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Anionic redox allows the direct formation of OâO bonds from lattice oxygens and provides higher catalytic in the oxygen evolution reaction (OER) than does the conventional metal ion mechanism. While previous theories have predicted and experiments have suggested the possible OâO bond, it has not yet been directly observed in the OER process. In this study, operando soft X-ray absorption spectroscopy (sXAS) at the O K-edge and the operando Raman spectra is performed on layered double CoFe hydroxides (LDHs) after intercalation with [Cr(C2O4)3]3-, and revealed a three-step oxidation process, staring from Co2+ to Co3+, further to Co4+ (3d6L), and ultimately leading to the formation of OâO bonds and O2 evolution above a threshold voltage (1.4 V). In contrast, a gradual oxidation of Fe is observed in CoFe LDHs. The OER activity exhibits a significant enhancement, with the overpotential decreasing from 300 to 248 mV at 10 mA cm-2, following the intercalation of [Cr(C2O4)3]3- into CoFe LDHs, underscoring a crucial role of anionic redox in facilitating water splitting.
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Structural modelling of operando pair distribution function (PDF) data of complex functional materials can be highly challenging. To aid the understanding of complex operando PDF data, this article demonstrates a toolbox for PDF analysis. The tools include denoising using principal component analysis together with the structureMining, similarityMapping and nmfMapping apps available through the online service 'PDF in the cloud' (PDFitc, https://pdfitc.org/). The toolbox is used for both ex situ and operando PDF data for 3â nm TiO2-bronze nanocrystals, which function as the active electrode material in a Li-ion battery. The tools enable structural modelling of the ex situ and operando PDF data, revealing two pristine TiO2 phases (bronze and anatase) and two lithiated Li x TiO2 phases (lithiated versions of bronze and anatase), and the phase evolution during galvanostatic cycling is characterized.
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Photoelectrochemical (PEC) hydrogen generation is a promising technology for green hydrogen production yet faces difficulties in achieving stability and efficiency. The scientific community is pushing toward the development of new electrode materials and a better understanding of the underlying reactions and degradation mechanisms. Advances in photocatalytic materials are being pursued through the development of heterojunctions, tailored crystal nanostructures, doping, and modification of solid-solid and solid-electrolyte interfaces. Operando and in situ techniques are utilized to deconvolute the charge transfer mechanisms and degradation pathways. In this review, both materials development and Operando characterization are covered for advancing PEC technologies. The recent advances made in the PEC materials are first reviewed including the applied improvement strategies for transition metal oxides, nitrites, chalcogenides, Si, and group III-V semiconductor materials. The efficiency, stability, scalability, and electrical conductivity of the aforementioned materials along with the improvement strategies are compared. Next, the Operando characterization methods and cite selected studies applied for PEC electrodes are described. Operando studies are very successful in elucidating the reaction mechanisms, degradation pathways, and charge transfer phenomena in PEC electrodes. Finally, the standing challenges and the potential opportunities are discussed by providing recommendations for designing more efficient and electrochemically stable PEC electrodes.
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Solar-driven photo-thermal dry reforming of methane (DRM) is an environmentally friendly production route for high-value-added chemicals. However, the lack of thorough understanding of the mechanism for photo-thermal reaction has limited its further development. Here, we systematically investigated the mechanism of photo-thermal DRM reaction with the representative of Ru/CeO2 catalyst. Through in situ DRIFTs and transient experiments, comprehensive investigation into the reaction steps and their reactive sites in the process of DRM reaction were conducted. Besides, the excitation and migration direction of photo-electron was determined by ISI-XPS experiments, and the change of surface defect structure induced by light was characterized by ISI-EPR experiments. Based on the above results, the photo-enhancement effect on each micro-reaction step was determined. This study provides a theoretical basis for the industrialization of photo-thermal DRM reaction and its development of catalysts.
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Electrical triggering of a metal-insulator transition (MIT) often results in the formation of characteristic spatial patterns such as a metallic filament percolating through an insulating matrix or an insulating barrier splitting a conducting matrix. When MIT triggering is driven by electrothermal effects, the temperature of the filament or barrier can be substantially higher than the rest of the material. Using X-ray microdiffraction and dark-field X-ray microscopy, we show that electrothermal MIT triggering leads to the development of an inhomogeneous strain profile across the switching device, even when the material does not undergo a pronounced, discontinuous structural transition coinciding with the MIT. Diffraction measurements further reveal evidence of unique features associated with MIT triggering including lattice distortions, tilting, and twinning, which indicate structural nonuniformity of both low- and high-resistance regions inside the switching device. Such lattice deformations do not occur under equilibrium, zero-voltage conditions, highlighting the qualitative difference between states achieved through increasing temperature and applying voltage in nonlinear electrothermal materials. Electrically induced strain, lattice distortions, and twinning could have important contributions in the MIT triggering process and drive the material into nonequilibrium states, providing an unconventional pathway to explore the phase space in strongly correlated electronic systems.
