Table 1 Operando/in-situ electrochemical techniques for MOF electrocatalysts

From: Harnessing the structural evolution of metal–organic frameworks under electrocatalytic conditions

Target Information

Technique

Operando/In-Situ Capability

Lab-Based or Synchrotron

Strengths

Limitations

Metal oxidation states and coordination information105

XAS (XANES/EXAFSa)

Yes (widely used)

Lab & Synchrotron

Element-specific, quantitative; ideal for monitoring metal sites; operando cells available

Requires synchrotron for high resolution; MOF model-dependent data fitting

Crystalline structure and phase change106,107

XRD, PDFb

Limited operando setups

Lab & Synchrotron

Tracks long-range structural evolution; ideal for bulk structural changes

Poor sensitivity to local or amorphous features

Cluster/Nanoparticle formation95,108

TEM/HR-TEM/EDc

Rare in-situ; mostly ex-situ

Lab & Advanced Centers

High spatial resolution; ideal for visualizing nanoscale evolution

In-situ liquid-cell TEM is complex and beam-sensitive for MOF; interpretation nontrivial

Functional group, M–L bond changes and reaction intermediates82,109

Raman/SERS, FTIR/SEIRASd

Yes (widely used)

Lab

Real-time tracking of ligand dissociation/adsorption; Sensitive to electrochemical adsorbates; useful for mechanistic insights

Interference in Raman; limited detection of symmetric/weakly IR-active species; Requires enhanced surface signal; overlaps common

Optoelectronic structure26

UV-vis, PL, UPSe

Some in-situ studies

Lab

Tracks changes in optical absorption and electronic structure; fast and simple

Cannot directly provide structural information; PL sensitive to defects and quenching

Conductivity and Electron transport110,111

EISf, UV-vis

Yes

Lab

Evaluates ionic/electronic conductivity and interface behavior

Indirect structural info; needs complementary techniques

  1. aXANES/EXAFS: X-ray Absorption Near Edge Structure/Extended X-ray Absorption Fine Structure.
  2. bPDF: Pair Distribution Function.
  3. cED: Electron Diffraction.
  4. dSEIRAS: Surface-Enhanced Infrared Absorption Spectroscopy.
  5. eUPS: Ultraviolet Photoelectron Spectroscopy.
  6. fEIS: Electrochemical Impedance Spectroscopy.
  7. Summary of commonly used techniques to probe MOF structural and electronic evolution under reaction conditions, including the type of information obtained, applicability in operando/in-situ setups, and key strengths and limitations.
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