The numbers tell the story. Laboratory studies of water-splitting catalysts are typically conducted below 10 milliamperes per square centimeter, a gentle regime where materials behave politely. Commercial alkaline electrolyzers are benchmarked above 0.2 amperes per square centimeter, while proton exchange membrane (PEM) and anion exchange membrane (AEM) systems are expected to deliver roughly 1.6 and 1 ampere per square centimeter respectively. At those loads, steep potential gradients, vigorous gas bubbling, local pH swings and mechanical stress conspire to tear catalysts apart. Redox conversions, surface reconstructions, phase transformations, dopant leaching and outright decomposition can occur at or even before the onset of catalysis, sometimes creating entirely new phases that turn out to be the true active sites.

Conventional ex-situ tools such as X-ray diffraction, X-ray photoelectron spectroscopy, electron microscopy and infrared spectroscopy can catalog what a catalyst looked like before the storm and what remains afterward, but they cannot witness the transformation itself. Worse, samples removed from an operating cell and exposed to air can develop artifacts that mislead interpretation entirely. The review’s central thesis is that operando Raman spectroscopy, which collects vibrational spectra from a fully functioning device while simultaneously recording its electrochemical performance, offers the molecular-level window the field has been missing. The distinction between in-situ and operando matters here: in-situ means real-time measurement under catalytically relevant conditions, while operando means the measurement happens inside a genuinely working cell, directly tying a catalyst’s chemical state to its output.

Raman spectroscopy has a particular advantage in water electrolysis that infrared techniques lack: water, the electrolyte itself, has a very low Raman cross-section, so aqueous environments do not swamp the signal. The technique works by shining monochromatic laser light onto the sample; most photons scatter elastically at the same wavelength (Rayleigh scattering), but a small fraction exchange energy with molecular vibrations and emerge shifted in wavelength. These Stokes and anti-Stokes shifts act as fingerprints of bond stretching, bending and lattice vibrations, revealing oxidation states, surface-bound intermediates and structural reorganizations without destroying the sample. Advanced variants amplify this capability dramatically: surface-enhanced Raman spectroscopy (SERS), shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) and tip-enhanced Raman spectroscopy (TERS) can boost sensitivity enough to catch trace intermediates and nanoscale heterogeneity that conventional Raman would miss.

The review highlights striking case studies of catalyst self-reconstruction captured live. In one, researchers tracking a nickel-iron oxide catalyst watched the Raman signature of iron oxide fade with increasing potential while defect-related nickel oxide vibrations grew, until at 600 to 700 millivolts only two peaks remained, corresponding to the bending and stretching modes of nickel oxyhydroxide (NiOOH). The mixed-phase starting material had rebuilt itself into NiOOH, the phase actually doing the oxygen-evolving work. In another study on a molybdenum-doped nickel sulphide coupled with vanadium dioxide, the NiOOH signature appeared at 1.30 volts, earlier than in the undoped material, and a sulphate band emerged at lower potential, showing that the vanadium additive accelerated reconstruction while improving stability.

Composition, it turns out, plays an unexpectedly subtle role in these transformations. In FeOOH-decorated nickel molybdate nanowires, the NiOOH phase emerged slightly later than in the pristine material, reflecting iron’s inhibition of trivalent nickel formation, yet the reconstructed phase was ultimately more stable and active. Meanwhile, a rigorously controlled study of nickel-iron oxyhydroxides under iron-free conditions found that the intrinsic activity of pure beta-NiOOH is significantly lower than earlier reports suggested, and that the celebrated activity boost attributed to iron incorporation stems from electronic interactions between nickel and iron sites rather than conductivity gains alone. These contradictions, the review notes, would remain invisible without operando measurements, and they underscore how promoter elements govern catalytic behavior in ways that static characterization cannot untangle.

