Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 144, Issue 11, Pages 5003-5009Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c13240
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Funding
- National Natural Science Foundation of China [21861132016, 22022406, 21775074]
- German Research Foundation [SCHL 594/17-1, 410889534]
- Natural Science Foundation of Tianjin [20JCJQJC00110, 20JCYBJC00590]
- 111 project [B12015]
- Haihe Laboratory of Sustainable Chemical Transformations
- University of Duisburg-Essen
- Center for Nanointegration Duisburg-Essen (CENIDE)
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The central dilemma in label-free in situ surface-enhanced Raman scattering (SERS) for monitoring of heterogeneously catalyzed reactions is the need of plasmonically active nanostructures for signal enhancement. By assembling catalytically active transition-metal nanoparticles into dimers, their plasmonic activity is significantly enhanced, enabling in situ SERS monitoring of various important heterogeneously catalyzed reactions.
The central dilemma in label-free in situ surface-enhanced Raman scattering (SERS) for monitoring of heterogeneouslycatalyzed reactions is the need of plasmonically active nanostructures forsignal enhancement. Here, we show that the assembly of catalyticallyactive transition-metal nanoparticles into dimers boosts their intrinsi-cally insufficient plasmonic activity at the monomer level by severalorders of magnitude, thereby enabling the in situ SERS monitoring ofvarious important heterogeneously catalyzed reactions at the single-dimer level. Specifically, we demonstrate that Pd nanocubes (NCs),which alone are not sufficiently plasmonically active as monomers, canact as a monometallic yet bifunctional platform with both catalytic andsatisfactory plasmonic activity via controlled assembly into single dimerswith an similar to 1 nm gap. Computer simulations reveal that the highestenhancement factors (EFs) occur at the corners of the gap, which has important implications for the SERS-based detection ofcatalytic conversions: it is sufficient for molecules to come in contact with thehot spot corners, and it is not required that theydiffuse deeply into the gap. For the widely employed Pd-catalyzed Suzuki-Miyaura cross-coupling reaction, we demonstrate thatsuch Pd NC dimers can be employed for in situ kinetic SERS monitoring, using a whole series of aryl halides as educts. Our genericapproach based on the controlled assembly into dimers can easily be extended to other transition-metal nanostructures.
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