TABLE OF CONTENTS:

1.KEYBOARDS:..........................................................................................................................................2
2.ABSTRACT:..............................................................................................................................................2
3.INTRODUCTION:...................................................................................................................................2
4.PHOTOCATALYTIC REDUCTION:....................................................................................................4
i.PHOTOCATALYTIC PROCESS USING TiO2 PELLETS:............................................................5
ii.PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE:....................................................5
iii.EFFECT OF METAL ION ON REDUCTION PRODUCTS:........................................................7
5.EXPERIMENTAL SET-UP:....................................................................................................................7
6.PROPOSED MECHANISM:...................................................................................................................9
7.CHARACTERIZATION OF CATALYTIC SYSTEM:........................................................................9
i.CHARACTERIZATION TECHNIQUES:......................................................................................11
a.UV–vis spectra of in-situ catalysts:..............................................................................................11
b.FT-IR spectra of catalysts:...........................................................................................................11
c.XRD spectra of catalysts:.............................................................................................................12
d.TG–DTA spectra of catalysts:......................................................................................................13
ii.PARTICLE SIZE DISTRIBUTION:....................................................................................................13
8.PROCEDURE FOR CATALYSTS PREPARATION:.........................................................................14
9.STUDY OF CATALYTIC PROCESS:..................................................................................................15
9.1.KEY ASPECTS FOR STYDYING CATALYTIC CO2 REDUCTION:....................................15
i.Types of Catalysts in CO2 Reduction:.........................................................................................15
ii.Methods of CO2 Reduction with Catalysts:...............................................................................16
iii.Titanium Dioxide (TiO2) as a Catalyst:.....................................................................................16
iv.Key Goals in CO2 Reduction Studies:........................................................................................17
v.Current Challenges in CO2 Reduction Catalysis:......................................................................17
10.FUTURE DIRECTIONS FOR CARBON DIOXIDE REDUCTION(CDR):.................................18
11.CONFLICT OF INTEREST STATEMENT:......................................................................................20
12.ACKNOWLEDGEMENTS:................................................................................................................20
13.CONCLUSION:....................................................................................................................................20
14.REFERENCES:....................................................................................................................................21
15. LIST OF ABBREVIATIONS:.............................................................................................................22

1
1.KEYBOARDS:
CO2 reduction, Photocatalysis, In-situ synthesis, CoPc/TiO2, Visible light, Energy storage, Titanium oxide
pellets.

2.ABSTRACT:

Elimination or reduction of carbon dioxide (CO2) in the atmosphere is a serious problem faced
by humankind, and it has become imperative for chemists to find ways of transforming
undesirable CO2 to useful chemicals. One of the best means is the use of solar energy for the
photochemical reduction of CO2. In spite of considerable efforts, discovery of stable
photocatalysts which work in the absence of scavengers has remained a challenge although
encouraging results have been obtained in the photocatalytic reduction of CO2 in both gas and
liquid phases. Semiconductor-based catalysts, multicomponent semiconductors, metal–organic
frameworks (MOFs), and dyes as well as composites involving novel composite materials
containing graphitic carbon nitride (C3N4) and molybdenum disulfide (MoS2) have been
employed for the photoreduction process. Semiconductor heterostructures, especially those
containing bimetallic alloys as well as chemical modification of oxides and other materials with
aliovalent anion substitution (N3– and F– in place of O2–), remain worthwhile efforts. In this
article, we provide a brief perspective of the present status of photocatalytic reduction of CO2 in
both liquid and gas phases.

3.INTRODUCTION:
The final aim of photo-catalysis is efficiently converting solar light energy into useful chemical
energy. The effective utilization of clean, safe and abundant solar energy will lead to promising
solution not only for energy issues due to the consumption of natural energy sources but also for
many problems caused by environmental pollution, for example, CO2. Greenhouse gas CO2 is
the primary cause of global warming. It can be transformed into hydrocarbons in photo-catalytic
reaction. Previous work on the photo-catalytic reduction of CO2 focused on titanium dioxide

