THE UNIVERSITY OF PUNJAB,

QUAID-E-AZAM CAMPUS, LAHORE

SCHOOL OF CHEMISTRY

HINA SHAHZAD

ROLL NO; 69

BS CHEMISTRY 6TH SEMESTER (MORNING)

PHYSICAL CHEMISTRY ASSIGNMENT

SUBMITTED TO: DR. ZAHOOR AHMED

FAROOQI
Kinetics and Mechanism of Catalytic
Reduction of CO2: A Review
1. Introduction:
Fossil fuels have been the primary source to produce energy for industrial applications and

human activities for decades leading to high concentration of atmospheric CO2 that create

serious environmental, ecological, and climate problems. It is now essential to find improved

catalysts to convert CO2 to useful chemicals. Indeed progress is being made in

electrochemical transformation of CO2 into chemical fuels, however, the extreme stability of

CO2 makes it inert for chemical reactions in aqueous solution, demanding a large

overpotential to overcome the high activation barrier. Moreover, the hydrogen evolution

reaction (HER) side reaction can easily dominate under the same conditions, diminishing

efficiency. Thus we want CO2 reduction catalysts with high faradic efficiency for CO but

negligible HER faradic efficiency.

Strategies are now being actively sought to mitigate CO2 emissions by improving fossil fuel

combustion efficiency or exploring clean and renewable energy sources (e.g., wind, tide, and

solar energy). Alternatively, great efforts are also being undertaken to develop carbon capture

and storage (CCS) techniques that fix atmospheric CO2 and store it underground in a

supercritical state. However, the CCS technique itself is energy-intensive and nonrenewable.
In nature, the photosynthesis of green plants plays an indispensable role in maintaining the

carbon/oxygen cycle which is vital for the maintenance of life on earth. It consists of two

sequential steps known as the light and dark reactions. In the light reaction, chlorophyll

absorbs sunlight, converts it to the chemical energy stored in adenosine triphosphate (ATP),

and meanwhile oxidizes water to O2. In the dark reaction, CO2 is fixed and reduced stepwise

to form carbohydrates using energy stored in ATP. The natural photosynthesis essentially

provides the energy needed for most lives on this planet and is the basis for the survival of

mankind.

For more than three decades, researchers have been ambitiously attempting to mimic what

Mother Nature does and pursuing artificial photosynthesis that aims at the spontaneous

transformation of atmospheric CO2 and water to chemical fuels using sunlight as the sole

energy input. Although still at very low efficiency currently, artificial photosynthesis is

believed to have the great potential to make a substantial contribution to our future energy

supply. It is now generally approached from two directions. As schematically illustrated in,

the first route uses photovoltaic (PV) cells to generate a sufficient photovoltage which is then

supplied to the cathode for the CO2 reduction and the anode for the water oxidation.

Proper electrocatalysts are employed on the two electrodes so as to expedite the reaction rate

and improve the reaction selectivity. The advantage of this route is the flexibility in the

design of PV and electrocatalyst pairs. Components can be individually optimized and then

combined together to enable the best overall performance. The second route is the direct

photocatalytic approach where light-absorbing semiconductor particles (photocatalysts)

decorated with suitable electrocatalysts (commonly referred as cocatalysts in photocatalysis)

are dispersed in an aqueous solution and achieve light harvesting, charge separation, and

interfacial charge transfer to drive corresponding reactions all within particles.

The merit of the second route is its wireless configuration which renders the device design

much more straightforward and compact. At this moment, it is too early to judge which route

will eventually dominate in the future. Their future success strongly relies on the

development of high-performance CO2 reduction electrocatalysts or photocatalysts. Since

CO2 is a thermodynamically stable molecule, its multistep reduction via the electrochemical

or photochemical approach is significantly more challenging than the splitting of water, and

confronted with many fundamental technical hurdles.The history of electrocatalytic CO2

reduction can be traced back to 19th century. In 1870, Royer first reported the reduction of

CO2 to formic acid on Zn electrodes.

Between 1970s and 1980s, a series of seminal works published by Japanese scientists marked

the advent of a new phase in electrocatalytic CO2 reduction research. Ito and Murata

examined the electrocatalytic performances of several metals such as In, Cd, Sn, Zn, and Pb

for reducing CO2 to formic acid. Hori et al. Discovered that polycrystalline Cu electrodes in

aqueous media could generate short-chain hydrocarbons with a promising activity. Studies on

photocatalytic CO2 reduction commenced in 1970s. In 1978, Halmannn first observed that

CO2 was reduced to CH3OH and CO on a p-type GaP electrode under light illumination. In

the year later, Inoue et al. Reported that formic acid, formaldehyde, and methyl alcohol were

produced from the photocatalytic reduction of CO2 in the aqueous suspensions of

semiconductors such as TiO2, ZnO, CdS, GaP, and SiC.

