Light-Driven Electron-Transfer Catalysis on Earth-Abundant CuFeS2 Nanocrystals Probed by Operando SERS
8 affiliations
- 1Institute of Chemistry
- 2University of Potsdam
- 3AG Theoretische Optik & Photonik
- 4Humboldt-Universität zu Berlin
- 5Max-Born-Institute
- 6Institute of Physics and Astronomy
- 7Helmholtz Zentrum Berlin, Albert-Einstein-Str. 15, Berlin, Germany, 12489
- 8Dynamics of Molecules and Clusters Department, J. Heyrovský Institute of Physical Chemistry of the CAS, Dolejškova 3, Prague, Czech Republic, 18223
Abstract
Plasmonic nanoparticles possess a strong optical absorption but suffer from low catalytic activity and limited sustainability. Here, we demonstrate that earth-abundant chalcopyrite CuFeS2 nanocrystals (NCs) can serve as a dual-functional platform benefitting from a strong polaritonic absorption enabling surfaceenhanced Raman scattering (SERS), and providing at the same time high activity for light-induced electrontransfer catalysis. The nanocrystals exhibit a prominent optical resonance at 500 nm, originating from interband transitions into a Fe 3d derived intermediate band that drives the dielectric function toward the Fröhlich condition. This localized resonance yields a SERS analytical enhancement factor of ~ 3×103 for 1,2-bis(4-pyridyl)ethylene (BPE), validated by Discontinuous Galerkin Time-Domain (DGTD) electrodynamic simulations and Density Functional Theory (DFT) calculations that motivates synergistic near-field and charge transfer contributions. In addition, the CuFeS2 NCs efficiently drive the selective photoconversion of p-nitrothiophenol (NTP) to 4,4′-dimercaptoazobenzene (DMAB). Crucially, wavelength-dependent SERS and kinetic measurements prove that both Raman amplification and surface reactivity follow the optical resonance profile. Power-dependent and substrate-heating controls further confirm that this reactivity is mediated by photoexcited electron transfer into adsorbate orbitals rather than photothermal heating. By integrating a polaritonic optical enhancement with long excited state lifetimes provided by the intermediate band electronic structure in a single earth-abundant material, this work establishes CuFeS2 nanocrystals as a versatile architecture for SERS diagnostics and non-thermal photochemistry.
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BibTeX
@misc{gahlaut2026lightdriven,
title = {{Light-Driven Electron-Transfer Catalysis on Earth-Abundant CuFeS2 Nanocrystals Probed by Operando SERS}},
author = {Shashank K. Gahlaut and Biswajit Bhattacharyya and Guilherme Carraro Carella and Gino Wegner and Evgenii Titov and Felix Stete and Laura Baier and Radwan M. Sarhan and Peter Saalfrank and Andreas Taubert and Matias Bargheer and Kurt Busch and Ilko Bald},
howpublished = {ChemRxiv},
year = {2026},
month = aug,
doi = {10.26434/chemrxiv.15007925/v2},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007925/v2},
note = {CC BY},
}
RIS
TY - UNPB
TI - Light-Driven Electron-Transfer Catalysis on Earth-Abundant CuFeS2 Nanocrystals Probed by Operando SERS
AU - Shashank K. Gahlaut
AU - Biswajit Bhattacharyya
AU - Guilherme Carraro Carella
AU - Gino Wegner
AU - Evgenii Titov
AU - Felix Stete
AU - Laura Baier
AU - Radwan M. Sarhan
AU - Peter Saalfrank
AU - Andreas Taubert
AU - Matias Bargheer
AU - Kurt Busch
AU - Ilko Bald
PY - 2026
DA - 2026/08/30
PB - ChemRxiv
DO - 10.26434/chemrxiv.15007925/v2
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007925/v2
AB - Plasmonic nanoparticles possess a strong optical absorption but suffer from low catalytic activity and limited sustainability. Here, we demonstrate that earth-abundant chalcopyrite CuFeS2 nanocrystals (NCs) can serve as a dual-functional platform benefitting from a strong polaritonic absorption enabling surfaceenhanced Raman scattering (SERS), and providing at the same time high activity for light-induced electrontransfer catalysis. The nanocrystals exhibit a prominent optical resonance at 500 nm, originating from interband transitions into a Fe 3d derived intermediate band that drives the dielectric function toward the Fröhlich condition. This localized resonance yields a SERS analytical enhancement factor of ~ 3×103 for 1,2-bis(4-pyridyl)ethylene (BPE), validated by Discontinuous Galerkin Time-Domain (DGTD) electrodynamic simulations and Density Functional Theory (DFT) calculations that motivates synergistic near-field and charge transfer contributions. In addition, the CuFeS2 NCs efficiently drive the selective photoconversion of p-nitrothiophenol (NTP) to 4,4′-dimercaptoazobenzene (DMAB). Crucially, wavelength-dependent SERS and kinetic measurements prove that both Raman amplification and surface reactivity follow the optical resonance profile. Power-dependent and substrate-heating controls further confirm that this reactivity is mediated by photoexcited electron transfer into adsorbate orbitals rather than photothermal heating. By integrating a polaritonic optical enhancement with long excited state lifetimes provided by the intermediate band electronic structure in a single earth-abundant material, this work establishes CuFeS2 nanocrystals as a versatile architecture for SERS diagnostics and non-thermal photochemistry.
ER -