2
(TiO2) and ultraviolet radiations (UV). For example, I-Hsiang has gained methanol 4.7 μmol/g
catal. in the system of TiO2 powder and aqueous solution illuminating at 254 nm for 6 h. The
quantum efficiency was 0.42% because TiO2 semiconductors had a relatively large band gap of
3.2 eV, corresponding to wavelengths shorter than 388 nm. In other words, TiO2 by itself can
make use of only 3–4% of the solar energy that reaches the earth, demanding a UV light source
for its use as a photo-catalyst. So many methods had been studied to widen the absorption
wavelength of TiO2, for example, nano-sized TiO2 particles, TiO2 thin films, highly dispersed
titanium oxide species within the zeolite cavities, titanium oxide-based binary catalysts, metal
ion loaded on surface of TiO2 photo-catalysts, etc.
Phthalocyanines (Pc-s) are a class of organic compounds which have received considerable
attention from scientists because of their potential applications in a variety of fields. Their unique
properties include excellent semi-conductivity, photoconductivity, chemical stability and optical
absorption in the ultraviolet-visible (UV–vis) region. Most of the studies conducted so far on Pc-
s are either in film, vapor or in any solvent medium, whereas only a limited amount of work has
been reported in solid matrices. For example, zinc-phthalocyanine (ZnPc) with tyrosine
substituent was attached to different nanocrystalline semiconductors tin oxide (SnO2) and zinc
oxide (ZnO) via carboxylic acid group. Anchoring of the dye complex to the nanocrystalline
semiconductors enables ultrafast injection of electrons from the excited state into the conduction
band of semiconductors and photon-to-current conversion efficiency was improved. We have
reported about the photo-reduction of CO2 using sol–gel derived titania-supported zinc or cobalt-
phthalocyanine. The catalysts were produced by sol–gel method. They could reduce CO2 under
visible light, but the yield of product was low. Cobalt-phthalocyanine (CoPc) is adsorbed and
supported on semiconductor to receive photo-catalysts (CoPc/TiO2) by in-situ method. The
characteristic CO2 photo-reduction is studied by these catalysts in aqueous solution. The effects
of cobalt phthalocyanine (CoPc) that modified on TiO2 surface on the catalytic activity are
discussed. In this work, we achieved the abiotic formation of formic acid (HCOOH),
formaldehyde (HCHO), methanol (CH3OH) from carbon dioxide (CO2) and water (H2O) under
visible light.
Solar reforming of hydrocarbons by photocatalytic reduction of carbon dioxide has been drawing
worldwide attention because of the simplicity and manageability of the system. The specificity
for the formation of fuel and low cost have even made it more attractive in research studies.
Besides lowering carbon dioxide emission, it could also be one of the most desirable goals for
storage of the solar energy if the UV band in the solar radiation is the only source used to power
the reduction process. The methods of reducing carbon dioxide could be electrochemical,
photochemical, photocatalytic and photoelectrochemical. Pioneering studies on methods for
recycling carbon dioxide into useful products, particularly using semiconductors in aqueous
suspension systems. Current active research studies focusing on the photocatalytic reduction of
carbon dioxide in the presence of water vapour using various titanium oxide catalysts in
heterogeneous systems were carried out and compiled by Anpo and Yamashita. These studies
provided a useful platform of fundamental information essential in pursuing research related to
photo-reduction of carbon dioxide through catalytic process. Titanium oxide has been widely
used as catalyst for UV irradiation and was considered the best choice among several other

3
oxides because it has low band-gap values of approximately 3.0 and 3.2 eV for rutile and
anatase, respectively. Besides fulfilling the thermodynamic requirements needed for the
occurrence of most of the photocatalytic reactions usually investigated, titanium oxide is
reasonably cheap, photo-stable and non-toxic, making it a perfect candidate for photocatalytic
process.
Interested groups have been focusing on extremely small titanium oxide particles as catalysts to
study the relevance of particle size to the photo-activities. The utilization of colloidal catalyst is
to promote specific redox process on its surface. Experimental studies of carbon dioxide
reduction into fuel-like hydrocarbon species in saturated water vapour with the aid of titanium
oxide film coated on copper substrates by the sol–gel and dip-coating technique has been
performed in Japan. The reduced species of methane, ethane and ethylene were detected.
However, the efficiency of the reduction of carbon dioxide is still very low. Although the true
reasons causing this low reduction rate are not obvious, all these investigations and studies
leading to a better understanding of the fundamental mechanisms behind the reaction will be
helpful for subsequent research in applying the principles for improving the efficiency and
selectivity. Another research team showed that titanium oxide highly dispersed within zeolite and
mesoporous molecular sieves exhibited high photocatalytic reactivity. In the preliminary study
conducted recently, the results showed that the pellet form of titanium oxide catalyst could be
also feasible for use in reduction of carbon dioxide although the products have not been
confirmed yet. In separate studies, pellet form of catalyst has been widely explored to investigate
heterogeneous photocatalytic oxidation of gas-phase organics for air purification and confirmed
to be a viable alternative to using thin-film catalyst. In this present research, pellet form of
catalyst was illuminated under UV irradiation in a quartz tube reactor attempting to reduce
carbon dioxide in the presence of saturated water vapour into gaseous hydrocarbons under room
conditions. The contact areas and adsorption/desorption capacity of the porous pellets are
expected to be better as compared with the thin-film form of catalyst. Thus, the photocatalytic
process would be enhanced between the reactants (carbon dioxide and water vapour) and catalyst
(TiO2). The effect of UV irradiation was also examined to understand how well the yields could
be influenced by its wavelength.

