Controlling Selectivity in Unsaturated Aldehyde Hydrogenation
Using Single-Site Alloy Catalysts
Posted on 2019-09-10 - 20:11
Selectivity
in catalysis is key to many industrial processes, yet it is often
difficult to control. One promising approach is to use so-called
single-atom catalysts, whereby one catalytic component is isolated
within a second phase to add a key but otherwise unavailable functionality.
Here, we report the use of metal alloys consisting of Pt single atoms
diluted within Cu nanoparticles to selectively promote the hydrogenation
of CO bonds in unsaturated aldehydes, a reaction of interest
in fine chemical manufacturing. Our rationale, that Cu surfaces may
favor CO over CC hydrogenation steps with atomic hydrogen
but may require Pt sites to promote the initial activation of molecular
hydrogen, was corroborated by kinetic catalytic experiments. However,
fundamental surface science studies and quantum mechanics calculations
showed that the explanation for the observed catalytic performance
is more nuanced. For one, titration experiments using carbon monoxide
failed to identify Pt atoms accessible on the surface of the catalysts,
suggesting that their catalytic contribution may involve indirect
electronic changes on neighboring Cu atoms. In addition, infrared
absorption and X-ray photoelectron spectroscopy results identified
the existence of a thin Cu oxide layer covering the metallic nanoparticles.
Finally, it was determined that hydrogenation selectivity with Cu-based
catalysts may be explained in part by their preference for bonding
unsaturated aldehydes via the terminal oxygen atom but is also affected
by competitive adsorption among the reactants and products. Single-atom
alloy catalysts appear to indeed help with selectivity in hydrogenation
catalysis, but more in situ (or operando) characterization experiments
are needed to better understand how they operate.
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Cao, Yueqiang; Chen, Bo; Guerrero-Sánchez, Jonathan; Lee, Ilkeun; Zhou, Xinggui; Takeuchi, Noboru; et al. (2019). Controlling Selectivity in Unsaturated Aldehyde Hydrogenation
Using Single-Site Alloy Catalysts. ACS Publications. Collection. https://doi.org/10.1021/acscatal.9b02547
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AUTHORS (7)
YC
Yueqiang Cao
BC
Bo Chen
JG
Jonathan Guerrero-Sánchez
IL
Ilkeun Lee
XZ
Xinggui Zhou
NT
Noboru Takeuchi
FZ
Francisco Zaera
KEYWORDS
metal alloysSingle-atom alloy catalystsControlling SelectivityCu atomscarbon monoxidetitration experimentsUnsaturated Aldehyde HydrogenationX-ray photoelectron spectroscopy resultschemical manufacturingsurface science studiesCu surfacesCu oxide layerCu nanoparticlescharacterization experimentsCu-based catalystshydrogenation selectivitysingle-atom catalystsSingle-Site Alloy Catalysts Selectivityterminal oxygen atomaldehydePt siteshydrogenation catalysisquantum mechanics calculationsPt atoms