You are here

Controlling Catalytic Properties of Pd Nanoclusters through Their Chemical Environment at the Atomic Level Using Isoreticular Metal-Organic Frameworks

TitleControlling Catalytic Properties of Pd Nanoclusters through Their Chemical Environment at the Atomic Level Using Isoreticular Metal-Organic Frameworks
Publication TypeJournal Article
Year of Publication2016
AuthorsLi, XL, Goh, TW, Li, L, Xiao, CX, Guo, ZY, Zeng, XC, Huang, WK
JournalAcs Catalysis
Volume6
Pagination3461-3468
Date Published06
Type of ArticleArticle
ISBN Number2155-5435
Accession NumberWOS:000377326700007
Keywordsacetalization, alcohols, atomic-level selectivity control, chemistry, clusters, co oxidation, dft, DRIFTS studies, efficient catalyst, encapsulation, Heterogeneous catalysis, isoreticular metal-organic framework, linker substitution, nanoclusters, nanoparticles, oxidation, pd/al2o3 catalysts, selectivity, structure-activity relationship, under-coordinated metal
Abstract

Control of heterogeneous catalytic sites through their surrounding chemical environment at an atomic level is crucial to catalyst design. We synthesize Pd nanoclusters (NCs) in an atomically tunable chemical environment using isoreticular metalorganic framework (MOF) supports (Pd@UiO-66-X, X = H, NH2, OMe). In an aerobic reaction between benzaldehyde and ethylene glycol, these catalysts show product distributions that are completely altered from the acetal to the ester when we change the functional groups on the MOF linkers from -NH2 to -H/-OMe. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies, along with density functional theory (DFT) calculations, show that the coordination of the-NH2 groups to the Pd NCs could weaken their oxidation capability to a greater extent in comparison to that of the-OMe group. Moreover, the limited number of-NH2 groups per cavity in the MOF change the electronic properties of the Pd NCs while still leaving open sites for catalysis.

DOI10.1021/acscataL.6b00397
Custom 1

Royalty

Alternate JournalACS Catal.