4.PHOTOCATALYTIC REDUCTION:
Photocatalytic reduction is a chemical process in which a photocatalyst, typically a
semiconductor material, is activated by light (usually ultraviolet or visible light) to facilitate the
reduction of a substance. In this process, light energy excites electrons in the photocatalyst,
causing them to jump to a higher energy state. These energized electrons can then be transferred
to a target molecule or ion, reducing it by adding electrons. Photocatalytic reduction is
commonly used in environmental applications, such as reducing pollutants, converting CO₂ into
useful fuels, and purifying water by breaking down contaminants.
The photo-catalytic reduction is carried out in a Pyrex glass cell with an optical window (volume
of the solution was 100 ml). Catalyst powder (150 mg) is suspended in 100 ml of 0.1 N sodium
hydroxide (NaOH) aqueous solution. Illuminations are performed with a visible light source of
500 W tungsten-halogen lamp. The reactor is tightly closed during the reaction and stirred

4
continuously by a magnetic stirring bar to prevent sedimentation of the catalyst, then CO2 is
bubbled through the reactor for at least 30 min to purge air and to saturate the solution. The
quantum yields for the formation of formic acid, methanol and formaldehyde are determined
with UV-vis spectrophotometer.
Blank reactions are conducted to ensure that hydrocarbon production is due to the photo-
reduction of CO2, and to eliminate surrounding interference. One blank is vis-illuminated
without the catalyst, and another is in the dark with the catalyst and CO2 under the same
experimental conditions. An additional blank test is vis-illuminated with the catalyst filling
nitrogen (N2) rather than CO2. No product is detected in the above three blank tests.

i.PHOTOCATALYTIC PROCESS USING TiO2 PELLETS:

Illumination of these very fine semiconductor particles in the catalyst pellets by band-gap
irradiation caused electron excitation from valence to the conductance band. Various sites on
these particles act as reducing/oxidising centres, which will provide electrons to carbon dioxide
as well as accept electrons from water vapour in the reactant mixture. The photocatalytic process
involves electrons (e−) and holes (h+) generated at these various sites with the aid of photonic
energy (hν) as shown in the schematic diagram in Fig. 1.

Figure 1.Photocatalytic process

The photon-generated e− and h+ are powerful oxidizing and reducing agents, respectively. The
formation of electron–hole pairs requires sufficient photonic energy with appropriate wavelength
to overcome the band-gap between valence band and conductive band. In the presence of the
photonic energy provided in the experiment, the pairs of electron-hole are created in these
semiconductor particles. They migrate to surface and serve as redox sources that react with
absorbed reactant on the semiconductor surface. Thus, the reduction of CO2 into CH4 and CO
compounds in the presence of H2O took place photocatalytically at the solid–gas interface.

ii.PHOTOCATALYTIC REDUCTION OF CARBON DIOXIDE:

Table 2 summarizes the yields of various catalysts with 10 h irradiation. The presence of CoPc
plays an important role. The reduction in total products has increased obviously after CoPc is

5
added into TiO2, especially using the in-situ CoPc/TiO2. The total organic carbon (TOC) can
reach 1714.9 μmol/g catal.

Contact between TiO2 and CoPc generally involves a redistribution of electric charge. Incident
photons are absorbed by CoPc and photo-excited electrons (e−) and positive holes (h+) are
produced and the electrons undergo transition from S0 to S1 (1). Because the CoPc oxidic
potential of S1 is higher than the conduction band of TiO2, but energy of titanium (Ti) is lower
than the conduction band of TiO2, so it is possible thermodynamically that CoPc transfers
electron to the conduction band (CB) of TiO2 (2), at the same time when CoPc changes into
CoPc+. This process is showed as:

CoPc rapidly transfers excited electrons to TiO2, and then CO2 adsorbed on TiO2 surface can
accept electrons that are to be reduced. This significantly promotes the separation of holes and
electrons, and greatly enhances the photo-efficiency of CO2 with H2O. The band gap of TiO2 is
3.22 eV, while the band gap of CoPc is 2.14 eV. CoPc can be promoted by visible light to
produce electron hole pairs. TiO2 then serves as an electron trapper and prohibits the
recombination of hole and electron. In addition, CoPc rapidly transfers excited electrons to TiO2
and enhances the separation of holes and electrons, significantly promoting photo-efficiency. At
the same time, CO2 can accept electron on TiO2 surface and be reduced to HCOOH, HCHO and

6
CH3OH. The conclusion on the stability of the immobilized metal complex is also confirmed by
the results of reference experiments without CO2, in which no HCOOH and HCHO were
detected. This allows us to consider that the products' source is only CO2(HCO3−).
Through in-situ synthesis, the reactants 1,2-dicyanobenzene (C6H4(CN)2) and metal ions are
isolated homogeneously in the pores of the titania matrix after the process of gel formation and
gel aging. This kind of “cage effect” can strongly prevent the CoPc molecules from migrating to
adjacent pores, then dimerization and aggregation can be effectively avoided resulting in the
CO2 photo-reduction efficiency being greatly enhanced.

