Assignment no 1

Subject: Essentials of Nanosciences and Engineering

Submitted to: Dr. Zakir Hussain
Submitted by: Summayya Shafique
Dated : December,20,2020
 Nanomaterials for Hydrogen Storage
Reason for Hydrogen storage
 Petroleum products causes severe health issues and environmental
changes and as you can see in following Fig.

 To overcome these problems, we come to the solution of hydrogen usage.

 Hydrogen produces less Carbon dioxide in combustion.
 Hydrogen is a non-toxic particle, opposes the arrival of ozone harming
substances and air contaminations.
 Hydrogen is a spotless and economical fuel source.
Hydrogen Storage:
Hydrogen store in following forms:

Sorbent and
Compre Liquid Cyro Metal carbon- Chemical
ssed H2 H2 Compressed Hydride based Hydride
materials

Hydrogen has an astoundingly high gravimetric energy thickness of (20 KJ g−1),

which is threefold to the energy density of gas and multiple times to the energy
thickness.
Importance of Nanomaterials:
 Nanomaterials used in Hydrogen storage because of their incredible traits
as adsorption on a superficial level, inter and intragrain limits, and mass
assimilation.
 They also contains high surface /volume ratio.
 Nanostructure frame work includes

Complex
Nano-magnesium Boron nitride Polymer
Carbon nanotubes hydride/carbon Alanates,
based hydrides nanotubes, nanocomposites,
nanocomposites

Physisorption assumes an imperative part in the carbon-based nanomaterials and

MOFs for hydrogen stockpiling, though chemisorption is essentially associated
with metal hydrides and complex hydrides.

Carbonaceous materials
 Carbon-based frameworks have collected huge exploration interest
because of their high surface territories, moderately low costs, quick
energy, and other advantageous adsorption properties.
 Carbon materials adsorbes hydrogen with strength under 10kJ/mol.

 Nanostructured Carbon Materials

 Carbon nanotube having Single Wall can be accepted to frame with rolling
a solitary sheet of Graphene.
o The interesting Property of Carbon nanotubes is that, they are
excellent in carring Hydrogen stock.
o In Carbon nanotubes of Single Wall, all C particles are at the Surface
which elevates the surface to mass ratio and makes the surface
dynamics.
 o Carbon nanotubes have densities lower than covalent organic
frameworks and metal organic frameworks.
o Nanoparticles are known for their large surface to volume ratios and
large numbers of pores, it significantely makes them good hydrogen
carrying material.
Carbon nanotubes adsorbs hydrogen by two process that are given bellow
 Storage of H2 in Gas form
Procedure:
o Take nanotube of weigh under 1g.
o Flow of H2 under different conditions of temperatures and pressure.
o H2 adsorbed by carbon nanotubes is measured by gravimetrically.
o Then do volumetric measurements to find the adsorbtion and
desorbtion of hydrogen gas.

Results:
o By doing volumetric analysis, we get that these nanotubes store upto
8.5wt% of H2 at pressure of 120 bars and bellow 123K temperature.

 Electrochemical cell
Process:
o Carbon nanotubes used as a working terminal.
o Platinum used in cathode.
o Well suited Electrolyte used.
o At some Potential decrease the amount of water to put the hydrogen away
from the cathode.
Result:
o At room temperature hydrogen storage is less than 1wt%. Also it’s capacity
storage is 110 mAh/g.

Carbon nanostructures with Metal Doping:

By doing metal doping we can increase the storage of Hydrogen in carbon
nanostructures.
 Pd-and V-doped CNT
o By using carbon nanotubes doped with Pd and V increases the adsorption
more than 70% onto the lower energy sites.
o Doping doesn't influence the noticed energy of desorption.

