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Selective molecular recognition by nanoscale environments in a supported iridium cluster catalyst

Nature Nanotechnology volume 9, pages 459–465 (2014)Cite this article

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Abstract

The active sites of enzymes are contained within nanoscale environments that exhibit exquisite levels of specificity to particular molecules. The development of such nanoscale environments on synthetic surfaces, which would be capable of discriminating between molecules that would nominally bind in a similar way to the surface, could be of use in nanosensing, selective catalysis and gas separation. However, mimicking such subtle behaviour, even crudely, with a synthetic system remains a significant challenge. Here, we show that the reactive sites on the surface of a tetrairidium cluster can be controlled by using three calixarene–phosphine ligands to create a selective nanoscale environment at the metal surface. Each ligand is 1.4 nm in length and envelopes the cluster core in a manner that discriminates between the reactivities of the basal-plane and apical iridium atoms. CO ligands are initially present on the clusters and can be selectively removed from the basal-plane sites by thermal dissociation and from the apical sites by reactive decarbonylation with the bulky reactant trimethylamine-N-oxide. Both steps lead to the creation of metal sites that can bind CO molecules, but only the reactive decarbonylation step creates vacancies that are also able to bond to ethylene, and catalyse its hydrogenation.

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Figure 1: Synthesis and schematic mechanical model of ligand stabilized open-site clusters.
Figure 2: Infrared spectra corresponding to bridged and terminal CO integrated intensity versus time.
Figure 3: Difference infrared spectroscopy was used to investigate binding of ethylene to various CO vacancies on the tetrairidium cluster core.
Figure 4: Kinetics of isotopic H2-D2 exchange was used to investigate the catalytic consequences of ethylene bonding to open sites on the tetrairidium cluster core.
Figure 5: Kinetic consequences of CO vacancies that either bond or are unable to bond to ethylene are investigated for ethylene hydrogenation catalysis.

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Acknowledgements

The authors acknowledge financial support from the Management and Transfer of Hydrogen via Catalysis Program funded by Chevron Corporation (to A.O. and X.O.) and the US Department of Energy, Office of Science, Basic Energy Sciences (contract no. DE-SC0005822, to J.L., C.A., B.G., R.R., A.K., S.Z. and D.D.). The NMR facility at Caltech was supported by the National Science Foundation (NSF; grant no. 9724240) and partially supported by the MRSEC Program of the NSF (award no. DMR-520565; to S.H.). Electron microscopy work was supported by the Department of Energy (DOE; Basic Energy Sciences grant no. DE-FG02-03ER46057, to C.A.) and the University of California Lab Fee Program. The Molecular Graphics and Computation Facility at UC Berkeley was supported by the NSF (award no. CHE 0840505, to O.O. and K.D.).

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Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of California at Berkeley, Berkeley, 94720, California, USA

    Alexander Okrut, Ron C. Runnebaum, Xiaoying Ouyang, Olayinka A. Olatunji-Ojo, Kathleen A. Durkin & Alexander Katz

  2. Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, 95616, California, USA

    Jing Lu, Ceren Aydin & Bruce C. Gates

  3. Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, 91125, California, USA

    Son-Jong Hwang

  4. Department of Chemistry, The University of Alabama, Tuscaloosa, 35487, Alabama, USA

    Shengjie Zhang & David A. Dixon

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Contributions

A.O., B.G. and A.K. conceived and designed the experiments and co-wrote the paper. A.O. synthesized all materials and performed solution-phase experiments and analysed spectroscopic data. R.R. performed ethylene hydrogenation experiments and analysed the data. X.O. performed the in situ FTIR experiments and analysed the data. J.L. performed the H2/D2 exchange experiment and analysed the data. C.A. performed scanning transmission electron microscopy experiments and analysed the data. O.O., S.Z., K.D. and D.D. performed molecular modelling studies and analysed the data. S.H. performed solid-state NMR experiments and analysed the data. All authors discussed the results and commented on the manuscript.

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Correspondence to Bruce C. Gates or Alexander Katz.

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Okrut, A., Runnebaum, R., Ouyang, X. et al. Selective molecular recognition by nanoscale environments in a supported iridium cluster catalyst. Nature Nanotech 9, 459–465 (2014). https://doi.org/10.1038/nnano.2014.72

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