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Operando spectroscopy

Operando spectroscopy is a specialized methodology in catalysis and materials science that integrates in situ spectroscopic characterization of materials—such as catalysts—with simultaneous, real-time measurements of their performance, including activity and selectivity, under actual operating reaction conditions like those in a functional reactor.^[1]^[2] This approach distinguishes itself from traditional in situ spectroscopy, which examines materials under controlled but non-operational environments (e.g., in a simple spectroscopic cell without concurrent product analysis), by providing a more accurate depiction of dynamic structural changes and structure-activity relationships during real-world processes.^[1]^[3] The term "operando" was coined around the early 2000s, with its formal introduction attributed to Miguel A. Bañares, marking a paradigm shift in understanding catalyst behavior beyond static or simulated conditions.^[1] Since then, the field has grown exponentially, with approximately 20% of recent heterogeneous catalysis publications incorporating operando methods to probe catalyst evolution, deactivation, and optimization.^[1] Key principles emphasize the use of specialized reaction cells or reactors that mimic industrial setups, enabling the correlation of spectroscopic data (e.g., surface species identification) with quantifiable outputs like gas chromatography-monitored product yields.^[2]^[3] Common techniques in operando spectroscopy span a range of modalities, including X-ray absorption spectroscopy (XAS) for electronic structure, X-ray diffraction (XRD) for crystallinity, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) for surface adsorbates, Raman spectroscopy for vibrational modes, and advanced methods like quick-extended X-ray absorption fine structure (QEXAFS) or Mössbauer emission spectroscopy (MES).^[1]^[3] These are often combined with online analytics, such as mass spectrometry or gas chromatography, to capture transient phenomena at temperatures, pressures, and compositions relevant to applications (e.g., up to 1000 °C and 40 bar).^[2]^[3] Applications of operando spectroscopy are pivotal in fields like thermal catalysis, electrocatalysis, photocatalysis, and energy storage, revealing mechanisms in processes such as CO oxidation on Pt/CeO₂ for emission control, isobutene oxidation to methacrolein using Bi-Mo-Co-Fe-O catalysts in the chemical industry, CO₂ hydrogenation to methanol on Cu/ZnO/Zr systems for power-to-X technologies, and non-oxidative methane conversion on Pt/CeO₂ at high temperatures.^[1]^[3] By elucidating how catalysts adapt or degrade under operational stress, this technique supports the design of more efficient, sustainable materials, bridging fundamental research with industrial scalability.^[1]^[3]

Introduction

Definition and Terminology

Operando spectroscopy is an analytical methodology that integrates the spectroscopic characterization of materials, particularly catalysts, under realistic reaction conditions with concurrent online analysis of reaction products, allowing researchers to establish direct correlations between material structure, catalytic activity, and selectivity.^[4]^[5] This approach ensures that observations reflect the dynamic behavior of the material during operation, rather than static or simulated states.^[4] The term "operando," derived from the Latin word meaning "while working," was coined to emphasize the study of catalysts in their active, functioning state, distinguishing it from earlier techniques.^[4] In contrast, "in situ" spectroscopy refers to measurements conducted on-site or under reaction-like conditions, but without the obligatory simultaneous assessment of catalytic performance or product analysis.^[6] "Ex situ" analysis, meanwhile, involves examining materials outside the reaction environment, often after quenching or removal, which can lead to artifacts due to the absence of operational dynamics.^[4] These distinctions highlight operando's focus on integrating structural insights with functional validation in real time.^[5] At its core, operando spectroscopy facilitates the identification of active sites by revealing their configuration and evolution under working conditions, which is challenging with non-operational methods.^[4] It also enables the detection of transient species—short-lived intermediates that play key roles in reaction mechanisms—providing snapshots of dynamic processes otherwise inaccessible.^[4] Ultimately, this methodology uncovers structure-performance relationships, linking atomic-level changes to macroscopic catalytic outcomes, thereby advancing the rational design of materials.^[5]

Principles and Importance

Operando spectroscopy encompasses the real-time interrogation of catalysts to capture dynamic alterations in their structure, electronic properties, and surface chemistry during active operation, under conditions mimicking industrial relevance such as elevated temperatures, pressures, and continuous reactant flow. This methodology integrates spectroscopic techniques directly within a reactor environment, allowing for the observation of evolving material states without interruption. Central to its principles is the concurrent execution of spectral acquisition and product analysis—typically via mass spectrometry or gas chromatography—to validate the catalyst's performance and preclude interpretive artifacts that arise from post-reaction handling or environmental decoupling. By maintaining these operational parameters, operando approaches yield representations of the catalyst as it truly functions, bridging the gap between idealized models and practical reactivity. The importance of operando spectroscopy lies in its capacity to delineate structure-activity relationships (SAR) in heterogeneous catalysis, where correlations between atomic-scale features and macroscopic performance drive rational catalyst design. Unlike ex-situ methods, which often capture static, deactivated states, operando techniques expose fleeting active sites and reaction pathways, including transient intermediates such as adsorbed species or evolving oxide layers that dictate selectivity and efficiency. This has proven pivotal in fields like energy conversion and chemical manufacturing, enabling the refinement of processes—for instance, in methanol synthesis or CO₂ reduction—by tying spectral signatures to key metrics like turnover frequency (TOF), thereby accelerating the development of sustainable technologies. Key advantages include the provision of high-fidelity data for mechanistic elucidation, fostering quantitative insights that inform predictive modeling. For example, selectivity S in competing reaction pathways may be quantified as

