High-Throughput Experimentation, Theoretical Modeling, and Human Intuition: Lessons Learned in Metal−Organic-Framework-Supported Catalyst Design

Katherine E. McCullough, Daniel S. King, Saumil P. Chheda, Magali S. Ferrandon, Timothy A. Goetjen, Zoha H. Syed, Trent R. Graham, Nancy M. Washton, Omar K. Farha, Laura Gagliardi*, Massimiliano Delferro*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

We have screened an array of 23 metals deposited onto the metal−organic framework (MOF) NU-1000 for propyne dimerization to hexadienes. By a first-of-its-kind study utilizing data-driven algorithms and high-throughput experimentation (HTE) in MOF catalysis, yields on Cu-deposited NU-1000 were improved from 0.4 to 24.4%. Characterization of the best-performing catalysts reveal conversion to hexadiene to be due to the formation of large Cu nanoparticles, which is further supported by reaction mechanisms calculated with density functional theory (DFT). Our results demonstrate both the strengths and weaknesses of the HTE approach. As a strength, HTE excels at being able to find interesting and novel catalytic activity; any a priori theoretical approach would be hard-pressed to find success, as high-performing catalysts required highly specific operating conditions difficult to model theoretically, and initial simple single-atom models of the active site did not prove representative of the nanoparticle catalysts responsible for conversion to hexadiene. As a weakness, our results show how the HTE approach must be designed and monitored carefully to find success; in our initial campaign, only minor catalytic performances (up to 4.2% yield) were achieved, which were only improved following a complete overhaul of our HTE approach and questioning our initial assumptions.

Original languageEnglish (US)
Pages (from-to)266-276
Number of pages11
JournalACS Central Science
Volume9
Issue number2
DOIs
StatePublished - Feb 22 2023

Funding

This work was supported as part of the Catalyst Design for Decarbonization Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-SC0023383. This work made use of the Center for Nanoscale Materials (CNM) at Argonne National Laboratory, a U.S. Department of Energy Office of Science User Facility, and was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. Metal analysis was performed at the Northwestern University Quantitative Bioelement Imaging Center. The authors acknowledge Dr. Ryan Hackler for his help in the postmodification synthesis of NU-1000. Additionally, the authors acknowledge Ricardo Almada Monter for help exploring initial models for the prediction of catalytic activity, Ms. Rebecca Sponenburg for assistance with ICP-OES analysis to quantify metal loading, Dr. Roshan Ashokbhai Patel for helpful discussions on the periodic DFT calculations, and the Minnesota Supercomputing Institute (MSI) at the University of Minnesota as well as the Research Computing Center (RCC) at the University of Chicago for access to computing resources. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. The SCGSR program is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under contract number DE-SC0014664. Z.H.S. is supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-2234667. All opinions expressed in this paper are the author\u2019s and do not necessarily reflect the policies and views of DOE, ORAU, or ORISE.

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering

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