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Photocatalytic conversion of CO2 with H2O is an attractive application that has the potential to mitigate environmental and energy challenges through the conversion of CO2 to hydrocarbon products such as methane. However, the underlying reaction mechanisms remain poorly understood, limiting real progress in this field. In this work, a mechanistic investigation of the CO2 photocatalytic reduction on Pt/TiO2 is carried out using an operando FTIR approach, combined with chemometric data processing and isotope exchange of (12CO2 + H2O) toward (13CO2 + H2O). Multivariate curve resolution analysis applied to operando spectra across numerous cycles of photoactivation and the CO2 reaction facilitates the identification of principal chemical species involved in the reaction pathways. Moreover, specific probe-molecule-assisted reactions, including CO and CH3COOH, elucidate the capacity of selected molecules to undergo methane production under irradiation conditions. Finally, isotopic exchange reveals conclusive evidence regarding the nature of the identified species during CO2 conversion and points to the significant role of acetates resulting from the C-C coupling reaction as key intermediates in methane production from the CO2 photocatalytic reduction reaction.
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The widespread application of Li4Ti5O12 (LTO) anode in lithium-ion batteries has been hindered by its relatively low energy density. In this study, we investigated the capacity enhancement mechanism of LTO anode through the incorporation of Na+ cations in an Li+-based electrolyte (dual-cation electrolyte). LTO thin film electrodes were prepared as conductive additive-free and binder-free model electrodes. Electrochemical performance assessments revealed that the dual-cation electrolyte boosts the reversible capacity of the LTO thin film electrode, attributable to the additional pseudocapacitance and intercalation of Na+ into the LTO lattice. Operando Raman spectroscopy validated the insertion of Li+/Na+ cations into the LTO thin film electrode, and the cation migration kinetics were confirmed by ab initio molecular dynamic (AIMD) simulation and electrochemical impedance spectroscopy, which revealed that the incorporation of Na+ reduces the activation energy of cation diffusion within the LTO lattice and improves the rate performance of LTO thin film electrodes in the dual-cation electrolyte. Furthermore, the interfacial charge transfer resistance in the dual-cation electrolyte, associated with ion de-solvation processes and traversal of the cations in the solid-electrolyte interphase (SEI) layer, are evaluated using the distribution of relaxation time, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Our approach of performance enhancement using dual-cation electrolytes can be extrapolated to other battery electrodes with sodium/lithium storage capabilities, presenting a novel avenue for the performance enhancement of lithium/sodium-ion batteries.
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Nickel/yttria-stabilized zirconia (YSZ) composites are the most commonly used fuel electrodes for solid oxide cells. While microstructural changes of Ni/YSZ during operational conditions have been thoroughly investigated, there is limited knowledge regarding Ni/YSZ surface chemistry under working conditions. In this study, we examine the interaction between Ni/YSZ electrodes and water vapor under open circuit and polarization conditions, utilizing near ambient pressure soft and hard X-ray photoelectron spectroscopies. Miniature cells with conventional porous Ni/YSZ composite cermet cathodes were modified to facilitate the direct spectroscopic observation of the functional electrode's areas close to the interface with the YSZ electrolyte. The results highlight dynamic changes in the oxidation state and composition of Ni/YSZ under H2 and H2O atmospheres. We also quantify the accumulation of impurities on the electrode surface. Through adjustments in the pretreatment of the cell, the correlation between the nickel surface oxidation state and the cell's electrochemical performance during H2O electroreduction is established. It is unequivocally shown that nickel surface oxidation in H2O electrolysis favors NiO over Ni(OH)x, providing critical insights into the mechanism of Ni-phase redistribution within the electrode during long-term operation. Depth-dependent photoemission measurements, combined with theoretical quantitative simulations, reveal that NiO and Ni phases are uniformly mixed on the surface during H2O electrolysis. This differs from the conventional expectation of a NiO-shell/Ni-core configuration in gas phase oxidation. These findings provide crucial insights into the surface chemistry of Ni/YSZ electrodes under conditions relevant to H2O electrolysis, elucidating their impact on the electrochemical performance of the cell.