S = \frac{k_{\text{active}}}{k_{\text{active}} + k_{\text{inactive}}},

where rate constants k are extracted from time-resolved operando spectra, such as those obtained via steady-state isotopic transient kinetic analysis (SSITKA) coupled with infrared spectroscopy. Such correlations not only validate proposed mechanisms but also guide optimization strategies, reducing reliance on trial-and-error experimentation in industrial applications.

Historical Development

Early In Situ Approaches

In situ spectroscopy in catalysis research originated in the mid-20th century, with pioneering applications of infrared (IR) spectroscopy to probe gas-solid interactions on catalyst surfaces. The first demonstrations involved transmission IR measurements of chemisorbed species, such as carbon monoxide on nickel oxide, enabling the identification of surface-bound intermediates under controlled atmospheres. These early efforts, led by researchers like Robert P. Eischens, focused on static adsorption studies at low pressures and temperatures, marking the shift from ex situ to environmentally relevant characterizations.^[7] By the 1960s, Eischens and collaborators expanded these techniques to a broader range of adsorbed species on metal oxides and supported metals, using IR to distinguish chemisorbed from physisorbed states and to infer active site geometries. The term "in situ" began appearing in catalysis literature during this decade, reflecting experiments conducted without exposing samples to ambient conditions.^[8] In the 1970s, complementary advancements emerged in ultraviolet-visible (UV-Vis) spectroscopy, particularly diffuse reflectance modes adapted for opaque powdered catalysts. This allowed investigations of electronic transitions in transition metal sites under simulated reaction environments, such as reduction-oxidation cycles, providing insights into coordination and oxidation states inaccessible by transmission methods. The popularization of in situ spectroscopy accelerated in the 1980s, driven by improvements in vacuum technology for high-pressure cells and sensitive detectors, including the widespread adoption of Fourier transform IR (FTIR) instruments.^[9] These enhancements enabled higher temporal resolution and signal-to-noise ratios, facilitating studies of dynamic surface processes like desorption and site activation.^[7] However, early in situ approaches were limited by the absence of simultaneous product analysis, often resulting in ambiguous correlations between spectral features and catalytic performance, as changes could arise from inactive species or non-representative conditions.^[8]

Emergence of Operando Methodology

The concept of operando spectroscopy emerged in the early 2000s as an evolution of in situ techniques, emphasizing the need to characterize catalysts under true working conditions while simultaneously monitoring reaction products to correlate structure with activity. The term "operando," derived from Latin meaning "working," was coined in the early 2000s by researchers Bert M. Weckhuysen, Eric M. Gaigneaux, Gerhard Mestl, and Miguel A. Bañares to highlight this integrated approach, distinguishing it from prior methods that often lacked concurrent product analysis.^[10]^[5] This shift was formalized in a seminal 2005 publication in Catalysis Today, which outlined operando methodology as the combination of spectroscopic characterization during reaction with simultaneous activity measurements, establishing a new paradigm for catalyst studies.^[5] Key milestones between 2005 and 2010 solidified operando spectroscopy through influential publications that demonstrated its application across diverse catalytic systems, particularly in heterogeneous catalysis. For instance, the first International Congress on Operando Spectroscopy, held in Lunteren, Netherlands, in 2003, marked an early gathering that propelled the field, leading to a surge in peer-reviewed works that integrated techniques like Raman and infrared spectroscopy with online gas analysis.^[4] These efforts, often published in high-impact journals such as Catalysis Today and Journal of Catalysis, emphasized the methodology's ability to identify active sites and reaction intermediates under realistic conditions, fostering widespread adoption. By the late 2000s, operando approaches had transitioned from conceptual frameworks to standard protocols in catalysis research. Pivotal events in the mid-2000s included operando Raman studies on working catalysts, such as the 2006 investigation of methanol oxidation over Mo/Al₂O₃ using combined EPR, Raman, and infrared spectroscopies coupled with product detection, which revealed dynamic surface species changes during selective oxidation.^[11] The 2010s saw further expansion through advanced synchrotron facilities enabling time-resolved X-ray absorption spectroscopy (XAS), allowing millisecond-scale observations of structural dynamics in catalysts under operando conditions, such as phase transformations in oxidation reactions.^[12] Concurrently, applications grew in electrocatalysis by the mid-2010s, with operando techniques applied to electrode materials to probe interfacial processes in fuel cells and electrolyzers, enhancing mechanistic insights into oxygen evolution and reduction.^[13]

