Pd Catalyzed, Acid Accelerated, Rechargeable, Liquid Organic Hydrogen Carrier System Based on Methylpyridines/Methylpiperidines

Yinjun Xie, David Milstein

Research output: Contribution to journalArticle

Abstract

Efficient, solvent-free, liquid to liquid hydrogen storage systems based on reversible dehydrogenation and hydrogenation using a single heterogeneous supported Pd catalyst are reported, including (a) 2-picoline/2-methylpiperidine, and (b) 2,6-lutidine/2,6-dimethylpiperidine, having 6.1 and 5.3 wt % theoretical hydrogen storage capacity, respectively. By a simple blend of Pd(OAc)2, activated carbon, and methylpiperidines, a very active supported Pd/CHS (Pd/CHS = Pd on activated carbon for hydrogen storage) and catalytic acetic acid were generated in situ, which catalyzed the dehydrogenation of 2-methylpiperidine or 2,6-dimethylpiperidine to 2-picoline or 2,6-lutidine in excellent yields (91% and 100% yields, respectively), and releasing H2 at a fast rate under mild conditions. Our studies revealed that mild acids or acidic groups on the support surface significantly accelerate the dehydrogenation. The reverse hydrogenation of both 2-picoline (2-7 bar) and 2,6-lutidine (1.6-5 bar) was achieved under exceptionally low H2 pressure. Furthermore, the Pd/CHS catalyst can be easily recovered and reused without a decrease in catalytic activity.

Original languageEnglish
Pages (from-to)4302-4308
Number of pages7
JournalACS Applied Energy Materials
Volume2
Issue number6
DOIs
Publication statusPublished - Jun 24 2019

Fingerprint

Hydrogen storage
Dehydrogenation
Hydrogen
Activated carbon
Hydrogenation
Acids
Liquids
Catalyst supports
Acetic acid
Acetic Acid
Catalyst activity
Catalysts
2-picoline
2,6-lutidine
2-methylpiperidine
nanofin

Keywords

  • acid accelerated
  • hydrogen storage
  • nitrogen heterocycles
  • palladium
  • piperidine dehydrogenation

ASJC Scopus subject areas

  • Energy Engineering and Power Technology
  • Chemical Engineering (miscellaneous)
  • Electrochemistry
  • Materials Chemistry
  • Electrical and Electronic Engineering

Cite this

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title = "Pd Catalyzed, Acid Accelerated, Rechargeable, Liquid Organic Hydrogen Carrier System Based on Methylpyridines/Methylpiperidines",
abstract = "Efficient, solvent-free, liquid to liquid hydrogen storage systems based on reversible dehydrogenation and hydrogenation using a single heterogeneous supported Pd catalyst are reported, including (a) 2-picoline/2-methylpiperidine, and (b) 2,6-lutidine/2,6-dimethylpiperidine, having 6.1 and 5.3 wt {\%} theoretical hydrogen storage capacity, respectively. By a simple blend of Pd(OAc)2, activated carbon, and methylpiperidines, a very active supported Pd/CHS (Pd/CHS = Pd on activated carbon for hydrogen storage) and catalytic acetic acid were generated in situ, which catalyzed the dehydrogenation of 2-methylpiperidine or 2,6-dimethylpiperidine to 2-picoline or 2,6-lutidine in excellent yields (91{\%} and 100{\%} yields, respectively), and releasing H2 at a fast rate under mild conditions. Our studies revealed that mild acids or acidic groups on the support surface significantly accelerate the dehydrogenation. The reverse hydrogenation of both 2-picoline (2-7 bar) and 2,6-lutidine (1.6-5 bar) was achieved under exceptionally low H2 pressure. Furthermore, the Pd/CHS catalyst can be easily recovered and reused without a decrease in catalytic activity.",
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author = "Yinjun Xie and David Milstein",
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AU - Xie, Yinjun

AU - Milstein, David

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Y1 - 2019/6/24

N2 - Efficient, solvent-free, liquid to liquid hydrogen storage systems based on reversible dehydrogenation and hydrogenation using a single heterogeneous supported Pd catalyst are reported, including (a) 2-picoline/2-methylpiperidine, and (b) 2,6-lutidine/2,6-dimethylpiperidine, having 6.1 and 5.3 wt % theoretical hydrogen storage capacity, respectively. By a simple blend of Pd(OAc)2, activated carbon, and methylpiperidines, a very active supported Pd/CHS (Pd/CHS = Pd on activated carbon for hydrogen storage) and catalytic acetic acid were generated in situ, which catalyzed the dehydrogenation of 2-methylpiperidine or 2,6-dimethylpiperidine to 2-picoline or 2,6-lutidine in excellent yields (91% and 100% yields, respectively), and releasing H2 at a fast rate under mild conditions. Our studies revealed that mild acids or acidic groups on the support surface significantly accelerate the dehydrogenation. The reverse hydrogenation of both 2-picoline (2-7 bar) and 2,6-lutidine (1.6-5 bar) was achieved under exceptionally low H2 pressure. Furthermore, the Pd/CHS catalyst can be easily recovered and reused without a decrease in catalytic activity.

AB - Efficient, solvent-free, liquid to liquid hydrogen storage systems based on reversible dehydrogenation and hydrogenation using a single heterogeneous supported Pd catalyst are reported, including (a) 2-picoline/2-methylpiperidine, and (b) 2,6-lutidine/2,6-dimethylpiperidine, having 6.1 and 5.3 wt % theoretical hydrogen storage capacity, respectively. By a simple blend of Pd(OAc)2, activated carbon, and methylpiperidines, a very active supported Pd/CHS (Pd/CHS = Pd on activated carbon for hydrogen storage) and catalytic acetic acid were generated in situ, which catalyzed the dehydrogenation of 2-methylpiperidine or 2,6-dimethylpiperidine to 2-picoline or 2,6-lutidine in excellent yields (91% and 100% yields, respectively), and releasing H2 at a fast rate under mild conditions. Our studies revealed that mild acids or acidic groups on the support surface significantly accelerate the dehydrogenation. The reverse hydrogenation of both 2-picoline (2-7 bar) and 2,6-lutidine (1.6-5 bar) was achieved under exceptionally low H2 pressure. Furthermore, the Pd/CHS catalyst can be easily recovered and reused without a decrease in catalytic activity.

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