Introduction to CO2 Reduction

• Need for CO2 Reduction: The rising

levels of atmospheric CO2, primarily due
to fossil fuel consumption, are a major
contributor to climate change. Reducing
CO2 is essential to mitigate global
warming and develop sustainable
energy solutions. CO2 reduction
technologies aim to convert this
greenhouse gas into value-added
products, thus closing the carbon cycle
and reducing net emissions.
 Methods For CO2 Reduction

Electrochemic Photocatalytic Thermocatalyti Biochemical

al Reduction Reduction c Reduction Reduction
•Utilizes light •Involves high- •Uses biological
•Uses Electrical
energy to excite temperature systems like
Energy to drive electrons in a reactions where enzymes or
CO2 Reduction semiconductor CO2 is reduced
material, which
microorganisms
in an by a hydrogen
then reduces CO2 source, typically
to convert CO2
electrochemic into organic
to various using metal
al cell products. compounds.
catalysts.

Zhang, W., Hu, Y., Ma, L., Zhu, G., & Chen, X. (2017). Electrochemical Reduction of CO2 to C2+ Products on Copper Catalysts: Mechanistic Insights. Joule, 1(4),
620-633. DOI: 10.1016/j.joule.2017.10.002.
 Why Electrochemical CO2 Reduction
• Sustainability: Produces lesser
Environmental effect.
• Mild Operating Conditions: Usually
occurs at ambient temperature and
pressure, which reduces the energy input
required.
• Scalability: Easily scalable with existing
renewable energy infrastructures.
• High Selectivity: Ability to precisely
control product distribution by varying
the electrode potential and catalyst
properties.
Review Article Electrolytic cell design for electrochemical CO2 reduction Shuyu Liang, Naveed Altaf, Liang Huang, Yanshan Gao, Qiang Wang⁎
College of Environmental Science and Engineering, Beijing Forestry University, 35 Qinghua East Road, Haidian District, Beijing, 100083, PR China
 Single Atom Catalyst
(SACs)
 Isolated metal atoms dispersed on a substrate

 Well-defined active sites for catalytic

reactions.

 Catalytic Efficiency
Ni–SAC model diagram containing Ni–N4 and Ni–
N2C2 moieties as active sites for CO2RR
 Applications in CO2RR
Ni N C

 Stability Challenges
Synthesis Of Cu-HOF
Synthesis of HOF-Cu-SAC
Synthesis of Cu-Sn-HOF
 Chemical Reactions

Hydrogen Bonding between

Melamine and TMA
C3​H6​N6⋯⋯
​ C9​H6​O6​
HF removes the silica
shell, exposing the thin-
SiO2​+4HF→SiF4​+2H2​O walled nanotube structure
of the final catalyst
Simplified structural form Melamine−NH2⋯
​ O=C−TMA
Pyrolysis decomposes
the organic framework,
Cu-HOF-T@SiO2​​→TWN-Cu-600-SACs + SiO2​ leaving behind a
nitrogen-doped carbon
HOF synthesized
matrix with dispersed Cu
atoms. The silica layer
prevents Cu from
Copper ion interacts with
clustering.
N and O donor sites CuCl2​→Cu2++2Cl− C8​H20​O4​Si (TEOS)+2H2​O→SiO2​+4C2​H5​OH
TEOS forms a protective
silica coating around Cu-
HOF-T, preventing the
These chloride ions are aggregation of Cu atoms
removed during washing
CuCl2​+HOF-T→Cu-HOF-T+2Cl− during pyrolysis.
process
 Characterization Techniques Required

1. Scanning Electron Microscopy (SEM)

2. Transmission Electron Microscopy (TEM)
3. High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy (HAADF-
STEM)
4. Energy-Dispersive X-ray Spectroscopy (EDS)
5. X-ray Diffraction (XRD)
6. X-ray Absorption Near Edge Structure (XANES)
7. Extended X-ray Absorption Fine Structure (EXAFS)
8. Fourier Transform Infrared Spectroscopy (FTIR)
9. Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES)
10.X-ray Photoelectron Spectroscopy (XPS)
11.Electrochemical Characterization (including Linear Sweep Voltammetry (LSV), Cyclic
Voltammetry (CV), and Chronoamperometry)
12.Surface-Enhanced Raman Spectroscopy (SERS)
13.Differential Scanning Calorimetry (DSC)
 Cu-HOF Cu-HOF-SiO2
Si

O O O
Trimesic Acid Si
O
O O
H
O O Si
H
O
O O
H H H H O O
N O H H H H
O
H H O O H H
N
N O O
N
N N N N
Cu O
N N N N H H
H H
N N N Si N N N
H H
H H N N N
N N N Cu H H
H H Cu
Cu Melamine H H
H H Si
Melamine
O
H H H H

H H H H N N N Cu N N N
H H H H O
N N N N N N O
H H
Cu H H
N N N N

O O
N N N N N N
H H H H H H O
O O O O
N N
H H H H Si
H H
O O
H
O O O Si
Melamine Melamine
O
H O
O O
O
Trimesic Acid O
Si O
Si
 TWN-Cu-SAC

O O
H

O O
H H
O O
O O
O O H H H H H
H N N

N N N N
O O
O O H H H H H
H H N N N N N N H

H
N
H
O O
H
N
H
H
H
H
Cu
H
H

H
H

H H H
O O
H
N
H
N
N N N N N N
N N H H H H
N N N N N N
H H N N N N
H H N H H H H
N N N N N N N N
N N N
H
H
H
Cu
H
H

H
H

H
H
N
H

O
H
N
H
H
H
H
H
Cu H
H

H
H

O
N N N N N N H N N N
H H H N N N
H H H H H H
O O
N N N N N N N N

N N N
H H N
H H H H H H
H O O
O O O
O
H H H
H O O
O O

H
H O O
O O
 Proposed Methodology

1- Coating HOF with TiO₂ or Al₂O₃ before pyrolysis (Ti[OCH(CH₃)₂]₄) or

TiO2 sol + HOF stir DI
(Al[OCH(CH₃)₂]₃)
water + stirring centrifuge
washing pyrolysis

2-Microwave-Assisted Synthesis for creating hydrogen- Dissolve all the chemicals inside a microwave-safe
bonded organic frameworks (HOF) Pyrex vessel Microwave( 150 degree, 100-
200psi, 10-30 minutes) Centrifuge
coating with SiO2
pyrolysis
3-Choose Alternative Ligands
Terephthalic Acid , or Isophthalic Acid
Metal-Organic Framework (MOF)-based Ligands:
Ligands like 2,6-naphthalenedicarboxylic acid (NDC)
or benzimidazole, which are often used in MOFs for
enhanced metal-ligand interactions.