Experimental Setup

Operando Cell and Reactor Design

Operando cells and reactors are engineered to replicate realistic reaction environments while enabling simultaneous spectroscopic probing of materials under working conditions. Key design principles emphasize maintaining structural integrity, precise control over reaction parameters, and unobstructed access for spectroscopic beams. Cells must support gas flow rates typically ranging from 10 to 200 cm³/min, temperature control from ambient to 1000°C or higher, and pressures up to 10 bar or more, often achieved through integrated heating elements like furnaces or fluid circulation systems. Spectroscopic access is facilitated by transparent windows, such as quartz for UV-visible and Raman spectroscopy (transmitting >90% in the 200-2500 nm range), CaF₂ or ZnSe for infrared, and beryllium or Kapton for X-ray techniques, positioned to minimize beam attenuation while preserving hermetic seals. These designs ensure that the reactor functions as a true chemical reactor, allowing online analysis of products via coupled gas chromatography if needed for performance validation.^[14]^[15]^[16] Various reactor types are tailored to specific applications in operando studies. For heterogeneous catalysis, plug-flow reactors (PFRs), often fixed-bed configurations, are widely used to simulate continuous industrial processes, with catalyst beds packed into quartz capillaries or tubes for uniform reactant distribution and product evacuation. Electrochemical cells, essential for battery and electrocatalysis research, commonly employ three-electrode setups comprising a working electrode (e.g., catalyst-coated carbon paper), a reference electrode (e.g., Hg/HgO), and a counter electrode (e.g., Pt wire), configured in H-cell or flow-cell geometries to separate anodic and cathodic compartments via ion-exchange membranes and prevent cross-contamination. Microreactors, featuring channels as small as 100 µm, offer high spatial resolution and enhanced mass/heat transfer, ideal for high-throughput screening of catalytic materials under operando conditions.^[14]^[17]^[18] Material selection prioritizes corrosion resistance, thermal stability, and compatibility with reactive gases and liquids to withstand harsh operando environments. Stainless steel (e.g., X13 grade) forms the structural body of many reactors due to its durability under pressures up to 1000 bar and temperatures exceeding 600°C, while ceramics or glassy carbon tubes provide inert linings for oxidative or reductive atmospheres, offering high X-ray transmittance (up to 83% at key edges). Sealing mechanisms, such as Kalrez O-rings, Viton joints, or threaded connections with multiple gaskets, are critical to prevent leaks during gas flow or pressure cycling, often supplemented by hydrophobic coatings on membranes to manage electrolyte wicking. Polymers like polyether ether ketone (PEEK) and polytetrafluoroethylene (PTFE) are favored for electrochemical cells, enabling operation across pH 0-14 without degradation.^[15]^[14]^[17]

Integration with Reaction Monitoring

Operando spectroscopy setups integrate spectroscopic measurements with real-time reaction monitoring to capture dynamic correlations between catalyst structure and performance under working conditions. Coupling methods typically involve online analytics such as gas chromatography (GC) or mass spectrometry (MS) for effluent analysis, enabling the identification of reaction products and byproducts alongside spectral data. For instance, in studies of CO oxidation on Pt/γ-Al₂O₃ catalysts, operando X-ray absorption spectroscopy (XAS) is combined with GC/MS to track oscillatory behavior and correlate spectral changes with product evolution. Software for time-synchronized data logging is essential, often using triggers or quasi-simultaneous acquisition protocols to align timestamps from spectrometers and analyzers, such as in multi-technique setups where EPR, UV-Vis, and ATR-IR data are recorded concurrently with GC outputs to correlate spectral peaks with conversion rates.^[19]^[14]^[19] Protocols for synchronization emphasize controlled reaction environments, particularly in flow systems equipped with mass flow controllers (MFCs) to regulate reactant feeds and maintain steady-state or transient conditions. These systems, such as capillary fixed-bed reactors with diameters of 1.5–6 mm, facilitate precise gas-solid interactions while allowing effluent diversion to GC/MS without interrupting spectroscopic probes. In electrochemical applications, integration via potentiostats enables potential-dependent spectra, where devices like the BioLogic SEC2020 synchronize voltage sweeps with spectroscopic acquisitions (e.g., UV-Vis or Raman) to monitor intermediates in redox processes, ensuring data reflect applied potentials in operando cells. Such setups, often using triggers for alignment, support thin-film or bulk configurations tailored to operational electrochemistry.^[19]^[20]^[21] Data handling in these integrated systems relies on multivariate analysis techniques, such as principal component analysis (PCA), to process high-dimensional spectroscopic datasets and link them to reaction kinetics. PCA decomposes time-resolved spectra to identify principal components representing key structural or compositional changes, as demonstrated in operando ATR-IR monitoring of aqueous phase reforming of lignin, where PC1 scores stabilized after 150 minutes, explaining 25.90% of variance and confirming reliable kinetic data free from artifacts. This approach enables derivation of rate dependencies, such as power-law forms r = k [\text{reactant}]^n, by correlating PCA-extracted features with synced conversion metrics from GC/MS, providing mechanistic insights into catalyst dynamics without assuming isolated variables.^[22]^[22]^[19]