Following these pioneering works on electrocatalytic or photocatalytic CO2 reduction,

increasing attention has been attracted to this field, and many exciting progresses have been

made in recent years. An overview of the recent progress on electrocatalytic or photocatalytic

CO2 reduction. Several previous high-quality review articles on similar topics are

available.16-26 Given the recent heightened research activities and increasingly deepened

understanding of these two processes, we believe that an up-to-date account on their status

and existing challenges is necessary so as to provide readers with a current snapshot of this

rapidly evolving area.

Even though the two approaches involve dissimilar experimental techniques, their nature is

essentially identical—that is how to activate the chemically inert CO2 molecule and promote

its conversion under external energy stimuli. In addition, the surface charge transfer step in

photocatalysis is in fact an electrochemical process and can be enhanced via the incorporation

of proper cocatalysts. These are the reasons why we think electrocatalytic and photocatalytic

CO2 reduction are inherently connected and decided to discuss them together here. This

review starts with a brief description of the basic principles and important performance merits

of electrocatalytic and photocatalytic CO2 reduction.

2. Characterization of Catalytic systems used for

reduction of CO2
Catalytic systems play a pivotal role in the reduction of CO2, determining the efficiency,

selectivity, and sustainability of the process. The characterization of these catalysts provides

insights into their structure, functionality, and interaction with CO2 molecules.
Types of Catalytic Systems;

Catalytic systems for CO2 reduction are broadly classified into three categories:

1. Metal catalysts

2. Organometallic catalysts

3. Enzymatic catalysts.

1. Metal Catalysts;

Metal catalysts, such as copper (Cu), nickel (Ni), platinum (Pt), and ruthenium (Ru), are

highly effective in activating CO2 by facilitating electron transfer. They are extensively used

in electrochemical and thermochemical reduction processes.

● High thermal stability.

● Versatility in forming multiple products, e.g., methane, methanol.

● Mechanism: Metals activate CO2 by forming a CO2-metal complex, which lowers the

activation energy for bond cleavage.

Fig. Activation of CO2 by metal catalyst

2. Organometallic Catalysts;

Organometallic catalysts, particularly Ru and Fe complexes, provide high selectivity and

tunability. Ligands in these complexes influence the reactivity of the central metal atom,

enhancing catalytic performance.

Example Reaction;

Figure: Structure of a Ru-based Organometallic Catalyst for CO2 Reduction

3. Enzymatic Catalysts;

Enzymatic catalysts such as formate dehydrogenase and carbon monoxide dehydrogenase

mimic natural biological processes for CO2 reduction. These systems exhibit high selectivity

under mild reaction conditions.

 ● Environmentally benign.

● Operate at room temperature and pressure.

Characterization Techniques;

To evaluate the efficiency and functionality of catalysts, various advanced characterization

techniques are employed. These techniques reveal information about structural,

morphological, and electronic properties.

Structural Characterization;

1. X-ray Diffraction (XRD):

XRD is used to determine the crystal structure, phase composition, and crystallinity of

catalysts. By identifying the phases present, XRD can indicate how the structure

might affect catalytic performance and stability. Changes in diffraction patterns

before and after reactions can provide insight into phase changes and catalyst

stability.

2. Electron Microscopy (SEM, TEM, and HRTEM):

Scanning Electron Microscopy (SEM): Provides high-resolution images of catalyst

morphology and particle size distribution, which helps in understanding surface

structure and roughness. Transmission Electron Microscopy (TEM) and High-

Resolution TEM (HRTEM): Offer detailed, atomic-scale structural information on

catalyst nanoparticles and support materials. HRTEM reveals crystallographic details

and the distribution of active sites.

 3. Energy Dispersive X-ray Spectroscopy (EDS):

Often integrated with SEM or TEM, EDS maps the elemental composition and

distribution of components on the catalyst’s surface.

4. Atomic Force Microscopy (AFM):

AFM creates high-resolution, three-dimensional surface images and provides

information on topography and surface roughness, essential for understanding the

active site exposure and nanoparticle distribution on the catalyst surface.

Surface and Electronic Characterization Techniques;

1. X-ray Photoelectron Spectroscopy (XPS):

XPS provides information on surface composition, chemical states, and oxidation

states of elements in the catalyst. This is particularly useful for studying how the

electronic structure of surface atoms changes during CO₂ adsorption and reduction.

By analyzing shifts in binding energy, XPS helps identify the nature of active sites

and any chemical modifications occurring during the reaction.

2. Auger Electron Spectroscopy (AES):

AES is used to analyze surface composition with high spatial resolution, detecting

elements on the surface of catalysts and tracking their changes under reaction

conditions.

