Volume 20, Issue 47 p. 15587-15604
Full Paper

Exploring the Potential of Fulvalene Dimetals as Platforms for Molecular Solar Thermal Energy Storage: Computations, Syntheses, Structures, Kinetics, and Catalysis

Dr. Karl Börjesson

Dr. Karl Börjesson

Department of Chemical and Biological Engineering, Chalmers University of Technology, 41296 Gothenburg (Sweden)

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Dr. Dušan Ćoso

Dr. Dušan Ćoso

Department of Mechanical Engineering, University of California at Berkeley, Berkeley, CA 94720-1740 (USA)

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Victor Gray

Victor Gray

Department of Chemical and Biological Engineering, Chalmers University of Technology, 41296 Gothenburg (Sweden)

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Prof. Dr. Jeffrey C. Grossman

Prof. Dr. Jeffrey C. Grossman

Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA)

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Prof. Dr. Jingqi Guan

Prof. Dr. Jingqi Guan

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

College of Chemistry, Jilin University, Changchun 130023 (PR China)

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Prof. Dr. Charles B. Harris

Prof. Dr. Charles B. Harris

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Dr. Norbert Hertkorn

Dr. Norbert Hertkorn

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

Analytical Biogeochemistry, Helmholtz Zentrum München, 85764 Neuherberg (Germany)

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Dr. Zongrui Hou

Dr. Zongrui Hou

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Prof. Dr. Yosuke Kanai

Prof. Dr. Yosuke Kanai

Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290 (USA)

Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, Livermore, CA 94550 (USA)

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Dr. Donghwa Lee 

Dr. Donghwa Lee 

Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290 (USA)

Condensed Matter and Materials Division, Lawrence Livermore National Laboratory, Livermore, CA 94550 (USA)

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Justin P. Lomont

Justin P. Lomont

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Prof. Dr. Arun Majumdar

Prof. Dr. Arun Majumdar

Department of Mechanical Engineering, University of California at Berkeley, Berkeley, CA 94720-1740 (USA)

Present address: Department of Mechanical Engineering, Stanford University, Stanford, California 94305-3030 (USA)

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Dr. Steven K. Meier

Dr. Steven K. Meier

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Prof. Dr. Kasper Moth-Poulsen

Prof. Dr. Kasper Moth-Poulsen

Department of Chemical and Biological Engineering, Chalmers University of Technology, 41296 Gothenburg (Sweden)

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Dr. Randy L. Myrabo

Dr. Randy L. Myrabo

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Son C. Nguyen

Son C. Nguyen

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Prof. Dr. Rachel A. Segalman

Prof. Dr. Rachel A. Segalman

Department of Chemical and Biomolecular Engineering, University of California at Berkeley, Berkeley, CA 94720-1462 (USA)

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Prof. Dr. Varadharajan Srinivasan

Prof. Dr. Varadharajan Srinivasan

Department of Chemistry, Indian Institute of Science Education and Research, Bhopal (India)

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Dr. Willam B. Tolman

Dr. Willam B. Tolman

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Dr. Nikolai Vinokurov

Dr. Nikolai Vinokurov

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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Prof. Dr. K. Peter C. Vollhardt

Corresponding Author

Prof. Dr. K. Peter C. Vollhardt

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)Search for more papers by this author
Dr. Timothy W. Weidman

Dr. Timothy W. Weidman

Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460 (USA)

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First published: 03 October 2014
Citations: 34

Graphical Abstract

Minding the store: Variation of the ligand framework around the dinuclear core of FvRu2 allows a significant extension of its potential as a photothermal energy storage molecule. DFT calculations provide insight into the effect of substituents, other metals, and CO exchange for other ligands on ΔHstorage. An extensive screen of potential catalysts for the thermal reversal identified AgNO3–SiO2 as a good candidate.

Abstract

A study of the scope and limitations of varying the ligand framework around the dinuclear core of FvRu2 in its function as a molecular solar thermal energy storage framework is presented. It includes DFT calculations probing the effect of substituents, other metals, and CO exchange for other ligands on ΔHstorage. Experimentally, the system is shown to be robust in as much as it tolerates a number of variations, except for the identity of the metal and certain substitution patterns. Failures include 1,1′,3,3′-tetra-tert-butyl (4), 1,2,2′,3′-tetraphenyl (9), diiron (28), diosmium (24), mixed iron-ruthenium (27), dimolybdenum (29), and ditungsten (30) derivatives. An extensive screen of potential catalysts for the thermal reversal identified AgNO3–SiO2 as a good candidate, although catalyst decomposition remains a challenge.