Spectroscopic Techniques

Raman and Infrared Spectroscopy

Raman and infrared (IR) spectroscopy are pivotal vibrational techniques in operando studies, enabling the real-time characterization of catalyst surfaces and bulk phases under working conditions by probing molecular vibrations associated with adsorbates and active sites.^[23] These methods provide complementary insights into reaction mechanisms, as Raman is sensitive to polarizability changes while IR detects dipole moment variations, allowing for the identification of species that may be inactive in one but active in the other.^[7] In operando setups, both techniques are integrated with reactors that maintain realistic temperature, pressure, and flow conditions to correlate spectral features with catalytic performance.^[24] Operando Raman spectroscopy has advanced through confocal configurations that enable spatial mapping of active sites across catalyst particles or beds, resolving heterogeneities at micrometer scales during reactions.^[23] Adaptations include high-temperature cells with quartz windows for gas-solid interfaces, supporting studies up to 800°C and ambient pressures while minimizing fluorescence interference via time-gating or enhanced setups like surface-enhanced Raman scattering (SERS).^[25] It excels at detecting vibrational modes of adsorbates, such as C-H stretches around 2800–3000 cm⁻¹ in hydrocarbon reactions on metal oxides, revealing intermediate formation and site-specific binding without interference from gas-phase species.^[23] In contrast, operando IR spectroscopy employs diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) for powdered catalysts and transmission modes for thin films or pellets, capturing surface adsorbates under flowing reactants.^[7] For liquid-phase systems, attenuated total reflectance (ATR)-IR facilitates in situ probing of interfaces with minimal sample preparation, ideal for electrocatalytic or homogeneous processes.^[7] A key application is monitoring CO adsorption bands, which shift within 2000–2100 cm⁻¹ for metal carbonyls on transition metals like Pt or Cu, indicating coverage-dependent electronic effects and reaction-induced reconstructions during oxidation or hydrogenation.^[7] Multimodal operando setups combining Raman and IR, such as integrated reactor cells with fiber optics and IR beams, yield comprehensive data by leveraging Raman's strength in symmetric vibrations (e.g., M=O stretches) and IR's for asymmetric ones (e.g., M-O-M bends), as demonstrated in vanadium oxide catalysts where both techniques confirm active site speciation during propane oxidation.^[24] This synergy enhances mechanistic understanding, for instance, by cross-validating adsorbate assignments in CO₂ reduction on Cu, where Raman tracks symmetric C-O modes and IR asymmetric ones.^[26]

UV-Visible Spectroscopy

UV-Visible (UV-Vis) spectroscopy in operando conditions primarily employs diffuse reflectance UV-Vis (DRUV) to probe the electronic structure of solid catalysts during active reaction states. This technique captures light scattering and absorption from powdered or heterogeneous materials under flow conditions, enabling the monitoring of d-d transitions in transition metal ions and charge transfer bands between metal centers and ligands or supports.^[27] These spectral features reveal changes in the catalyst's electronic environment without interrupting the reaction, providing insights into active site evolution in real-time.^[28] A key advantage of operando DRUV is its sensitivity to oxidation state variations, such as the detection of Ti³⁺ species at approximately 500 nm during redox reactions on TiO₂-based catalysts, which indicates the formation of oxygen vacancies critical for CO₂ activation in processes like the reverse water-gas shift reaction.^[29] Additionally, time-resolved UV-Vis spectra allow for the determination of transient species lifetimes, tracking dynamic processes like surface intermediate buildup or catalyst deactivation on timescales from seconds to minutes, as demonstrated in studies of CO oxidation on Au/TiO₂ where spectral shifts correlate with transient inactivation effects.^[30] Adaptations for operando setups often incorporate fiber-optic probes integrated into reactors, such as plug-flow or spectroelectrochemical cells, to collect diffuse reflectance spectra directly from the catalyst bed under controlled gas flow and temperature.^[31] Quantitative analysis is achieved by applying the Kubelka-Munk function to convert reflectance data into pseudo-absorbance values proportional to concentration:

F(R) = \frac{(1 - R)^2}{2R}

where R is the reflectance, facilitating correlation between spectral intensity and species abundance during operation.^[32] This setup can be briefly coupled with gas chromatography for correlating electronic changes to product yields in catalytic flows.^[33]

