Investigation on the Catalytic and

Electrochemical Conversion of
Carbon Dioxide to Fuel
Presented by: Catherine Firmase-Monarquia
2001129903
 Background of the Study

As of September 16, 2017

406.95 PPM CO2 in the atmosphere
Ideal Carbon Dioxide Cycle
Process Solutions

Catalytic Conversions

Artificial Photosynthesis
Objectives of the Study

This study aims to investigate the conversion of CO2 via catalytic

and electrochemical methods

Explore suitable catalyst with minimum energy requirement for

the conversion of Carbon Dioxide to useful fuel feedstock
employing principles in inorganic chemistry for evaluation.
Catalysis

• A catalyst increases the rates of

processes by introducing new
pathways with lower Gibbsenergies
of activation; the reaction profile
contains no high peaks and no deep
troughs
Photocatalytic Reduction of CO2
CO2 Hydrogenation

• Alkenes are hydrogenated on

supported metal particles by a
process that involves H2
dissociation and migration of H. to
an adsorbed ethene molecule.
Skeletal nickels can be used to
reduce alkanals to alkanols.
The nature of heterogeneous catalysts

Surface area and porosity

• Heterogeneous catalysts are high-surface-area materials formed as either
finely divided substrates or crystallites with accessible internal pores.
Surface acidic and basic sites
• Surface acids and bases are highly active for catalytic reactions such as the
dehydration of alcohols and isomerization of alkenes.
• Surface metal sites
• Key points: Very small metal
particles on ceramic oxide
substrates are very active
catalysts for a range of
reactions.
• The metal atoms on the
surface of metal clusters are
capable of forming bonds
such as MCO, MCH2R, MH,
and MO
• Chemisorption and desorption
• Adsorption is essential for heterogeneous
catalysis to occur but must not be so
strong that it blocks the catalytic sites
and prevents further reaction.
• Surface migration
• Adsorbed atoms and molecules migrate over metal surfaces.
• These diffusion pathways generally involve the adsorbed molecules moving
through a variety of different coordination sites on the metal surface.
• The energy barrier to this process is relatively low, a few tens of kilojoules
per mole, and thus migration rates are very high under typical catalytic
reaction conditions.
• This mobility is important in catalytic reactions as it allows atoms or
molecules to find and approach one another rapidly.
Relevant Studies

High-Selectivity Electrochemical Conversion of CO2 to Ethanol using a

Copper Nanoparticle/N-Doped Graphene Electrode

• an electrocatalyst which operates at room temperature and in water for

the electroreduction of dissolved CO2 with high selectivity for ethanol.
• the high selectivity for a 12-electron reaction suggests that
nanostructured surfaces with multiple reactive sites in close proximity
can yield novel reaction mechanisms.
• This suggests that the synergistic effect from interactions between Cu
and CNS presents a novel strategy for designing highly selective
electrocatalysts.
Relevant Studies

Directly Converting CO2 into a Gasoline

• we have succeeded in preparing a highly

selective Na–Fe3O4/HZSM-5 multifunctional
catalyst for the direct production of gasoline
from CO2 hydrogenation.
• This catalyst enables RWGS over Fe3O4 sites,
olefin synthesis over Fe5C2 sites, and
oligomerization/ aromatization/ isomerization
over zeolite acid sites.
• The concerted action of the active sites calls
for precise control of their structures and
proximity.
The catalyst for investigation on Carbon Dioxide
conversion to fuel precursors are:

• Cu/ N-dopped Graphene (Carbon Nanospikes)

• Cu/TiO2

• Fe3O4/Zeolite (ZSM-5)
Methodology

• Linear Sweep Voltametry

• X-Ray Absorption Fine Structure
• Products and Reactants determination via GC MS & ICP-OES
• Surface characterization via Scanning Electron Microscopy
Establish Correlation between

• Catalytic activity
• High selectivity to formation of desired product (ethanol)
• Long life (re use)

• Coordination Number of catalyst support

• Surface Structure
Coordination Number

Titanium Dioxide: Rutile

Titanium (IV)
Rutile has a tetragonal unit cell. The
titanium cations have a coordination
number of 6, meaning they are
surrounded by an octahedron of 6
oxygen atoms. The oxygen anions
have a coordination number of 3,
resulting in a trigonal planar
coordination.
• Titanium Dioxide: Anatase

• Cordination no. 6
• Due to its functionality as a semiconductor
oxide photocatalyst and its considerable
interest towards Grätzel-cell photovoltaics, a
majority of studies into anatase materials
have focused on synthetic materials in
powder and thin film forms rather than
naturally occurring minerals.
Graphene Coordination Number

• Graphene

• Graphene is an allotrope (form) of carbon

consisting of a single layer of carbon atoms
arranged in an hexagonal lattice.
• The electron hybridization predetermines the
ability of carbon atoms to arrange numerous
compounds with other elements of the periodic
table, but also the various allotropes, such as
carbyne/carbyte, graphene/graphite and
diamond which are structured with linear, planar
and tetrahedral symmetry, coordination numbers
of 2, 3 and 4.
 ZSM-5 Zeolite

• ZSM-5, Zeolite Socony Mobil–5 (framework

type MFI from ZSM-5 (five)), is
an aluminosilicate zeolite belonging to the
pentasil family of zeolites. Its chemical
formula is NanAlnSi96–nO192·16H2O (0<n<27).
Patented by Mobil Oil Company in 1975, it is
widely used in the petroleum industryas
a heterogeneouscatalyst for hydrocarbon iso
merization reactions.
• The estimated pore size of the channel
running parallel with the corrugations is
5.4–5.6 Å.[3] The crystallographic unit cell of
ZSM-5 has 96 T sites (Si or Al), 192 O sites,
and a number of compensating cations
depending on the Si/Al ratio, which ranges
from 12 to infinity.
Expected Results and Discussion

• High selectivity electrochemical conversion of CO2 to ethanol can be

carried out using a Cu Nanoparticle/N-Doped Graphene Electrode.
• The CNS structure is disordered due to the high nitrogen content which
prevents well-ordered stacking
• It was suggested that synergistic effect from the interaction of Cu and
the Carbon Nano Spike provided a highly selective approach for the
formation of ethanol.
• Wei et al, reports a highly efficient, stable and multifunctional Na–
Fe3O4/HZSM-5 catalyst, which can directly convert CO2 to gasoline-
range (C5–C11) hydrocarbons with selectivity up to 78% of all
hydrocarbons
Expected Results and Discussion

• The search for a catalyst contemplating conversion, selectivity

and deactivation problems is still continuing and some researchers
have tried to use transition metal carbides.
• Different carbides were then tested and the results indicated that
Mo2C and Fe3C showed high CO2 conversion and good methanol
selectivity, while TaC and SiC were almost inactive.
• there is a significant room for further catalyst development
studies incorporating also reaction engineering aspects.
Thank you!
• For the the Nickel/Ceria-Zirconia studies by Cai, et all have
investigated Ni/ceria–zirconia solid solution (Ni/CexZr1 − xO2) with
Ce and Ni enriched on the surface of the catalysts are prepared
via a simple, low-cost method was successful in the conversion of
CO2 to a variety of products including ethanol.
• The impregnation method makes the Ni enriching on the surface of
products which enhances the efficiency of active component.
These catalysts exhibit significantly high catalytic performance.
• https://www.differ.nl/research/solar-fuels
• http://newenergyandfuel.com/http:/newenergyandfuel/com/201
5/08/12/new-catalyst-makes-carbon-dioxide-into-methanol-fuel/