 Ti-doped CNTs
o Each carbon nanotubes with Ti particles able to store four atoms of
Hydrogen which gives us 8wt% storage of Hydrogen.
Procedure:
Hydrogen storage in Ti doped carbon nanotubes done through stepwise as shown
above.
a) Firstly, hydrogen detaches with chemisorbes and tie itself on titanium
molecucle surface.
b) Without any energy resistance two particles of hydrogen try to
physisorbed.
c) Next hydrogen try to physisorbed on C-Ti plane to Ti molecule.
Results:
Unexpected bonding explains as
 Doping with Ti causes Hybridization.
 Antibonding in hydrogen atom.
 P orbitals in carbon nanotubes with single wall .
Results are still dubious because:
 The enormous difference in the capacity limits estimated in different
examinations.
Reason for the changes consider as:
 Carbon nanotubes synthesis may contain some metallic contaminations.
 Might be mistake at the end of Volumetric measurements because of the
o There will be some vulnerability in the complete volume of the framework
when the parts are fixed together.
o Hydrogen gas in holes with change in temperatures also changes that we
measure from gravimetric techniques.

Metal-Organic Frameworks:

 These structures have uniformed size enormous cubic holes.

 Metal organic Frameworks of various structures makes them permeable.
 Metal organic Frameworks Surface area is larger than carbon nanotubes ,
clathrates and zeolites.
 Hydrogen storage limit of MOF-5 is 1.0 wt% under ambient conditions.
  H2 storage limit increased upto 1.65 wt% by adding moieties into the
systems at 48 bars of pressure.
 Hydrogen positions on Metal organic frameworks are acquired from the
information of neutron diffraction.
 Atomic structure shows in below diagram tells us where hydrogen particles
are combined.
 COFs are translucent, exceptionally permeable, and enormous surface
territory.
 Covalent organic frameworks have similar properties like metal organic
frameworks, also have low thickness due to the presence of carboxylates of
carbon, silicon, boron, oxygen and bunches of carboxylates.
 Covalent organic frameworks also used for the storage of hydrogen due to
the properties as mentioned earlier.

MOF-5 Structures

Metal-Organic Frameworks with Metal doping:

 To improve storage of hydrogen in MOFs one of the techniques is doping.

 Various strategies of metal doping into MOFs were utilized; the well-known
methods are
o early wetness
o ball processing
 CuBTC take-up limit of hydrogen was expanded upto 3.5 at temperature of
298 K and pressure of 20 bars by using Pt/C as a catalyst.
  Examination of storage of hydrogen limit of unadulterated MIL-101 doped
with MIL-101 through overflow component and adsoption curve is
appeared in Fig.

 Clathrate Hydrates
 They are referred to likewise as confined mixes, since in these frameworks
visitor atoms are blocked in the enclosures shaped by the host particles.
 When water molecules form the confines they are called as clathrate hydrate.
 Structure is of two kinds of Polyhedra
o dodecahedra
o hexadecahedra
 Clathrates stables at very high temperatures and pressure of about 120 bars
 Clathrate known lately for the storage of hydrogen, it is conceivable to
functionalize them at low pressure through blocking enormous natural atoms.
(e. g . tetrahydrofuran)
 They can store hydrogen upto 5 wt% which can be measured by gravimetric.
 These are good for storage of hydrogen also they are economical.

Intermetallic and Metallic Hydrides

 At high temperature hydrogen combinations with metals gives us different

hydrides.
 Element that are reactive towards hydrogen and gives us different hydrides
are:
o Lanthanide
o Actinides
o Titanium group
o Vanadium group
 These are metal in nature and gives us metallic hydrides.
 They expressed in formula as MHx.
 Intermetallic Hydrides are expressed in Formula like ABnHx.
 A shows the alkaline earth metals and transition metals are shown by B.
 The combinations of intermetallic hydrides depends on the amount of A and B
we used, also their properties changes with respect to their compositions.
 Let’s take an example of LaNiH6 here lanthanum shows A and nickel is B.
 Metallic Hydrides are good in storing hydrogen as the can store upto 3wt%.
 People seeks more ways to enhance the property of hydrogen storage upto
5wt%.