X-ray Diffraction and Absorption

X-ray diffraction (XRD) under operando conditions enables the real-time monitoring of structural changes in catalytic materials during active reactions, particularly through in-situ powder XRD to track phase transformations and crystallite dynamics.^[34] This technique reveals how catalysts evolve, such as the formation or decomposition of phases under reaction flows, providing insights into deactivation mechanisms or active site restructuring.^[35] Synchrotron sources enhance temporal resolution to the millisecond scale, allowing observation of transient events like crystallite growth in metal oxide catalysts during oxidation processes.^[36] X-ray absorption spectroscopy (XAS), encompassing X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), offers complementary electronic and local structural information in operando setups.^[37] Advanced variants like quick-EXAFS (QEXAFS) enable time-resolved measurements of local structure changes on timescales of seconds or faster, crucial for capturing transient species in dynamic reactions such as CO oxidation.^[1] XANES detects shifts in absorption edge positions to infer oxidation states; for instance, the Cu K-edge at 8979 eV shifts to higher energies with increasing Cu oxidation state, as observed in copper-based electrocatalysts under working conditions.^[38] EXAFS quantifies coordination environments by analyzing the oscillatory fine structure beyond the edge, where the EXAFS signal χ(k) is modeled as:

\chi(k) = \sum N e^{-2R^2 \sigma^2} \frac{f(k)}{k R^2} \sin(2kR + \phi(k))

This equation relates the backscattering amplitude to coordination number N, interatomic distance R, disorder σ², scattering amplitude f(k), and phase shift φ(k), enabling determination of local geometry changes, such as bond length variations in active sites during catalysis.^[39] Operando XRD and XAS often employ specialized high-pressure cells to mimic ambient reaction conditions, such as gas flows or electrochemical potentials, while maintaining beamline compatibility.^[40] These setups excel at detecting amorphous phases or low-crystallinity structures that are overlooked by conventional laboratory XRD due to weaker scattering signals, thus uncovering hidden intermediates in catalytic transformations.^[41] Mössbauer emission spectroscopy (MES), another nuclear technique, complements XAS by providing hyperfine interaction data on iron-containing catalysts, revealing electronic and magnetic state changes under operando conditions, such as in Fischer-Tropsch synthesis.^[1]

Mass Spectrometry and Gas Chromatography

Mass spectrometry (MS) and gas chromatography (GC) are essential analytical techniques in operando spectroscopy for real-time monitoring and quantification of gaseous and volatile liquid products during catalytic reactions. These methods enable the identification and measurement of reaction outcomes under working conditions, providing insights into conversion, selectivity, and deactivation without interrupting the process. In operando setups, they are integrated into reactor systems to sample effluent streams continuously or intermittently, capturing transient species that inform mechanistic understanding. Gas chromatography excels in separating complex mixtures of reaction products, particularly in heterogeneous catalysis. Capillary columns, such as the GS-GasPro type with 30 m length and 0.32 mm inner diameter, are commonly employed to resolve hydrocarbons like alkenes produced in dehydrogenation reactions; for instance, in propane dehydrogenation over Ga-Pt catalysts, these columns separate propane from propene with high resolution at oven temperatures around 70°C.^[42] For quantification under continuous flow conditions, thermal conductivity detectors (TCD) are widely used due to their universal response to most gases, excluding the carrier gas like helium; in ethane oxidative dehydrogenation studies, TCD connected in series with molecular sieve columns achieves precise measurement of C1-C2 hydrocarbons and oxygenates at pressures of 200-950 mbar.^[43] This setup supports detection limits as low as 0.4 ppb, allowing turnover numbers below 10^{-5} s^{-1} to be quantified in low-conversion regimes typical of model catalyst studies.^[44] Mass spectrometry provides rapid, real-time identification of volatile species through ionization and mass-to-charge (m/z) analysis. Quadrupole MS is favored for its speed and sensitivity in operando environments, monitoring gases like CO, NO, and CO2 during reactions such as NO-CO conversion over Rh nanoparticles at 700°C.^[45] Coupling to high-pressure reactors is achieved via differential pumping systems, which maintain ultra-high vacuum in the MS chamber (typically 10^{-6} to 10^{-7} Torr) while handling reactor pressures up to 1 atm, using multi-stage turbomolecular pumps to bridge pressure differentials without sample loss.^[46] Species identification relies on characteristic fragmentation patterns; for example, the m/z 44 peak corresponds to CO2 in oxidation catalysis over Au/TiO2, where signals track product evolution during transient H2 promotion experiments.^[47] Integration of GC and MS enhances quantitative accuracy by combining separation with sensitive detection, often in hybrid GC-MS configurations. Quantitative yields are determined using calibration curves derived from known gas mixtures, referenced to internal standards like N2, to account for response factors of species such as C2H4, CO2, and H2. Conversion is calculated as X = \frac{\text{inlet} - \text{outlet}}{\text{inlet}} \times 100\%, applied spatially across catalyst beds in oxidative dehydrogenation to map activity profiles from 0-50% for ethane.^[43] These data are briefly synchronized with spectroscopic outputs to link product distributions to active site dynamics.^[48]

