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Hydrogen Storage

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Hydrogen Storage. in Nano-Porous Materials. The University of Oklahoma ... (30 bar) H2 fills the majority of the. void regions of material ... – PowerPoint PPT presentation

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Title: Hydrogen Storage


1
Hydrogen Storage in Nano-Porous Materials
Dimitrios Argyris
The University of Oklahoma
School of Chemical, Biological, and Materials
Engineering
2
Hydrogen Storage in Nano-Porous Materials
Introduction
Hydrogen storage
  • Petroleum dependence ? U.S. imports 55 of its
    oil
  • expected to grow to 68 in 2025
  • Hydrogen as energy carrier ? clean, efficient,
    and can be derived from
  • domestic resources

Renewable (biomass, hydro, wind, solar, and
geothermal)
Fossil fuels (coal ,natural gas, etc.)
Nuclear Energy
3
Hydrogen Storage in Nano-Porous Materials
Introduction
Hydrogen storage
  • Hydrogen storage is a critical enabling
    technology for the
  • acceptance of hydrogen powered vehicles
  • Storing sufficient hydrogen on board to meet
    consumers
  • requirements (eg. driving range, cost, safety,
    and performance)
  • is a crucial technical parameter
  • No approach currently exists that meets
    technical requir.
  • driving range gt 300 miles
  • U.S. DoE ? develop on board storage systems
  • achieving 6 and 9 wt for 2010 and 2015

4
Hydrogen Storage in Nano-Porous Materials
Storage Approaches
Reversible on board
  • Compressed hydrogen gas, Liquid hydrogen tanks,
    Metal hydrides,
  • Porous materials

Regenerable off-board
  • Hydrolysis reactions, hydrogenation/dehydrogenati
    on reactions,
  • ammonia borane and other boron hydrides, alane
    (metal hydride), etc.

Porous materials usually carbon based materials
with high surface area
5
Hydrogen Storage in Nano-Porous Materials
Storage Approaches
Porous Materials
  • Single walled carbon nanotubes (CNT)
  • Graphite materials
  • Carbon nanofibers
  • Metal-organic framework
  • Theoretical studies organometallic buckyball
    fullerenes, Si-C nanotubes

High surface area sorbents
Advantages High surface area ? fast
hydrogen kinetics and low hydrogen binding
energies ? fewer thermal management
issues
6
Hydrogen Storage in Nano-Porous Materials
Synthesis
Metal-Organic Frameworks
O (red) C (gray) H (white) Cu (purple)
HKUST-1, Cu2(C9H3O6)4/3
  • benzene-1,3,5-tricarboxylic acid
  • heated with
  • copper nitrate hemipentahydrate
  • in solvent consisting of equal parts of
  • N,N-dimethylformamide (DMF),
  • ethanol, and deionized water ?
  • filtration, drying, and solvent removal ?
  • porous material HKUST-1

3 different metal organic frameworks
HKUST-1
www.esrf.eu/
7
Hydrogen Storage in Nano-Porous Materials
Synthesis
Metal-Organic Frameworks
HKUST-1 MIL-101
Covalent-Organic Frameworks
COF-1
8
Hydrogen Storage in Nano-Porous Materials
Characterization
X-ray diffraction
X-ray diffraction patterns of (a) COF-1, HKUST-1,
and (b) MIL-101.
All samples show good crystallinity
9
Hydrogen Storage in Nano-Porous Materials
Characterization
Infra-red spectra
Vibrational bands 1376 and 1340 cm-1? BO
stretching 1023 cm-1 ? BC bonds 708 cm-1 ?
B3O3 ring units
Infra-red spectra of COF-1 (a)
10
Hydrogen Storage in Nano-Porous Materials
Characterization
Scanning Electron Microscopy
Particles Size
  • COF-1 0.3-0.4 µm
  • HKUST-1 4.0-8.0 µm
  • MIL-101 0.2-0.3 µm

COF-1 (a)
MIL-101 (c)
Unique morphology of particles in each material
HKUST-1 (b)
11
Hydrogen Storage in Nano-Porous Materials
Characterization
BET surface area
BET surface area and pore volume ? N2 adsorption
at 77 K
BET surface area (m2/g)
Pore volume (cm3/g)
  • COF-1 628 0.36
  • HKUST-1 1296 0.69
  • MIL-101 2931 1.45

12
Hydrogen Storage in Nano-Porous Materials
Characterization
Hydrogen Adsorption
H2 Uptake (wt ) (77 K and 1 atm)
H2 Uptake (wt ) (298 K and 10 MPa)
  • COF-1 1.28 0.26
  • HKUST-1 2.28 0.35
  • MIL-101 1.91 0.51

13
Hydrogen Storage in Nano-Porous Materials
Characterization
Hydrogen Adsorption
MIL-101
Hydrogen adsorption at 298 K
MIL-101 - bridges - Pt/AC
Pt/AC and MIL-101 physical mixture (19 mass)
Pure MIL-101
Bridged spillover ? hydrogen adsorption increased
by a factor of 2.6 3.2
14
Hydrogen Storage in Nano-Porous Materials
Molecular Simulations
GCMC simulations ? Predict adsorption isotherm
for H2 ? 10 isoreticular metal organic
frameworks (IRMOFs)
IRMOFs
Oxide - centered Zn4O tetrahedra each connected
by six dicarboxylate linkers
3D cubic network very high porosity
variety of linkers can be used to get different
pore sizes
15
Hydrogen Storage in Nano-Porous Materials
Molecular Simulations
Results
Adsorption isotherms at 77 K
High uptake of H2
Low Pressure
Low Pressure
High Pressure
High levels of adsorption
Narrow pores materials
IRMOF-1, -4 , -6, -7
High Pressure
High levels of adsorption
Materials with high free volume
IRMOF-10, -16
16
Hydrogen Storage in Nano-Porous Materials
Molecular Simulations
Simulation Snapshots
Low pressure (0.01 bar)
High pressure (120 bar)
Intermediate pressure (30 bar)
H2 fills the majority of the void regions of
material
Molecules preferentially in zinc corners and
along linkers
H2 near zinc corners
17
Hydrogen Storage in Nano-Porous Materials
Questions?
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