iii.EFFECT OF METAL ION ON REDUCTION PRODUCTS:

Fig.2 shows the effect of metal ion on reduction products of CO2. When cobalt ion was added to
TiO2 sol the activity of in-situ CoPc/TiO2 was higher than that of zinc phthalocyanine
ZnPc/TiO2 and NiPc/TiO2. Cobalt phthalocyanine (CoPc) and Nickel phthalocyanine (NiPc)
have higher selectivity at gas-diffusion electrodes for reduction of CO2, the current efficiency of
them was almost 100%. The metals of groups VIII–X have higher activity in catalytic
hydrogenation of CO2. At the same time CoPc has strong electron donating ability. The electric
charge of cobalt (Co) and nickel (Ni) is 1.45 and 0.79, respectively. So, in-situ CoPc/TiO2 is the
better catalyst to reduce CO2. The effect of metal ion also needs research in the future.

Figure 2.Effect of metal ion on reduction products

5.EXPERIMENTAL SET-UP:
A fixed-bed photocatalytic reactor was newly designed and built in the laboratory. The detail
schematic drawing of the experimental set-up is shown in Fig. 3.

7
 Figure 3.Experimental set-up
The main part of the experimental rig is a cylindrical quartz tube reactor. A flat glass tray was
integrated in the tube to hold the catalysts. The reactor has the size of 300 mm (length) × 74 mm
(outside diameter) × 3.0 mm (thickness). It was connected to a flask containing de-ionised water
and a gas cylinder supplying highly purified (99.999%) carbon dioxide gas. Above the reactor
were three National Electrical Code (NEC) Germicidal lamps (GL8) which were made of special
glass that allowed ultraviolet rays to pass through, and were designed to radiate large amounts of
UVC (253.7 nm) rays with emitting power output of 1.6 W each lamp. Due to the sensitivity of
the expected results, any possible external influence on the experiment outcome was minimised
by shielding the entire experimental rig away from ambient light with an opaque insulation
jacket throughout the whole experiment cycle.
The catalysts used were TiO2 pellets, Aerolyst 7708, which were cylindrical in shape with
dimension of 4 mm in both diameter and height. They were extruded from P25, Degussa's
pyrogenic TiO2, 80% anatase and 20% rutile, with particle size of 30 nm and surface area of 50
m2/g. The catalysts were pre-treated before being used in the experiment to minimise any
possible contamination in the porous pellets. After heated-up to 200 °C in oven, the TiO2 pellets
were placed in a vacuum desiccator connected to a conventional vacuum system. The desiccator
containing the heated TiO2 pellets was degassed for few hours and purged with the highly
purified CO2 gas. These degassing and purging processes were repeated for three times before
the pellets were used for the experiment. One hundred grams of TiO2 pellets were then spread
out on the flat tray in the reactor.
Before the UV illumination, highly purified CO2 gas was first flowed through the de-ionised
water in the flask and purged out the air in the reactor via a fully opened valve located at the
other end. The amount of moisture (water vapour) in the gas flowing through the rig could be
estimated based on the temperature of the water in the flask. The rig was then isolated with a
pressure of approximately 10 kPa above ambient pressure. After the whole rig is properly set-up,
the rig and its contents were allowed to settle for 2 h before the first gas sample was taken to
verify the mixture as the baseline and UV light was then switched on to start the experiment. The
light remained on continuously for the next 48 h. At the end of the experiment, the gaseous
products accumulated inside the reactor were abstracted to analyse the product yields using gas
chromatography and investigate the effectiveness of this photocatalytic process.

8
In the second set of the experiments, TiO2 catalysts were replaced by a new batch of pre-treated
catalysts and spread out on the flat tray in the reactor. The UVC lamps were replaced by three
NEC black light blue fluorescent lamps (FL8BL-B) which emit ultra-violet radiation with
wavelength peaking at 365 nm and have energy power output of 1.0 W for each lamp. The whole
process as before was repeated. At the end of two days illumination, the final product
concentrations accumulated inside the reactor were again analysed to investigate the effect of the
radiation wavelength on the photocatalytic reduction of CO2.

6.PROPOSED MECHANISM:
Various reaction schemes for the photocatalytic reduction of CO2 by H2O on TiO2 catalysts
have been proposed in different studies. Although the exact production mechanism of CH4 and
CO are not absolutely clear in our present study, the results obtained in the present study show
good correspondence with these reports and suggest that the process would have undergone the
following reforming reaction shown below, when the reactants and catalysts are in contact with
UV irradiation.

When illuminated by UV light with sufficient photonic energy (hν) and appropriate wavelength,
photon-generated electrons (e−) and holes (h+) are created on the surface of the TiO2 catalysts.
The holes first react with water vapour adsorbed on the catalyst, resulting in producing hydroxyl
radicals (•OH) and hydrogen ions (H+). The water is further oxidized by radical dotOH producing
oxygen and H+. At the same time, carbon radicals (C•) are formed from CO2 through the
intermediate product of CO. The carbon radicals then react with H+ generated from H2O and e−
on the catalyst surface to finally produce CH4.