Electrochemical Impedance Spectroscopy

Electrochemical impedance spectroscopy (EIS) is a powerful technique in operando studies that applies a small alternating current (AC) perturbation, typically over a frequency range spanning millihertz to megahertz (often 5 mHz to 1 MHz, with key insights from 5-100 kHz for interfacial processes), to an electrochemical system to measure its impedance response.^[49] The impedance Z(\omega), where \omega is the angular frequency, is a complex quantity expressed as Z(\omega) = Z' + jZ'', with Z' and Z'' representing the real and imaginary parts, respectively, capturing resistive and capacitive/reactance behaviors.^[50] This non-destructive method probes charge transfer kinetics, ion diffusion, and double-layer capacitance at electrode-electrolyte interfaces without significantly perturbing the system.^[49] In operando applications, EIS monitors dynamic processes in working electrochemical devices such as lithium-ion batteries and proton exchange membrane fuel cells (PEMFCs), revealing interface evolution under real operating conditions like cycling or load variation.^[51] For instance, in lithium-ion batteries, time-resolved EIS spectra track the formation and growth of the solid electrolyte interphase (SEI) layer on anode surfaces during initial charging, where increasing charge transfer resistance R_{ct} indicates SEI buildup that passivates the electrode and influences long-term stability.^[52] Similarly, in fuel cells, operando EIS detects changes in triple-phase boundaries and catalyst layer hydration, with evolving impedance arcs signaling degradation or performance shifts at the cathode-electrolyte interface.^[53] These measurements are often integrated into specially designed operando cells that allow simultaneous electrical testing and environmental control.^[54] Data analysis in EIS relies on graphical representations and equivalent circuit modeling to interpret frequency-dependent behaviors and validate reaction mechanisms. Nyquist plots, plotting -Z'' versus Z', display characteristic semicircles for processes like charge transfer in a Randles circuit model, where the diameter corresponds to R_{ct} and the high-frequency intercept gives ohmic resistance R_s; deviations from ideal semicircles indicate non-ideal capacitance via constant phase elements.^[55] Bode plots complement this by showing the logarithm of impedance magnitude |Z| and phase angle versus log frequency, highlighting time constants for distinct processes such as diffusion (low-frequency tail) or interfacial polarization.^[49] In operando contexts, these analyses correlate electrical data with spectroscopic techniques, such as Raman or infrared, to confirm mechanisms; for example, rising R_{ct} in battery EIS aligns with SEI-related vibrational peaks in operando Raman spectra, providing mechanistic validation of interphase formation.^[56]

Applications

Heterogeneous Catalysis

Operando spectroscopy plays a pivotal role in heterogeneous catalysis by enabling the real-time observation of solid catalysts during gas-solid or liquid-solid reactions, such as those in industrial processes like ammonia synthesis and hydrocarbon conversion. This approach reveals the dynamic evolution of active sites and surface species under working conditions, bridging the gap between static structural characterization and catalytic performance. By combining spectroscopic techniques with reaction monitoring, researchers can correlate transient structural changes with activity and selectivity, facilitating the design of more efficient catalysts. In ammonia synthesis over iron-based catalysts, operando spectroscopy has provided key insights into the tracking of active Fe sites during the Haber-Bosch process. For instance, operando scanning electron microscopy on multi-promoted Fe catalysts demonstrates the structural evolution and nitridation of iron particles under reaction conditions, highlighting how promoters stabilize active phases for enhanced nitrogen activation. Similarly, operando X-ray absorption spectroscopy (XAS) on Fe-containing systems reveals the oxidation state changes and coordination environments of Fe sites, confirming their role in N2 dissociation at elevated temperatures and pressures. Deactivation mechanisms, such as sintering, are also elucidated through operando methods, which monitor particle agglomeration and loss of active surface area in real time. Operando XAS studies on supported metal catalysts show that sintering occurs via Ostwald ripening or particle migration under high-temperature reaction flows, leading to reduced dispersion and activity; this has been observed in cobalt-based systems where thermal stress promotes coalescence, informing strategies for improved thermal stability. These observations underscore how operando spectroscopy quantifies deactivation kinetics, aiding in the development of sintering-resistant formulations. A representative example is the application of operando Raman spectroscopy to zeolite catalysts in the methanol-to-olefins (MTO) process, where it tracks the formation of coke precursors and hydrocarbon pool species within the zeolite framework. In H-SAPO-34 zeolites, UV-Raman spectra under reaction conditions identify methylated benzene intermediates as key active species, correlating their evolution with olefin selectivity and catalyst deactivation due to pore blocking. This real-time mapping helps optimize zeolite topology for prolonged activity in converting methanol to valuable olefins. Operando infrared (IR) spectroscopy has similarly advanced understanding in Fischer-Tropsch synthesis, linking surface adsorbates to product selectivity. On Co/Al2O3 catalysts, operando IR reveals that high CO surface coverage suppresses chain growth, favoring methane over longer hydrocarbons (C5+), with linear on-top CO species dominating under low H2/CO ratios. In Pt-promoted Co systems, operando DRIFTS identifies metal-support interface sites for dissociative CO adsorption, enhancing oxygenate selectivity by modulating hydrogenation pathways. The impacts of these insights are evident in industrial applications, such as improved structure-activity relationships (SAR) for Pt catalysts in automotive exhaust treatment. Operando spectroscopy on Pt-based three-way catalysts demonstrates that metallic Pt nanoparticles (2-5 nm) are the primary active phase for CO and NOx oxidation under lean-burn conditions, while oxidized Pt species lead to deactivation; this SAR guides the engineering of high-dispersion Pt for better pollutant conversion efficiency. Overall, operando approaches have accelerated catalyst optimization, reducing reliance on empirical testing and enhancing sustainability in heterogeneous processes.