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Ambient pressure X-ray photoelectron spectroscopy (APXPS) is combined with simultaneous electrical measurements and supported by density functional theory calculations to investigate the sensing mechanism of tungsten disulfide (WS2)-based gas sensors in an operando dynamic experiment. This approach allows for the direct correlation between changes in the surface potential and the resistivity of the WS2 sensing active layer under realistic operating conditions. Focusing on the toxic gases NO2 and NH3, we concurrently demonstrate the distinct chemical interactions between oxidizing or reducing agents and the WS2 active layer and their effect on the sensor response. The experimental setup mimics standard electrical measurements on chemiresistors, exposing the sample to dry air and introducing the target gas analyte at different concentrations. This methodology applied to NH3 concentrations of 100, 230, and 760 and 14 ppm of NO2 establishes a benchmark for future APXPS studies on sensing devices, providing fast acquisition times and a 1:1 correlation between electrical response and spectroscopy data in operando conditions. Our findings contribute to a deeper understanding of the sensing mechanism in 2D transition metal dichalcogenides, paving the way for optimizing chemiresistor sensors for various industrial applications and wireless platforms with low energy consumption.
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In situ and operando investigation of photocatalysts plays a fundamental role in understanding the processes of active phase formation and the mechanisms of catalytic reactions, which is crucial for the rational design of more efficient materials. Using a custom-made operando photocatalytic cell, an in situ procedure to follow the formation steps of Pd/TiO2 photocatalyst by synchrotron-based X-ray absorption spectroscopy (XAS) is proposed. The procedure resulted in the formation of â¼1â nm Pd particles with a much narrower size distribution and homogeneous spreading over TiO2 support compared with the samples generated in a conventional batch reactor. The combination of in situ XAS spectroscopy with high-angle annular dark-field scanning transmission electron microscopy demonstrated the formation of single-atom Pd(0) sites on TiO2 as the initial step of the photodeposition process. Palladium hydride particles were observed for all investigated samples upon exposure to formic acid solutions.
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There is a growing demand for research and development of advanced energy storage devices with high energy density utilizing earth-abundant metal anodes such as sodium metal. Tellurium, a member of the chalcogen group, stands out as a promising cathode material due to its remarkable volumetric capacity, comparable to sulfur, and significantly high electrical conductivity. However, critical issues arise from soluble sodium polytellurides, leading to the shuttle effect. This phenomenon can result in the loss of active materials, self-discharge, and anode instability. Here, we introduce polypyrrole-coated tellurium nanotubes as the cathode materials, where polypyrrole plays a crucial role in preventing the dissolution of polytellurides, as confirmed through operando optical microscopy. The polypyrrole-coated tellurium nanotubes exhibited an outstanding rate performance and long cycle stability in sodium-tellurium batteries. These research findings are anticipated to bolster the viability of polypyrrole-coated tellurium nanotubes as promising cathode materials, making a substantial contribution to the commercialization of sodium-ion battery technology.
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Scanning microscopy methods are crucial for the advancement of nanoelectronics. However, the vertical nanoprobes in such techniques suffer limitations such as the fragility at the tip-sample interface, complex instrumentation, and the lack of in operando functionality in several cases. Here, we introduce scanning plasmon-enhanced microscopy (SPEM) and demonstrate its capabilities on MoS2 and WSe2 nanosheets. SPEM combines a nanoparticle-on-mirror (NPoM) configuration with a portable conductive cantilever, enabling simultaneous optical and electrical characterization. This distinguishes it from other current techniques that cannot provide both characterizations simultaneously. It offers a competitive optical resolution of 600 nm with local enhancement of optical signal up to 20,000 times. A single gold nanoparticle with a 15 nm radius forms pristine, nondamaging van der Waals contact, which allows observation of unexpected p-type behavior of MoS2 at the nanoscale. SPEM reconstructs the NPoM method by eliminating the need for extensive statistical analysis and offering excellent nanoscale mapping resolution of any selected region. It surpasses other scanning techniques in combining precise optical and electrical characterization, interactive simplicity, tip durability, and reproducibility, positioning it as the optimal tool for advancing nanoelectronics.
