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Mechanistic insights into carbon–carbon coupling on NiAu and PdAu single-atom alloys

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0048977· OSTI ID:1837210
 [1];  [2];  [1];  [1];  [3];  [2];  [1]
  1. Tufts Univ., Medford, MA (United States)
  2. Univ. College London (United Kingdom)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
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Carbon–carbon coupling is an important step in many catalytic reactions, and performing sp3–sp3 carbon–carbon coupling heterogeneously is particularly challenging. It has been reported that PdAu single-atom alloy (SAA) model catalytic surfaces are able to selectively couple methyl groups, producing ethane from methyl iodide. In this work, we extend this study to NiAu SAAs and find that Ni atoms in Au are active for C–I cleavage and selective sp3–sp3 carbon–carbon coupling to produce ethane. Furthermore, we perform ab initio kinetic Monte Carlo simulations that include the effect of the iodine atom, which was previously considered a bystander species. We find that model NiAu surfaces exhibit a similar chemistry to PdAu, but the reason for the similarity is due to the role the iodine atoms play in terms of blocking the Ni atom active sites. Specifically, on NiAu SAAs, the iodine atoms outcompete the methyl groups for occupancy of the Ni sites leaving the Me groups on Au, while on PdAu SAAs, the binding strengths of methyl groups and iodine atoms at the Pd atom active site are more similar. These simulations shed light on the mechanism of this important sp3–sp3 carbon–carbon coupling chemistry on SAAs. Furthermore, we discuss the effect of the iodine atoms on the reaction energetics and make an analogy between the effect of iodine as an active site blocker on this model heterogeneous catalyst and homogeneous catalysts in which ligands must detach in order for the active site to be accessed by the reactants.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Leverhulme Trust; Engineering and Physical Sciences Research Council (EPSRC)
Grant/Contract Number:
SC0012704
OSTI ID:
1837210
Alternate ID(s):
OSTI ID: 1838173
OSTI ID: 1784580
Report Number(s):
BNL--222521-2021-JAAM
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 154; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
DFT
KMC
STM
TPD
Würtz coupling
heterogeneous catalysis