Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density fun...

Full description

Saved in:
Bibliographic Details
Published in:Journal of the American Chemical Society 2012-08, Vol.134 (30), p.12807-12816
Main Authors: Vilhelmsen, Lasse B, Walton, Krista S, Sholl, David S
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster’s adsorption energy and diffusion barrier is established, confirming that Au clusters are highly mobile in the MOF-74 framework and Pd clusters are less mobile.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja305004a