On the hydrogen evolution side, Raman has resolved equally fine details. Work on ruthenium surfaces in alkaline media distinguished hydrogen species adsorbed on metallic ruthenium from those bound to ruthenium oxide: after electrochemical reduction, the oxide band vanished and only the Ru(0)-H feature at 1825 wavenumbers remained, proving that a neighboring peak belonged to hydrogen on oxidized sites. On atomically flat palladium single crystals, operando Raman combined with computation showed that hydrogen-bonded and sodium-hydrated interfacial water reorganizes from a random to an ordered structure under bias, enhancing electron transfer and boosting activity. High-speed compressive Raman imaging of layered iridate and cobaltate oxygen-evolution electrodes revealed that at high current density, oxygen evolution outpaces cation exchange, confining charge compensation to the surface, whereas at lower overpotentials cations intercalate into the bulk lattice.

The technique also reads the electrolyte itself, the third leg of the catalyst-interface-electrolyte triad. In methanol oxidation on niobia, only one polymorph developed a distinctive Raman peak associated with short niobium-oxygen bonds in edge-sharing octahedra, and that in-situ-generated feature correlated precisely with the highest activity and formate selectivity, identifying the true active site. Similar studies have tracked formate formation during glycerol oxidation and mapped intermediates in 5-hydroxymethylfurfural oxidation to the plastic-recycling feedstock 2,5-furandicarboxylic acid. Because the three-dimensional porous substrates used in industrial electrodes, metal foams, meshes and carbon fabrics, do not obscure Raman signals and even allow deeper laser penetration, the method can capture gradients across electrode thickness under realistic loads.

Honest limitations remain. Raman scattering is inherently weak, fluorescence from dyes and pigments can bury signals, laser heating can damage sensitive materials, and gas bubbles disrupt optical paths at high current densities. The review points to engineering answers: carefully chosen laser wavelengths and power densities, longer relaxation times between scans, specialized temperature-monitoring probes, and cell architectures ranging from windowless thin-layer designs to flow cells with gas-diffusion electrodes that sweep bubbles away, and fiber-optic probes inserted directly into membrane electrode assemblies. Looking forward, the authors envision embedded Raman probes in commercial electrolyzer stacks feeding real-time data into digital durability dashboards, machine-learning spectral deconvolution for predictive maintenance, and multimodal platforms pairing Raman with X-ray absorption or mass spectrometry. Standardized protocols and reference spectral libraries for benchmark catalysts such as iridium dioxide, ruthenium dioxide and nickel-iron layered double hydroxides would be essential for industrial adoption.

The stakes are considerable. For hydrogen to compete with fossil-derived alternatives, electrolyzers must run reliably at industrial current densities for lifetimes exceeding 60,000 to 80,000 hours, whether the failure mode is ruthenium dissolution in PEM systems, nickel and iron leaching in alkaline devices or ionomer decomposition in AEM units. By catching degradation markers as they form rather than reconstructing them afterward, operando Raman spectroscopy promises to shift catalyst development from trial-and-error toward rational, data-driven engineering. If the vision of Raman-equipped smart electrolyzers materializes, the technique that lets chemists watch molecules vibrate could become the quality-control backbone of a global hydrogen economy.

Subject of Research: Operando Raman spectroscopy for monitoring catalyst degradation and structural dynamics in industrial green hydrogen water electrolyzers

Article Title: Operando Raman spectroscopy for exploring catalyst structural and interfacial dynamics in industrial green hydrogen electrolyzers

Article References: Rajani, N., Bhakhar, S. A., Pataniya, P. M., & Sumesh, C. K. (2026). Operando Raman spectroscopy for exploring catalyst structural and interfacial dynamics in industrial green hydrogen electrolyzers. Discover Electrochemistry, 3(1), Article 55. https://doi.org/10.1007/s44373-026-00142-1

Image Credits: AI Generated

DOI: 10.1007/s44373-026-00142-1

Keywords: green hydrogen, water electrolysis, Raman spectroscopy, operando characterization, electrocatalysis, catalyst degradation, PEM electrolyzer, alkaline electrolyzer, AEM electrolyzer, oxygen evolution reaction, hydrogen evolution reaction, surface reconstruction