Homogeneous Catalysis

Operando spectroscopy in homogeneous catalysis enables the real-time observation of molecular catalysts in solution-phase reactions, providing insights into dynamic processes such as metal speciation and ligand exchanges that are often obscured in ex situ analyses. Unlike static characterizations, these techniques capture transient intermediates under actual turnover conditions, revealing the true active species and deactivation pathways in processes like hydroformylation and polymerization. This approach is particularly valuable for optimizing catalyst design in industrial applications, where understanding speciation helps mitigate inefficiencies from dormant forms. Infrared (IR) spectroscopy detects vibrational signatures of carbonyl ligands in rhodium-catalyzed hydroformylation, confirming active site occupancy and ligand influences on selectivity toward linear aldehydes. Operando high-pressure IR and NMR spectroscopy have elucidated the formation of hydrido and acyl rhodium species during CO and H₂ addition, tracking their role in regioselectivity.^[57] Operando nuclear magnetic resonance (NMR) spectroscopy provides atomic-level detail on catalyst states, particularly in polymerization reactions involving early transition metals. In olefin polymerization with metallocene or post-metallocene catalysts, high-pressure ¹H and ³¹P NMR distinguishes active alkylidene species from dormant ones, such as those involved in chain transfer or β-hydride elimination, under continuous monomer feed. This reveals how reaction conditions modulate catalyst lifetime and polymer microstructure, with spectra acquired in flow cells to mimic industrial slurry processes. Vibrational spectroscopies like IR further aid in ligand detection by identifying subtle bond stretches associated with coordination changes. To correlate spectroscopic observations with performance, operando setups frequently integrate online high-performance liquid chromatography (HPLC) for real-time product analysis. In hydroformylation, this coupling tracks aldehyde isomers alongside spectroscopic-monitored speciation, demonstrating how transient Rh species directly impact regioselectivity. Such multidimensional monitoring addresses key challenges in homogeneous catalysis, including the identification of dormant versus active forms under turnover, where low catalyst concentrations (often <1 mM) and fast exchange rates complicate signal attribution. By quantifying these dynamics, operando methods guide the development of more robust ligands and conditions, reducing waste in sustainable processes.^[57]

Electrocatalysis and Energy Storage

Operando spectroscopy plays a pivotal role in elucidating the dynamic processes in electrocatalysis and energy storage systems, where electrochemical potentials drive structural and chemical transformations at electrode interfaces. In electrocatalytic reactions, such as the oxygen evolution reaction (OER) essential for water splitting in fuel cells, operando X-ray absorption spectroscopy (XAS) has been instrumental in tracking the oxidation states of iridium oxide (IrO_x) catalysts. For instance, studies on monolayer IrO_x supported on RuO_x reveal that the Ir oxidation state saturates at high potentials, indicating full surface coverage by atomic oxygen just below the OER onset, which informs the role of surface oxygen in stabilizing active sites during catalysis.^[58] Similarly, for the hydrogen evolution reaction (HER) on platinum (Pt) surfaces, operando Raman spectroscopy detects vibrational signatures of adsorbed hydrogen intermediates. In Pt-based catalysts, these signatures reveal the strength of Pt-H adsorption, correlating with HER activity in alkaline media and highlighting the influence of surface modifications on reaction kinetics.^[59] In energy storage devices like lithium-ion batteries, operando techniques provide real-time insights into electrode evolution. For cathodes based on LiCoO_2 (LCO), operando X-ray diffraction (XRD) monitors phase transitions during charging, such as the shift from the hexagonal H1 phase of LCO to the H2 phase of delithiated Li_{1-x}CoO_2, and further to the H3 phase approaching CoO_2 at high voltages, which is critical for understanding capacity fade due to structural instability.^[60] On the anode side, operando electrochemical impedance spectroscopy (EIS) quantifies the growth of the solid electrolyte interphase (SEI) layer, revealing its evolution from a thin, passivating film to a thicker, resistive barrier over cycles, as observed in silicon anodes where impedance rises correlate with SEI thickening and lithium trapping.^[61] These operando studies uncover dynamic electrode restructuring under applied bias, such as IrO_x lattice expansion during OER or Pt surface amorphization in HER, which directly impact activity and durability.^[62] In the 2020s, synchrotron-based operando spectroscopy has advanced beyond Li-ion systems, enabling detailed mechanistic probes in emerging technologies; for Na-ion batteries, operando XAS on TiS_2 cathodes tracks Na intercalation-induced phase changes and sulfur redox, aiding design for cost-effective storage, while in Li-S batteries, operando X-ray imaging reveals polysulfide dissolution and shuttle effects in real time, guiding electrolyte optimizations for higher sulfur utilization.^[63]^[64]