3. Infrared Spectroscopy (IR) and Raman Spectroscopy:

Fourier-Transform Infrared Spectroscopy (FTIR): FTIR detects vibrational modes of

surface-bound species, providing information on adsorption and interaction with CO₂.

 In-situ FTIR can monitor changes in real time, helping to identify reaction

intermediates.

4. X-ray Absorption Spectroscopy (XAS):

X-ray Absorption Near Edge Structure (XANES) offers insights into the oxidation

state and local atomic structure of elements, helping to identify changes in the

electronic structure during the reaction.

5. Extended X-ray Absorption Fine Structure (EXAFS):

Provides details on the coordination environment and distances between atoms, which

is crucial for understanding active sites and metal-support interactions in

heterogeneous catalysts.

Kinetic and Mechanistic Characterization Techniques

1. Temperature-Programmed Desorption (TPD):

TPD measures the desorption of adsorbed species from a catalyst’s surface as

temperature increases, providing data on adsorption strength and active sites.

2. Temperature-Programmed Reduction (TPR) and Temperature-Programmed Oxidation

(TPO):

TPR and TPO reveal the reducibility and oxidation behavior of catalysts, which are

important for understanding catalyst stability and reaction conditions.

 3. Mass Spectrometry (MS):

Often coupled with TPD or FTIR, MS identifies and quantifies gaseous products

during reactions, allowing for real-time analysis of reaction products and

intermediates.

4. Electrochemical Techniques (EIS and CV):

Electrochemical Impedance Spectroscopy (EIS): Provides insights into electron

transfer properties and resistance in electrocatalytic systems, essential for

understanding charge transfer at the electrode-electrolyte interface.

5. Cyclic Voltammetry (CV):

Measures current response to a variable voltage, helping to study redox reactions and

adsorption-desorption behavior of catalysts under electrocatalytic conditions.

Additional Characterization Techniques

1. Nuclear Magnetic Resonance (NMR) Spectroscopy:

NMR is useful for analyzing homogeneous catalysts and reaction intermediates in

solution, providing information on molecular structure, reaction pathways, and

catalyst-ligand interactions.

2. Electron Paramagnetic Resonance (EPR):

EPR detects unpaired electrons, which is useful for studying radicals and reaction

intermediates in catalytic systems, especially for photocatalytic and electrocatalytic

applications.
The characterization of catalytic systems is critical for optimizing CO2 reduction processes.

Techniques such as XRD, SEM, BET, and XPS provide valuable insights into the structure

and performance of catalysts. Metal and organometallic catalysts dominate industrial

applications due to their efficiency, while enzymatic catalysts offer eco-friendly alternatives.

3. Study of Catalytic Process

The catalytic reduction of CO2 involves intricate processes that depend on the type of

catalyst, reaction conditions, and the interaction between CO2 and the catalytic surface.

Reaction Pathway;

CO2 reduction can proceed through multiple pathways depending on the catalyst and

operating conditions. One of the primary pathways is;

● Electrochemical reduction

Electrochemical Reduction of CO2;

The electrolytic reduction of CO2, also known as electrochemical reduction, is a process

where CO2 is converted into value-added products such as formic acid, carbon monoxide,

methane, and methanol using electricity. This reaction occurs in an electrochemical cell and

involves multiple proton-electron transfer steps.

● Cathode: Reduction of CO2 occurs at this electrode. Common materials include

copper, silver, and gold.

● Anode: Oxygen evolution reaction occurs here, typically using platinum or iridium

oxide.
 ● Electrolyte: An aqueous or non-aqueous medium to facilitate ionic conductivity (e.g.,

KHCO3)

● Voltage: Depends on the product targeted (formate, CO, etc.).

● pH: Controls the availability of protons for the reaction.

● Catalyst: Determines product selectivity.

General Mechanistic Steps;

1. CO2 Adsorption: CO2 molecules are adsorbed onto the cathode surface, where they

interact with the catalyst.

2. Electron Transfer: The adsorbed CO2 molecule undergoes sequential electron-proton

transfer reactions, forming reactive intermediates.

3. Formation of Products: Depending on the pathway, intermediates stabilize into

specific products such as formate, methane, or methanol.

Fig; Electrolytic cell for the electrochemical reduction of CO2

The Mechanism of Electrocatalytic Reduction of CO2;

The electrocatalytic reduction of CO2 often occurs at the interface between the electrode and

the electrolyte, and the electrolyte is usually an aqueous solution of potassium bicarbonate.
As shown in Figure, the multiphase catalytic process generally consists of four main steps:

(i) The CO2 in the solution diffuses to the surface of the working electrode.