7.CHARACTERIZATION OF CATALYTIC SYSTEM:

The characterization of a catalytic system for carbon dioxide (CO₂) reduction involves a detailed
analysis of its components, particularly focusing on efficiency, activity, selectivity, and overall
performance. Titanium dioxide (TiO₂) is a highly favored catalyst in CO₂ reduction due to its
strong photocatalytic properties, resilience under various reaction conditions, and non-toxic
nature. TiO₂ exists in three primary crystalline phases-anatase, rutile, and brookite. Of these,

9
anatase is generally preferred for photocatalytic applications because it has an optimal electronic
structure, a relatively large surface area, and a higher reactivity than the other phases, which
together enhance its ability to catalyze reactions efficiently. TiO₂ in the anatase form has a band
gap of approximately 3.2 eV, enabling it to absorb ultraviolet (UV) light. However, this band gap
restricts TiO₂ to UV light absorption, which limits its energy capture potential since UV light
represents only a small fraction of the solar spectrum. Beyond its photocatalytic properties, TiO₂
is chemically stable, non-toxic, and corrosion-resistant, making it durable for repeated use and
minimizing environmental impact.
In terms of the reaction mechanism, the photocatalytic reduction of CO₂ on TiO₂ begins with the
absorption of UV light, which excites electrons from the valence band to the conduction band.
This transition generates electron-hole pairs on the TiO₂ surface. The excited electrons in the
conduction band can then interact with CO₂ molecules adsorbed on the catalyst’s surface,
facilitating reduction reactions that produce various carbon-based products such as methane
(CH₄), methanol (CH₃OH), and carbon monoxide (CO), depending on reaction conditions.
Meanwhile, the positively charged holes in the valence band act as oxidizing agents, typically
interacting with water or sacrificial reagents to produce protons. These protons are crucial as they
are involved in the reduction process, helping balance charge distribution within the system and
maintaining reaction stability.
Despite the promising photocatalytic capabilities of TiO₂, its restricted absorption of only UV
light has led researchers to explore modifications that enable it to utilize more of the solar
spectrum, particularly visible light. This enhancement is typically achieved through doping-
introducing foreign elements into the TiO₂ crystal lattice. Doping with non-metals like nitrogen
or sulfur or with transition metals such as iron or chromium can reduce the band gap, allowing
TiO₂ to absorb visible light and thereby increase its overall photocatalytic efficiency. Another
effective strategy is to develop composite structures that incorporate TiO₂ with materials that
enhance charge separation and broaden its light absorption range. For instance, combining TiO₂
with carbon-based materials such as graphene not only expands the range of light it can absorb
but also improves electron mobility and minimizes electron-hole recombination.
Further, the surface area and density of active sites on TiO₂ can be significantly increased by
nanoscale structuring, such as forming TiO₂ into nanoparticles, nanorods, or nanotubes. A higher
surface area enhances CO₂ adsorption, leading to more frequent interactions between CO₂
molecules and active catalytic sites, which can enhance the reaction rate and yield. Additionally,
introducing cocatalysts such as platinum (Pt), copper (Cu), or silver (Ag) can facilitate electron
transfer and further reduce electron-hole recombination rates, thereby improving overall catalytic
efficiency and longevity.
Product selectivity is another critical aspect of TiO₂ photocatalysis in CO₂ reduction, as the
reaction can produce multiple products depending on the conditions. The primary products such
as methane, methanol, or carbon monoxide are formed through various pathways influenced by
factors such as light intensity, reaction time, and specific modifications to the TiO₂ surface. By
carefully designing the catalyst structure or selecting dopants that favor particular reaction
pathways, the selectivity for a targeted product can be optimized. Tailoring reaction conditions

10
and catalyst modifications to improve selectivity toward desired compounds, such as methane for
fuel applications or methanol for chemical synthesis, allows TiO₂ photocatalysis to be tuned for
specific end-use applications.

