, 6-pyridinedicarbonitrile (DCP) to achieve the first synthesis of crystalline, dual-porous, pyridine-based CTF (Fe-CTF). The FeCl3 could not only act as a highly active Lewis acid catalyst for promoting the two-dimensional ordered polymerization of DCP monomers, but also in situ coordinate with the tridentate chelators generated between pyridine and triazine groups to yield unique Fe-N3 single-atom active sites in Fe-CTF. Abundant few-layer crystalline nanosheets (Fe-CTF NSs) could be prepared through simple ball-milling exfoliation of the bulk layered Fe-CTF and exhibited remarkable electrocatalytic performance for oxygen reduction reaction (ORR) with a half-wave potential and onset potential up to 0.902 and 1.02 V respectively, and extraordinary Zn-air battery performance with an ultrahigh specific capacity and power density of 811 mAh g-1 and 230 mW cm-2 respectively. By combining operando X-ray absorption spectroscopy with density functional theory calculations, we revealed a dynamic and reversible evolution of Fe-N3 to Fe-N2 during the electrocatalytic process, which could further accelerate the electrocatalytic reaction.

Highly selective and low-overpotential electrocatalytic CO2 reduction to ethanol by Cu-single atoms decorated N-doped carbon dots

Selective, low-overpotential and high Faradaic efficiency electroreduction of CO2 to ethanol is in prominent global demand and lies in structuring, loading, and modulating the coordination states of Cu single atom catalysts (SACs) with support matrix. Here, the low-temperature (160 °C) synthesis of Cu–SACs–N-doped carbons dots (Cu–SACs–N–CQDs) is reported via Cu–dopamine complex process. The optimized Cu–SACs–N–CQDs electrocatalyst brings remarkably high Faraday efficiency (> 80%) and selectivity for ethanol with 50 h operation stability, which far exceeds previous results in terms of overpotential, stability, and Faraday efficiency. Surprisingly, the Faraday efficiency and selectivity of ethanol are highly sensitive to the coordination states of copper SACs with variation of Cu loadings. Operando X-ray absorption spectroscopy indicates in situ-generated neighboring metallic Cu–Cu atom coordination as real catalytic active sites from isolated single Cu atom during CO2 reduction, which favors the ethanol selectivity.

A novel electrochemical flow-cell for operando XAS investigations in X-ray opaque supports.

Improvement of electrochemical technologies is one of the most popular topics in the field of renewable energy. However, this process requires a deep understanding of the electrode-electrolyte interface behavior under operando conditions. X-ray absorption spectroscopy (XAS) is widely employed to characterize electrode materials, providing element-selective oxidation state and local structure. Several existing cells allow studies as close as possible to realistic operating conditions, but most of them rely on the deposition of the electrodes on conductive and X-ray transparent materials, from where the radiation impinges the sample. In this work, we present a new electrochemical flow-cell for operando XAS that can be used with X-ray opaque substrates, since the signal is effectively detected from the electrode surface, as the radiation passes through a thin layer of electrolyte (∼17 μm). The electrolyte can flow over the electrode, reducing bubble formation and avoiding strong reactant concentration gradients. We show that high-quality data can be obtained under operando conditions, thanks to the high efficiency of the cell from the hard X-ray regime down to ∼4 keV. We report as a case study the operando XAS investigation at the Fe and Ni K-edges on Ni-doped γ-Fe2O3 films, epitaxially grown on Pt substrates. The effect of the Ni content on the catalytic performances for the oxygen evolution reaction is discussed.

Operando insights into correlating CO coverage and Cu-Au alloying with the selectivity of Au NP-decorated Cu2O nanocubes during the electrocatalytic CO2 reduction.

Electrochemical reduction of CO2 (CO2RR) is an attractive technology to reintegrate the anthropogenic CO2 back into the carbon cycle driven by a suitable catalyst. This study employs highly efficient multi-carbon (C2+) producing Cu2O nanocubes (NCs) decorated with CO-selective Au nanoparticles (NPs) to investigate the correlation between a high CO surface concentration microenvironment and the catalytic performance. Structure, morphology and near-surface composition are studied via operando X-ray absorption spectroscopy and surface-enhanced Raman spectroscopy, operando high-energy X-ray diffraction as well as quasi in situ X-ray photoelectron spectroscopy. These operando studies show the continuous evolution of the local structure and chemical environment of our catalysts during reaction conditions. Along with its alloy formation, a CO-rich microenvironment as well as weakened average CO binding on the catalyst surface during CO2RR is detected. Linking these findings to the catalytic function, a complex compositional interplay between Au and Cu is revealed in which higher Au loadings primarily facilitate CO formation. Nonetheless, the strongest improvement in C2+ formation appears for the lowest Au loadings, suggesting a beneficial role of the Au-Cu atomic interaction for the catalytic function in CO2RR. This study highlights the importance of site engineering and operando investigations to unveil the electrocatalyst's adaptations to the reaction conditions, which is a prerequisite to understand its catalytic behavior.

Design principles of operando ultraviolet-visible and electron paramagnetic resonance spectroscopy setups for active site characterization in ion-exchanged zeolites

Cu- and Fe-exchanged zeolites have been widely investigated for their applicability in selective partial oxidation of CH4 and abatement of environmentally harmful nitrogen oxides. However, the differentiation between spectator and active sites is cumbersome due to their dynamic co-existence, which aggravates the elucidation of the redox dynamics of the latter. Therefore, correlated multi-spectroscopic approaches carried out under operando conditions are needed in order to disentangle the inherent reactivity of specific species. Here we describe the conceptualization of complementary operando spectroscopic methods for the investigation of ion-exchanged zeolites employed in redox reactions. The potential and versatility of this approach are demonstrated by means of two exemplary case studies. First, we present the insight generated by two custom operando ultraviolet-visible and electron paramagnetic resonance spectroscopy setups operating in batch mode into CH4-to-CH3OH conversion over Cu-exchanged mordenite. In addition to recording the method-dependent spectroscopic fingerprints of distinct Cu centers, the overall CH4 consumption is simultaneously monitored in both setups. The extracted apparent activation energies of the reactive centers obtained from the two systems are in good agreement with each other allowing to link the bulk reactivity to the intrinsic site-specific kinetics of all Cu centers. Second, the EPR setup is equipped with a flow reactor designed to carry out modulated excitation experiments with phase-sensitive detection in order to improve the signal-to-noise ratio and time resolution. The cell is employed to study the conversion of NO via selective catalytic reduction over Fe-exchanged ferrierite. In combination with operando X-ray absorption spectroscopy, a small portion of active Fe species consisting of monomers in gamma-positions and oligomeric structures located in the main channel is identified, which are kept in a redox active state under relevant reaction conditions and thus sustain the chemical transformation of NO.