(ii) The electrocatalyst adsorbs CO2 from the solution.

(iii) Electron transfer or proton migration is used to cleave C-O bonds or form C-H bonds.

(iv) The generated products are detached from the electrocatalyst surface and diffused into

the electrolyte.

The adsorption of CO2 on the electrocatalyst surface is an important step

in the whole reaction. During the adsorption process, the C=O bonding is

strongly perturbed by the substrate, and the electrons are shared

between the CO2 and the catalyst. A number of reaction mechanisms

have been proposed for the conversion of CO2. It is widely accepted that

the reactive species are the neutral hydrated CO2 molecules, and they will

convert into CO2•− in the adsorption process on most of the main-group

metal electrodes in aqueous media. Then the absorbed CO2•− reacts with

the H2O molecules to form HCO2•. The intermediate would convert into to

HCO2− because of its unstable unpaired electron, followed by the

desorption of HCO2− species

Reaction mechanism of electrochemical CO2 reduction

Reaction Pathways;

1. Single-Electron Reduction:

The initial reduction of CO2 involves a single-electron transfer to form a CO2 radical anion:

CO2+e−→CO2−

Proton-Electron Coupling Pathways:

1. Formic Acid Pathway;

CO2+2H++2e−→HCOOH

Common in catalysts like Sn, Pb, and In.

2. Carbon Monoxide Pathway:

CO2+2H++2e−→CO+H2O

Catalyzed by Ag, Au, and Zn.

3. Methane Pathway:

CO2+8H++8e−→CH4+2H2O

Occurs on copper electrodes under low overpotentials.

4. Methanol Pathway:

CO2+6H++6e−→CH3OH+H2O

Catalyzed by Cu or Ni complexes.
Energy Diagram;

Fig; Free energy diagram for the electrochemical reduction of CO 2 to CH 4 on Pt(111) using
the computational hydrogen electrode at 0 V vs. RHE. Each step along the horizontal axis
represents the transfer of a proton (from the solution) and an electron (from the electrode) to
the adsorbate. The present work focuses on the barriers for the first four numbered steps.

Catalyst Role in Pathways;

Copper:
● Versatile catalyst for producing CH4, C2H4, and CH3OH.
● Stabilizes multi-carbon intermediates.

Silver/Gold:

● Excellent for CO production due to low overpotentials.

Tin/Lead:
● Favor formic acid/formate formation under mild conditions.

4. Challenges and Future Directions

Despite significant advances, challenges remain in achieving high selectivity, efficiency, and

stability in CO₂ reduction catalysts. Future research directions include:

● Developing catalysts with higher selectivity and stability: Designing catalysts with

tailored active sites can improve selectivity towards specific products.

 ● Understanding the reaction mechanism in detail: In situ and operando techniques can

provide insights into intermediate species and reaction dynamics.

● Improving energy efficiency: For practical applications, reducing the energy input

required for CO₂ reduction is crucial.

● Scaling up: Moving from laboratory-scale experiments to industrial applications

requires catalysts that can operate efficiently at larger scales and in real-world

conditions.

5. Conclusions and Outlook

The study of electrocatalytic CO2 reduction is of great importance for spacecraft life support

systems and energy storage conversion. However, research on CO2 electrocatalytic reduction

is still at the laboratory stage due to the high overpotential of CO2 electrocatalytic reduction,

the low reduction yield, and the lack of in-depth research on the catalytic mechanism. In

order to solve these problems, researchers need to make continuous improvements in catalyst,

electrolyte, and reactor design, and explore efficient methods for the electrocatalytic

reduction of CO2.

(1) The core of electrocatalytic CO2 reduction is how to prepare efficient electrocatalysts that

can use their catalytic activity to reduce external electron energy input and energy

consumption, while improving the selectivity and controllability of the reduction products.

Meanwhile, the catalyst must be able to achieve multielectron and multiproton transfer to

enable efficient electrocatalytic reduction of CO2 on the same surface.

(2) It is necessary to find new electrolyte systems that can synergize with the catalyst in

organic systems and to analyze the specific functions of the electrolyte in the electrocatalytic
reduction of CO2 and the mechanism of action in situ in order to better understand the

electrocatalytic reduction of CO2.

(3) Although the design of the reactor is still at a preliminary stage, the size, shape, and

structure of the reactor are of great importance to improve the efficiency and selectivity of

electrocatalytic CO2. Therefore, to further promote the practical application of CO2

electrocatalytic reduction, this research needs to be further strengthened.

In conclusion, as an effective means of CO2 recycling in space stations, the electrocatalytic

reduction of CO2 has bright research prospects, and this field can further enrich catalytic

science and catalytic technology, thus advancing the progress of scientific research in related

fields.

References;

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