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Understanding the strain dynamic behavior of catalysts is crucial for the development of cost-effective, efficient, stable, and long-lasting catalysts. Using time-resolved Bragg coherent diffraction imaging at the fourth generation Extremely Brilliant Source of the European Synchrotron (ESRF-EBS), we achieved subsecond time resolution during operando chemical reactions. Upon investigation of Pt nanoparticles during CO oxidation, the three-dimensional strain profile highlights significant changes in the surface and subsurface regions, where localized strain is probed along the [111] direction. Notably, a rapid increase in tensile strain was observed at the top and bottom Pt {111} facets during CO adsorption. Moreover, we detected oscillatory strain changes (6.4 s period) linked to CO adsorption during oxidation, where a time resolution of 0.25 s was achieved. This approach allows for the study of adsorption dynamics of catalytic nanomaterials at the single-particle level under operando conditions, which provides insight into nanoscale catalytic mechanisms.
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A mechanism for carbon deposition and its impact on the reaction kinetics of Methane Dry Reforming (MDR) using Rhodium-based catalysts is presented. By integrating Raman spectroscopy with kinetic analysis in an operando-annular chemical reactor under strict chemical conditions, we discovered that carbon deposition on a Rh/α-Al2O3 catalyst follows a nucleation-growth mechanism. The dynamics of carbon aggregates at the surface is found to be ruled by the CO2/CH4 ratio and the inlet CH4 concentration. The findings elucidate the spatiotemporal development of carbon aggregates on the catalyst surface and their effects on catalytic performance. Furthermore, the proposed mechanism for carbon formation shows that the influence of CO2 on MDR kinetics is an indirect result of carbon accumulation over time frames exceeding the turnover frequency, thus reconciling conflicting reports in the literature regarding CO2's kinetic role in MDR.
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The CH4 oxidation performance of Cu-chabazite zeolites characterized by distinct Si/Al ratios and Cu loadings has been studied and the observed variations in reactivity have been correlated to the differences in the nature of the formed active centers. Plug flow reactor tests, in situ Fourier-transform infrared, and X-ray absorption spectroscopy demonstrate that a decrease in Cu loading shifts the reactivity/redox profile to higher temperatures and increases the CH3OH selectivity and Cu-efficiency. In situ electron paramagnetic resonance, Raman, ultraviolet-visible, Fourier-transform infrared, and photoluminescence spectroscopies reveal that this behavior is associated with the presence of monomeric Cu active sites, including bare Cu2+ and [CuOH]+ present at low Si/Al ratio and Cu loading. Formation of two distinct [Cu2(µ-O)]2+ moieties at higher Si/Al ratio or Cu loading forces these trends into the opposite direction. Operando electron paramagnetic resonance and ultraviolet-visible spectroscopy show that the apparent activation energy of monomeric Cu active species decreases with increasing Si/Al ratio, whereas the one of dimeric centers is unaffected.
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Photocatalytic CO2 reduction to CO under unassisted (unbiased) conditions was recently demonstrated using heterostructure catalysts that combine p-type GaN with plasmonic Au nanoparticles and Cu nanoparticles as cocatalysts (p-GaN/Al2O3/Au/Cu). Here, we investigate the mechanistic role of Cu in p-GaN/Al2O3/Au/Cu under unassisted photocatalytic operating conditions using Cu K-edge X-ray absorption spectroscopy and first-principles calculations. Upon exposure to gas-phase CO2 and H2O vapor reaction conditions, the composition of the Cu nanoparticles is identified as a mixture of CuI and CuII oxide, hydroxide, and carbonate compounds without metallic Cu. These composition changes, indicating oxidative conditions, are rationalized by bulk Pourbaix thermodynamics. Under photocatalytic operating conditions with visible light excitation of the plasmonic Au nanoparticles, further oxidation of CuI to CuII is observed, indicating light-driven hole transfer from Au-to-Cu. This observation is supported by the calculated band alignments of the oxidized Cu compositions with plasmonic Au particles, where light-driven hole transfer from Au-to-Cu is found to be thermodynamically favored. These findings demonstrate that under unassisted (unbiased) gas-phase reaction conditions, Cu is found in carbonate-rich oxidized compositions rather than metallic Cu. These species then act as the active cocatalyst and play an oxidative rather than a reductive role in catalysis when coupled with plasmonic Au particles for light absorption, possibly opening an additional channel for water oxidation in this system.