i.CHARACTERIZATION TECHNIQUES:
a.UV–vis spectra of in-situ catalysts:
Fig. 4 is the UV–vis spectra of in-situ CoPc/TiO2. It shows that in the process of in-situ
synthesis, the visible absorption band appeared at around 600-700 nm. There are three bands of
690 nm, 668 nm and 625 nm. Molecules of Metal Phthalocyanine (MPc) are known to exist in
the matrix in mainly two forms: monomer and dimer. The profile of Q-band of MPc changes
with various molecular forms. Monomers of MPc have a strong absorption band at around 670
nm and a weak absorption band at around 625 nm. Dimers have a blue shift band at around 640
nm while aggregations have a red shift band at around 700 nm. The Soret band is thought to be
diagnostic of the form of CoPc so in this figure the absorption spectra at 668 nm and 690 nm of
Q-band are the absorption of CoPc monomer, while the band at 640 nm is the absorption of the
dimer. With the gel formation and gel aging the dimer absorption spectrum is increased
obviously. The reason may be that during the transformation of sol and gel the solvent is severely
evaporated and the volume is shrinking, the molecules of CoPc are subjected to aggregation. In
aggregations, the close proximity of two or more rings can lead to coupling between the
transition dipoles for two identical transitions. This interaction gives rise to a separation which is
referred to as the exciting splitting energy. The result is the generation of a new energy level. The
dimers will affect the UV-vis absorption spectra of CoPc and decrease the optical characteristics
of it. So, the time of aging is inclined to not too long so as to restrain the aggregation. At the
same time, the UV-vis spectrum shows that there indeed produces CoPc in the sol of TiO2.

Figure 4.UV–vis spectra of in-situ CoPc/TiO2

b.FT-IR spectra of catalysts:
The Fourier Transform Infrared (FT-IR) absorption spectra of in-situ CoPc/TiO2, TiO2 and
market bought CoPc are shown in Fig. 5. The spectra of in-situ CoPc/TiO2 show the
characteristic absorption of pure CoPc and TiO2. It can be seen from Fig. 4 that the bands are
assigned to the vibration of Pc ring. The 740 cm-1 band is assigned to the phthalocyanine (Pc)

11
ring vibration. The 1025 cm-1 band is assigned to the C–H vibration of Pc ring. The 1507 cm-1
and 1589 cm-1 bands are the vibrations of Cdouble bondN and pyrrole ring, respectively. The
1684 cm-1 band is the Cdouble bondC stretching. Two intermediate strong peaks at 1407 cm-1
and 1471 cm-1 are the stretchings of C–C and C–N, respectively. This proves that CoPc is
synthesized successively in sol–gel TiO2. The 913 cm-1 band is assigned to the metal–ligand
Co–N vibration. It proves that metal has coordinated with nitrogen of Pc ring. Particularly the
peak at 872 cm-1 is possibly due to Co (II) center metal of Pc coordinated with atom or ion
which owned lone electron pair. So, a new Co–O stretching vibration at 872 cm-1 can be
observed. Coordinate covalent bond of Co–O is due to the lone electron pair of TiO2 surface
oxygen accessing the empty orbit of Co (II). So CoPc is stably loaded on surface of TiO2.

Figure 5.FT-IR spectra of in-situ CoPc/TiO2

c.XRD spectra of catalysts:
The X-Ray Diffraction (XRD) spectrum in Fig. 6 verifies that the samples are mainly crystallized to
be in anatase phase and have a small quantity of rutile by calcinations. The peaks at 2θ values of
24.88, 37.42, 47.66, 53.49, 54.51, 62.29, 68.55, 69.97 and 74.69 are identified by comparison
with literature data and confirm that the particles are polycrystalline with an anatase structure
corresponding to the diffractions of (101), (004), (200), (105), (211), (204), (116), (220) and
(215), respectively. It is noteworthy that the diffractograms of the samples in-situ CoPc/TiO2
Fig. 5 (b) do not present signals of CoPc. The absence of CoPc peaks could be attributed to their
complete dispersion into TiO2 with the form of molecular for they are added along with the
hydrolysis of titanium butoxide or low loading quantity.

12
 Figure 6.XRD spectra of catalysts
d.TG–DTA spectra of catalysts:
Fig. 7 shows the Differential Thermal Analysis (DTA) and Thermogravimetric Analysis (TG)
curves of the catalyst prepared by in-situ method. Three weight loss stages are observed in the
TG curves, coinciding with two endothermic peaks in the DTA profiles. The first weight loss is
ascribed to the removal of hydroxyl groups from the surface of TiO2. The second weight loss can
be attributed to the decomposition of CoPc. As shown in Fig. 6, the first weight loss temperature
is 251.5 °C, while the second weight loss temperature is 401.2 °C. This further indicates that the
CoPc is synthesized by the in-situ method. At the same time, the catalysts prepared by two
different methods have almost the same thermal decomposition behaviors.

Figure 7.TG–DTA spectra of catalysts

ii.PARTICLE SIZE DISTRIBUTION:

Table 1 summarizes the properties of the catalysts. The particles of in-situ CoPc/TiO2 are
uniform and the diameter is 11 nm. It suggested that pure TiO2 grain sizes with a diameter
ranging from 11 to 21 nm were of a size that maximized photo-catalytic efficiency. When the
particle size was less than 5–10 nm, the surface recombination of electron hole pairs becomes
significant, resulting in low photocatalytic efficiency. The specific surface area (SBET) of in-situ
CoPc/TiO2 and TiO2 is 75.23 and 83.41 m2/g, respectively. It shows that the incorporation of
CoPc itself leads to a decrease in SBET. The SBET is obviously not a main factor in photo-
catalytic reaction but the CoPc is.