Challenges and Future Directions

Current Limitations

One significant technical limitation in operando X-ray spectroscopy arises from beam damage, where prolonged exposure to high-flux synchrotron radiation can induce photoreduction of high-valent catalytic intermediates or evaporate electrolytes, altering the observed reaction dynamics.^[65]^[66] In dense reactor environments, signal attenuation further complicates measurements, as self-absorption distorts spectra in concentrated samples and air scattering reduces intensity in the tender X-ray regime (4–5 keV).^[65] Spatial resolution also poses challenges across techniques; for instance, Raman spectroscopy typically achieves lateral resolutions greater than 1 μm due to diffraction limits, hindering nanoscale analysis in heterogeneous catalysts.^[67] Practical hurdles include the high costs associated with synchrotron access and specialized in situ cells, which restrict widespread adoption and require significant investment in materials and beamtime allocation.^[66] Operando experiments often generate vast datasets—tens to hundreds of spectra per run—leading to data overload that demands advanced multivariate analytics like multivariate curve resolution-alternating least squares (MCR-ALS) for interpretation, yet standardized protocols remain lacking.^[66]^[16] Safety concerns are paramount in high-pressure (up to 10 MPa) and high-temperature (up to 600°C) setups, where reactor designs must incorporate robust sealing and shielding to prevent leaks or structural failures during real-time monitoring.^[68] Specific gaps persist in probing certain systems; liquid-phase operando studies for homogeneous catalysis face difficulties from scattering and absorption by solvents, complicating techniques like soft X-ray absorption spectroscopy that require ultrahigh vacuum compatibility.^[66]^[69] Additionally, detection of transient species with lifetimes shorter than 1 second remains incomplete, as most spectroscopic methods offer temporal resolutions on the order of seconds to minutes, missing ultrafast intermediates in dynamic reactions.^[16]^[70] Cell designs can contribute to opacity or minor leaks in such setups, further attenuating signals.^[16]

Emerging Trends

Recent advancements in operando spectroscopy have introduced operando transmission electron microscopy (TEM) as a powerful tool for capturing atomic-scale dynamics in catalytic processes under working conditions. This technique enables real-time visualization of structural changes, such as nanoparticle sintering or atomic rearrangements, at sub-nanometer resolution during reactions like CO oxidation or electrocatalysis.^[71] For instance, operando TEM has revealed the dynamic evolution of single metal atoms on supports, providing insights into active site formation and deactivation mechanisms that were previously inaccessible.^[72] Complementing this, multimodal platforms integrating multiple spectroscopic methods with AI-driven analysis are emerging, particularly for handling complex datasets from X-ray absorption spectroscopy (XAS). Machine learning models, such as random forests and deep neural networks, automate the interpretation of XAS spectra by predicting local coordination environments and oxidation states, reducing analysis time from hours to minutes while improving accuracy for operando studies.^[73]^[74] These AI-enhanced approaches address the growing data complexity in multimodal setups, where combining XAS with techniques like Raman or infrared spectroscopy yields richer, but more intricate, datasets.^[75] Key trends in the 2020s include the expanded application of operando spectroscopy to single-atom catalysts (SACs), where techniques like XAS and TEM track the stability and evolution of isolated active sites during operation. Reviews from this decade highlight how operando methods have elucidated clustering or leaching in SACs for reactions such as oxygen reduction, guiding the design of more durable materials.^[76]^[77] Additionally, portable operando setups are gaining traction for in-field studies, exemplified by laboratory-based XAS systems that mimic synchrotron capabilities without requiring large facilities, enabling on-site analysis of catalysts in industrial or environmental settings.^[78] Integration with computational modeling is another prominent trend, where operando data feeds into machine learning frameworks to develop predictive structure-activity relationships (SARs), forecasting catalyst performance under realistic conditions and accelerating optimization.^[79] Looking ahead, operando spectroscopy is poised for broader adoption in sustainable energy applications, particularly for CO₂ reduction, where time-resolved techniques will refine catalyst selectivity and efficiency in converting greenhouse gases to fuels.^[80] Emerging 4D (three-dimensional space plus time) imaging in TEM, such as 4D scanning transmission electron microscopy (4D-STEM), enables mapping of spatiotemporal dynamics at sub-nanometer spatial and millisecond temporal resolutions, offering insights into transient processes in energy conversion systems.^[81] These developments are expected to drive innovations in scalable, low-carbon technologies by 2030.^[82]

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