دورية أكاديمية
Dynamical Study of Adsorbate-Induced Restructuring Kinetics in Bimetallic Catalysts Using the PdAu(111) Model System.
| العنوان: | Dynamical Study of Adsorbate-Induced Restructuring Kinetics in Bimetallic Catalysts Using the PdAu(111) Model System. |
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| المؤلفون: | Zhou C; Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States.; Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, New York 11790, United States., Ngan HT; Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, California 90095, United States., Lim JS; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States., Darbari Z; Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States.; Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, New York 11790, United States., Lewandowski A; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States., Stacchiola DJ; Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States., Kozinsky B; Harvard John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States.; Robert Bosch LLC, Research and Technology Center, Cambridge, Massachusetts 02139, United States., Sautet P; Department of Chemical and Biomolecular Engineering, University of California, Los Angeles, California 90095, United States.; Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States., Boscoboinik JA; Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States. |
| المصدر: | Journal of the American Chemical Society [J Am Chem Soc] 2022 Aug 24; Vol. 144 (33), pp. 15132-15142. Date of Electronic Publication: 2022 Aug 11. |
| نوع المنشور: | Journal Article |
| اللغة: | English |
| بيانات الدورية: | Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: PubMed not MEDLINE; MEDLINE |
| أسماء مطبوعة: | Publication: Washington, DC : American Chemical Society Original Publication: Easton, Pa. [etc.] |
| مستخلص: | Dynamic restructuring of bimetallic catalysts plays a crucial role in their catalytic activity and selectivity. In particular, catalyst pretreatment with species such as carbon monoxide and oxygen has been shown to be an effective strategy for tuning the surface composition and morphology. Mechanistic and kinetic understanding of such restructuring is fundamental to the chemistry and engineering of surface active sites but has remained challenging due to the large structural, chemical, and temporal degrees of freedom. Here, we combine time-resolved temperature-programmed infrared reflection absorption spectroscopy, ab initio thermodynamics, and machine-learning molecular dynamics to uncover previously unidentified timescale and kinetic parameters of in situ restructuring in Pd/Au(111), a highly relevant model system for dilute Pd-in-Au nanoparticle catalysts. The key innovation lies in utilizing CO not only as a chemically sensitive probe of surface Pd but also as an agent that induces restructuring of the surface. Upon annealing in vacuum, as-deposited Pd islands became encapsulated by Au and partially dissolved into the subsurface, leaving behind isolated Pd monomers on the surface. Subsequent exposure to 0.1 mbar CO enabled Pd monomers to repopulate the surface up to 373 K, above which complete Pd dissolution occurred by 473 K, with apparent activation energies of 0.14 and 0.48 eV, respectively. These restructuring processes occurred over the span of ∼1000 s at a given temperature. Such a minute-timescale dynamics not only elucidates the fluxional nature of alloy catalysts but also presents an opportunity to fine-tune the surface under moderate temperature and pressure conditions. |
| تواريخ الأحداث: | Date Created: 20220811 Latest Revision: 20220824 |
| رمز التحديث: | 20231215 |
| DOI: | 10.1021/jacs.2c04871 |
| PMID: | 35952667 |
| قاعدة البيانات: | MEDLINE |
Find this issue from the American Chemical Society | تدمد: | 1520-5126 |
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| DOI: | 10.1021/jacs.2c04871 |