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Rigorous comparisons between single site- and nanoparticle (NP)-dispersed catalysts featuring the same composition, in terms of activity, selectivity, and reaction mechanism, are limited. This limitation is partly due to the tendency of single metal atoms to sinter into aggregated NPs at high loadings and elevated temperatures, driven by a decrease in metal surface free energy. Here, we have developed a unique two-step method for the synthesis of single Cu sites on ZSM-5 (termed CuS/ZSM-5) with high thermal stability. The atomic-level dispersion of single Cu sites was confirmed through scanning transmission electron microscopy, X-ray absorption fine structure (XAFS), and electron paramagnetic resonance spectroscopy. The CuS/ZSM-5 catalyst was compared to a CuO NP-based catalyst (termed CuN/ZSM-5) in the oxidation of NH3 to N2, with the former exhibiting superior activity and selectivity. Furthermore, operando XAFS and diffuse reflectance infrared Fourier transform spectroscopy studies were conducted to simultaneously assess the fate of the Cu and the surface adsorbates, providing a comprehensive understanding of the mechanism of the two catalysts. The study shows that the facile redox behavior exhibited by single Cu sites correlates with the enhanced activity observed for the CuS/ZSM-5 catalyst.
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Supported nonprecious metal catalysts such as copper (Cu) are promising replacements for Pt-based catalysts for a wide range of energy-related electrochemical reactions. Direct electrochemical deposition is one of the most straightforward and versatile methods to synthesize supported nonprecious metal catalysts. However, further advancement in the design of supported nonprecious metal catalysts requires a detailed mechanistic understanding of the interplay between kinetics and thermodynamics of the deposition phenomena under realistic reaction conditions. Here, we study the electrodeposition of Cu on carbon nanotubes and graphene derivatives under electrochemical conditions using in situ liquid cell transmission electron microscopy (TEM). By combining real-time imaging, electrochemical measurements, X-ray photoelectron spectroscopy (XPS), and finite-element analysis (FEA), we show that low-dimensional support materials, especially carbon nanotubes, are excellent for generating uniform and finely dispersed platinum group metal-(PGM)-free catalysts under mild electrochemical conditions. The electrodeposited Cu on graphene and carbon nanotubes is also observed to show good electrochemical activity toward nitrate reduction reactions (NO3RRs), further supported by density functional theory (DFT) calculations. Nitrogen doping plays an important role in guiding nonprecious metal deposition, but its low electrical conductivity may give rise to lower NO3RR activity compared to its nondoped analogue. The development of supported nonprecious metals through interfacial and surface engineering for the design of supported catalysts will substantially reduce the demand for precious metals and generate robust catalysts with better durability, thereby presenting opportunities for solving the critical problems in energy storage and electrocatalysis.
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The technology of CO2 electrochemical reduction (CO2ER) provides a means to convert CO2, a waste greenhouse gas, into value-added chemicals. Copper is the most studied element that is capable of catalyzing CO2ER to obtain multicarbon products, such as ethylene, ethanol, acetate, etc., at an appreciable rate. Under the operating condition of CO2ER, the catalytic performance of Cu decays because of several factors that alters the surface properties of Cu. In this review, these factors that cause the degradation of Cu-based CO2ER catalysts are categorized into generalized deactivation modes, that are applicable to all electrocatalytic systems. The fundamental principles of each deactivation mode and the associated effects of each on Cu-based catalysts are discussed in detail. Structure- and composition-activity relationship developed from recent in situ/operando characterization studies are presented as evidence of related deactivation modes in operation. With the aim to address these deactivation modes, catalyst design and reaction environment engineering rationales are suggested. Finally, perspectives and remarks built upon the recent advances in CO2ER are provided in attempts to improve the durability of CO2ER catalysts.
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Urea electrosynthesis from co-electrolysis of NO3 - and CO2 (UENC) offers a promising technology for achieving sustainable and efficient urea production. Herein, a diatomic alloy catalyst (CuPd1Rh1-DAA), with mutually isolated Pd and Rh atoms alloyed on Cu substrate, is theoretically designed and experimentally confirmed to be a highly active and selective UENC catalyst. Combining theoretical computations and operando spectroscopic characterizations reveals the synergistic effect of Pd1-Cu and Rh1-Cu active sites to promote the UENC via a tandem catalysis mechanism, where Pd1-Cu site triggers the early C-N coupling and promotes *CO2NO2-to-*CO2NH steps, while Rh1-Cu site facilitates the subsequent protonation step of *CO2NH2 to *COOHNH2 toward the urea formation. Impressively, CuPd1Rh1-DAA assembled in a flow cell presents the highest urea Faradaic efficiency of 72.1% and urea yield rate of 53.2 mmol h-1 gcat -1 at -0.5 V versus RHE, representing nearly the highest performance among all reported UENC catalysts.