13
8.PROCEDURE FOR CATALYSTS PREPARATION:
In-situ CoPc/TiO2 is prepared with the advanced sol–gel procedure illustrated in Fig. 8. The
precursor is titanium (IV) butoxide. To avoid precipitation during polycondensation and
formation of unstable colloidal sols, the hydrolyzing water is homogeneously released by the
esterification of alcohol and acetic acid. Then 1,2-dicyanobenzene and analytically pure soluble
cobalt chloride are used as the reactants of CoPc and added into the sol precursors. The mixed
solutions are adjusted to pH 4 by the addition of hydrochloric acid (HCl) and stirred for 12 h at
ambient temperature, then aged for 48 h, left in an oven at 60 °C for about 24 h, and finally the
resulting xerogels are transferred to a furnace and calcined at 360 °C for 1 h. The sample is
crushed into powder.

Figure 8.Procedure for catalysts preparation

For comparison, the CoPc/TiO2 catalysts are prepared by equilibrium adsorption of CoPc on
TiO2 from a solution in dimethylformamide for about 12 h. The amorphous state of the prepared

14
catalysts is confirmed by X-ray diffraction spectra (XRD) recorded on a Rigaku 2304
diffractometer with Ni-filtered Cu Kα radiation from 8° to 80° at a scanning speed of 2°/min. FT-
IR and UV–vis spectra of the solid catalysts are recorded on a Perkin–Elmer FT-IR1760
spectrometer and a Lambda Bio40 spectrophotometer, respectively. UV–vis spectrum of the
liquid sol sample is recorded by a TU-1901 spectrophotometer. To understand the thermal
behavior of the catalysts, we carried out thermogravimetry and differential thermal analysis
(DTA–TG) using a Wet Capping Test-2 (WCT-2) equipment in the temperature range of 25-900
°C at a heating rate of 10 °C/min in air.

9.STUDY OF CATALYTIC PROCESS:

Catalytic processes for the reduction of carbon dioxide (CO2) are highly significant for
addressing climate change by converting CO2, a major greenhouse gas, into useful chemicals or
fuels. Reducing carbon dioxide (CO2) emissions has become essential in efforts to mitigate
climate change. A major focus in environmental chemistry is converting CO2, a primary
greenhouse gas, into useful chemicals or fuels. This can be achieved through catalytic processes,
where catalysts are employed to facilitate the chemical transformation of CO2 under various
conditions. There are various methods and catalysts used in this transformation, with each
method working through a different reaction pathway, depending on the catalyst and conditions.
Among the many catalysts studied for CO2 reduction, titanium dioxide (TiO2) is one of the most
widely explored, particularly due to its stability, affordability, and ability to absorb light, making
it suitable for photocatalytic applications. This review provides an overview of the types of
catalysts used in CO2 reduction, methods of catalysis, and the significance of TiO2 as a
promising catalyst.

9.1.KEY ASPECTS FOR STYDYING CATALYTIC CO2

REDUCTION:
i.Types of Catalysts in CO2 Reduction:
Catalysts play a central role in CO2 reduction, enabling reactions that otherwise would require
prohibitively high energy. Catalysts are chosen based on the desired reaction pathway and
product, with various types offering different benefits and challenges.

a.Metal-Based Catalysts:
Metals such as copper, iron, cobalt, and titanium dioxide (TiO2) are frequently employed in CO2
reduction. These metals facilitate electron transfer to CO2 molecules, initiating the reduction
process. For example, TiO2 is well-regarded due to its strong light absorption capabilities and
stability, making it effective in photocatalytic reduction applications.

b.Photocatalysts:
Photocatalysts like TiO2 utilize light energy to drive CO2 reduction reactions. Upon exposure to
sunlight or UV light, these catalysts generate excited electrons that react with CO2, converting it
into more complex molecules. TiO2 is particularly advantageous in this domain because it is
affordable, abundant, and stable under reaction conditions, making it a prominent choice for
solar-driven CO2 reduction.

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c.Electrocatalysts:
Electrocatalysts enable the reduction of CO2 through the application of electrical energy. Using
electricity from renewable sources, these catalysts convert CO2 into products such as carbon
monoxide (CO), methane, or ethanol. This approach is flexible and adaptable, allowing
researchers to tailor products by adjusting catalyst materials and electrical configurations.

d.Enzymatic Catalysts:
Natural enzymes, or synthetic analogs, are employed to mimic biological CO2 reduction
processes. These catalysts are inspired by natural organisms that convert CO2 as part of their
metabolic processes, making them a valuable area of study for sustainable CO₂ reduction.

ii.Methods of CO2 Reduction with Catalysts:

