Hydrogen storage with spectroscopic identification of chemisorption sites in Cu-TDPAT via spillover from a Pt/activated carbon catalyst

Cheng Yu Wang, Jennifer L. Gray, Qihan Gong, Yonggang Zhao, Jing Li, Emmanuel Klontzas, George Psofogiannakis, George Froudakis, Angela D. Lueking

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Hydrogen spillover to the Cu-TDPAT (TDPAT = 2,4,6-tris(3,5-dicarboxylphe-nylamino)-1,3,5-triazine) metal-organic framework is probed with adsorption measurements, ex situ characterization techniques, and density functional theory (DFT) calculations. At 1 bar and 300 K, hydrogen chemisorption to Pt/AC/Cu-TDPAT exceeds that expected for physisorption by 8-fold, which is attributable to both catalyst insertion and the creation of structural defects. Hydrogenation of (a) the Cu-O-C bond of the Cu paddlewheel, (b) the sp2 N heterocycle, and (c) the secondary amine is demonstrated with ex situ spectroscopy. Exothermic (with respect to H2) hydrogenation at the Cu-O-C bond of the paddlewheel is substantiated by DFT. However, hydrogenated Cu-O-C is metastable, as evidence for dissociation is found at higher temperature (i.e., 473 K H2). DFT calculations demonstrate hydrogenation of the N groups may occur exothermically only for a charged ligand, suggestive that defects may contribute to hydrogen chemisorption. At high pressure, slow adsorption rates and material instability render the material unsuitable for practical hydrogen storage applications. (Figure Presented).

Original languageEnglish
Pages (from-to)26750-26763
Number of pages14
JournalJournal of Physical Chemistry C
Volume118
Issue number46
DOIs
Publication statusPublished - Nov 20 2014

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Hydrogen storage
activated carbon
Chemisorption
Activated carbon
chemisorption
Hydrogenation
Density functional theory
Hydrogen
hydrogenation
catalysts
Catalysts
hydrogen
density functional theory
Adsorption
Triazines
Defects
Physisorption
adsorption
Amines
defects

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Hydrogen storage with spectroscopic identification of chemisorption sites in Cu-TDPAT via spillover from a Pt/activated carbon catalyst. / Wang, Cheng Yu; Gray, Jennifer L.; Gong, Qihan; Zhao, Yonggang; Li, Jing; Klontzas, Emmanuel; Psofogiannakis, George; Froudakis, George; Lueking, Angela D.

In: Journal of Physical Chemistry C, Vol. 118, No. 46, 20.11.2014, p. 26750-26763.

Research output: Contribution to journalArticle

Wang, CY, Gray, JL, Gong, Q, Zhao, Y, Li, J, Klontzas, E, Psofogiannakis, G, Froudakis, G & Lueking, AD 2014, 'Hydrogen storage with spectroscopic identification of chemisorption sites in Cu-TDPAT via spillover from a Pt/activated carbon catalyst', Journal of Physical Chemistry C, vol. 118, no. 46, pp. 26750-26763. https://doi.org/10.1021/jp507395p
Wang, Cheng Yu ; Gray, Jennifer L. ; Gong, Qihan ; Zhao, Yonggang ; Li, Jing ; Klontzas, Emmanuel ; Psofogiannakis, George ; Froudakis, George ; Lueking, Angela D. / Hydrogen storage with spectroscopic identification of chemisorption sites in Cu-TDPAT via spillover from a Pt/activated carbon catalyst. In: Journal of Physical Chemistry C. 2014 ; Vol. 118, No. 46. pp. 26750-26763.
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