Controlling the chemical environments of the active metal atom including both coordination number (CN) and local composition (LC) is vital to achieve active and stable single-atom catalysts (SACs), but remains challenging. Here we synthesized a series of supported Pt 1 SACs by depositing Pt atoms onto the pretuned anchoring sites on nitrogen-doped carbon using atomic layer deposition. In hydrogenation of para-chloronitrobenzene, the Pt 1 SAC with a higher CN about four but less pyridinic nitrogen (N pyri ) content exhibits a remarkably high activity along with superior recyclability compared to those with lower CNs and more N pyri . Theoretical calculations reveal that the four-coordinated Pt 1 atoms with about 1 eV lower formation energy are more resistant to agglomerations than the three-coordinated ones. Composition-wise decrease of the Pt−N pyri bond upshifts gradually the Pt-5d center, and minimal one Pt−N pyri bond features a high-lying Pt-5d state that largely facilitates H 2 dissociation, boosting hydrogenation activity remarkably.
Selective C–C coupling of
oxygenates is pertinent to the
manufacture of fuel and chemical products from biomass and from derivatives
of C1 compounds (i.e., oxygenates produced from methane
and CO2). Here we report a combined experimental and theoretical
study on the temperature-programmed reaction (TPR) of acetaldehyde
(AcH) on a partially reduced CeO2–x
(111) thin film surface. The experiments have been carried out under
ultra-high-vacuum conditions without continuous gas exposure, allowing
better isolation of active sites and reactive intermediates than in
flow reaction conditions. AcH does not undergo aldol condensation
in a typical TPR procedure, even though the enolate form of AcH (CH2CHO) is readily produced on CeO2–x
(111) with oxygen vacancies. We find however that a tailored
“double-ramp” TPR procedure is able to successfully
produce an aldol adduct, crotonaldehyde (CrA). Using density functional
theory calculations and microkinetic modeling we explore several possible
C–C coupling pathways. We conclude that the double-ramp procedure
allows surface oxygen vacancy dimers, stabilized by adsorbate occupation,
to form dynamically during the TPR. The vacancy dimers in turn enable
C–C coupling to occur between an enolate and an adjacent AcH
molecule via a bifunctional enolate–keto mechanism that is
distinct from conventional acid- or base-catalyzed aldol condensation
reactions. The proposed mechanism indicates that CrA desorption is
rate-limiting while C–C coupling is facile.
Core-shell bimetallic nanocatalysts have attracted long-standing attention in heterogeneous catalysis. Tailoring both the core size and shell thickness to the dedicated geometrical and electronic properties for high catalytic reactivity is important but challenging. Here, taking Au@Pd core-shell catalysts as an example, we disclose by theory that a large size of Au core with a two monolayer of Pd shell is vital to eliminate undesired lattice contractions and ligand destabilizations for optimum benzyl alcohol adsorption. A set of Au@Pd/SiO2 catalysts with various core sizes and shell thicknesses are precisely fabricated. In the benzyl alcohol oxidation reaction, we find that the activity increases monotonically with the core size but varies nonmontonically with the shell thickness, where a record-high activity is achieved on a Au@Pd catalyst with a large core size of 6.8 nm and a shell thickness of ~2–3 monolayers. These findings highlight the conjugated dual particle size effect in bimetallic catalysis.
Using in situ diffuse
reflectance infrared Fourier transform spectroscopy
(DRIFTS) and density functional theory (DFT) calculations, we conclusively
demonstrate that acetaldehyde (AcH) undergoes aldol condensation when
flown over ceria octahedral nanoparticles, and the reaction is desorption-limited
at ambient temperature.
trans
-Crotonaldehyde (CrH)
is the predominant product whose coverage builds up on the catalyst
with time on stream. The proposed mechanism on CeO
2
(111)
proceeds via AcH enolization (i.e., α C–H bond scission),
C–C coupling, and further enolization and dehydroxylation of
the aldol adduct, 3-hydroxybutanal, to yield
trans
-CrH. The mechanism with its DFT-calculated parameters is consistent
with reactivity at ambient temperature and with the kinetic behavior
of the aldol condensation of AcH reported on other oxides. The slightly
less stable
cis
-CrH can be produced by the same mechanism
depending on how the enolate and AcH are positioned with respect to
each other in C–C coupling. All vibrational modes in DRIFTS
are identified with AcH or
trans
-CrH, except for
a feature at 1620 cm
–1
that is more intense relative
to the other bands on the partially reduced ceria sample than on the
oxidized sample. It is identified to be the C=C stretch mode
of CH
3
CHOHCHCHO adsorbed on an oxygen vacancy. It constitutes
a deep energy minimum, rendering oxygen vacancies an inactive site
for CrH formation under given conditions.
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