10.1002/anie.202106515
Angewandte Chemie International Edition
RESEARCH ARTICLE
result using D2O as the reaction solvent. To further illustrate this
conclusion, we performed a kinetic analysis based on the
Langmuir–Hinshelwood mechanism. We considered both a two-
site model in which H and crotonaldehyde do not compete for
sites and a one-site model where they do compete. This analysis
is similar to what we recently performed for hydrogenation of
furfural,[24] which also includes a conjugated C=C and C=O bonds.
The kinetics analysis (Table S4), combined with our DFT
calculation discussed above, suggests the reaction is limited by
H2 dissociation; this agrees with the experimentally measured 1st
order of reaction rate with respect to H2 pressure. Interestingly,
though it does not determine the rate, the reaction selectivity is
indeed determined by hydrogenation of the C=C and C=O bonds;
the higher overall barrier for hydrogenation of the C=C than C=O
SC0013897) for Early Career Research. This research used
resources of the Advanced Photon Source, a U.S. Department of
Energy (DOE) Office of Science User Facility operated for the
DOE Office of Science by Argonne National Laboratory under
Contract No. DE-AC02-06CH11357. L.Q. was supported by the
U.S. Department of Energy (DOE), Office of Basic Energy
Sciences, Division of Chemical Sciences, Geosciences, and
Biosciences through the Ames Laboratory Catalysis program.
The Ames Laboratory is operated for the U.S. DOE by Iowa State
University under Contract No. DE‐ AC02‐07CH11358. We
thank Matt Besser for the use of the X-ray diffractometer. We
thank Taehoon Kim for assistance in STEM imaging at Ames
Laboratory Sensitive Instrument Facility. We are grateful to Yujia
Ding and Chengjun Sun for their help during the XANES
bonds thus explains the high selectivity to the unsaturated alcohol. measurement at stations 10-ID and 20-BM-B of Advanced Photon
Source.
Conclusion
Keywords: intermetallic phases • metastable compounds • α,β-
unsaturated aldehydes • heterogeneous catalysis • nanoparticles
In summary, we demonstrated the use of in-situ techniques that
enables the synthesis of intermetallic PdSn nanocatalysts. Both
in-situ PXRD and XANES studies confirm that a temperature
above 550 °C is necessary to obtain the pure PdSn phase, while
Pd2Sn and Pd3Sn2 intermediates present at lower temperatures.
In addition, the PdSn phase reverts to a thermodynamically
preferred Pd3Sn2 phase over a slow cooling process, but an
efficient quenching method harvests the PdSn nanocatalyst
successfully. We believe that this surface-specific phase
transition appears uniquely on nanomaterials. As for bulk material,
such transition would be masked by the dominant bulk phase in
PXRD measurements. This could nurture future studies about
distinct behaviors of nanomaterials. Applied to the hydrogenation
of crotonaldehyde as well as other α,β-unsaturated aldehydes,
the PdSn nanocatalyst exhibits excellent C=O hydrogenation
selectivity. Other catalysts, such as Pd, Pd3Sn, and Pd3Sn2, show
either poor selectivity or low activity. To the best of our knowledge,
this is the highest selectivity reported for this reaction with Pd-
based catalysts. Further studies demonstrate the significance of
efficient quenching in obtaining high activity and selectivity: a
Pd3Sn2-surfaced catalyst obtained after a natural cooling process
results in impaired catalytic selectivity and similar activity to pure
phase Pd3Sn2. CO-DRIFTS studies indicate that the reversion
from PdSn to Pd3Sn2 likely started at the surface of the catalyst.
Isotope-labelling studies show a short lifetime of adsorped
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Acknowledgements
This work is partially supported by NSF grant CHE-1808239. The
computations were performed at the OU Supercomputing Center
for Education & Research and the National Energy Research
Scientific Computing Center (NERSC), a U.S. Department of
Energy Office of Science User Facility, and were supported by the
U.S. Department of Energy, Basic Energy Sciences (Grant DE-
SC0018284). This work was partially supported by the US
Department of Energy, Basic Energy Science (Grant No. DE-
8
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