The reduction of CO2 can be achieved through different catalytic methods, each of which
involves specific energy sources and reaction mechanisms. These methods include
electrochemical, photocatalytic, and thermocatalytic reduction.

a.Electrochemical Reduction:
In electrochemical reduction, an electrical current is applied to a CO2 containing solution,
facilitating its conversion into valuable products. This process can yield different outputs (e.g.,
methane or ethanol) depending on the chosen catalyst and electrode setup, offering high
versatility in CO2 utilization.

b.Photocatalytic Reduction:
Photocatalytic reduction involves using light energy, typically from sunlight or UV lamps, to
excite the catalyst material. When TiO2 is used, it absorbs UV light, generating electrons and
holes that interact with CO2. With the presence of water, this process can produce fuels like
methane or methanol, offering a renewable approach to CO2 reduction.

c.Thermocatalytic Reduction:
Thermocatalytic reduction uses heat to drive CO2 reduction reactions. By heating CO2 and
hydrogen in the presence of a catalyst, hydrocarbons such as methane can be produced. The
Fischer-Tropsch process, which synthesizes longer-chain hydrocarbons, is an example of
thermocatalytic CO2 reduction used for fuel production.

iii.Titanium Dioxide (TiO2) as a Catalyst:

TiO₂ is a particularly promising catalyst for CO2 reduction, especially in photocatalytic
applications. Its advantages include:

a.UV Light Absorption:

TiO2 readily absorbs UV light from sunlight, which energizes its electrons and facilitates
catalytic reactions. The UV absorption enables TiO2 to drive the reduction of CO2 in the
presence of light.

16
b.Stability and Safety:
As a stable and non-toxic material, TiO2 maintains its structural integrity during reactions,
reducing the risk of contamination and extending catalyst life. This stability is essential for
continuous operation in different environments.

c.Modifiability:
TiO2 can be "doped" with small amounts of metals like silver (Ag) or platinum (Pt) to enhance
its photocatalytic efficiency by broadening its light absorption range. This doping process
improves the catalyst's light-capturing ability and reaction speed, making TiO2 more effective
under various lighting conditions. Modifying TiO2 with metal dopants expands its light
absorption into the visible spectrum, potentially improving photocatalytic efficiency.
Furthermore, TiO2 can be used in different media, including aqueous and gaseous phases,
making it adaptable to diverse reaction setups.

iv.Key Goals in CO2 Reduction Studies:

Research in CO2 reduction focuses on optimizing several parameters to enhance the efficiency,
selectivity, and feasibility of catalytic processes:

a.Efficiency and Selectivity:

High selectivity toward specific products (like methane or methanol) and efficiency (low energy
input with high output) are primary objectives. Selective and efficient processes minimize waste,
conserve energy, and create valuable products from CO2.

b.Optimal Environmental Conditions:

Variables such as temperature, pressure, light intensity, and CO2 concentration significantly
affect reaction rates and product yields. Studies aim to find the best combination of these factors
to maximize efficiency and selectivity.

c.Renewable Energy Integration:

To further reduce the carbon footprint, renewable energy sources like sunlight (for
photocatalysis) or wind-generated electricity (for electrocatalysis) are ideal for powering these
reactions. This approach aligns CO2 reduction with sustainable energy practices, increasing the
process's environmental benefits.

v.Current Challenges in CO2 Reduction Catalysis:

Despite advancements, several challenges persist in scaling CO2 reduction technologies for
broader application:

a.Catalyst Durability:
Catalysts may lose activity over time or under repeated cycles. Identifying durable materials and
protective modifications is essential to extend catalyst lifespan.

b.High Energy Demand:

Some catalytic processes, especially thermocatalytic and electrochemical methods, can be
energy-intensive. Researchers are focused on developing methods that require minimal energy

17
without sacrificing reaction speed or product yield.

c.Scalability:
Although laboratory results are promising, scaling catalytic CO2 reduction to an industrial level
remains challenging. Engineers are working to develop robust, high-capacity systems that
maintain efficiency and selectivity while processing larger volumes of CO2.
Research on catalytic processes for CO2 reduction, especially those involving TiO2, holds
promise for creating sustainable solutions that convert greenhouse gases into valuable products.
By advancing catalyst design, optimizing reaction conditions, and integrating renewable energy
sources, scientists are working towards scalable, efficient, and economically feasible methods for
CO2 reduction. These efforts contribute to addressing climate change by transforming CO2
emissions into useful fuels and materials, benefiting both the environment and the economy.

10.FUTURE DIRECTIONS FOR CARBON DIOXIDE

REDUCTION(CDR):
a.Integration of Network Diagram Analysis for Literature Data:
The rapid expansion of carbon dioxide reduction (CDR) research makes it challenging to stay
updated on all relevant developments. Advanced network diagrams could help researchers
navigate this field by visualizing trends, connections, and emerging areas, allowing for strategic
targeting of research efforts. This approach can help identify specific pathways that are gaining
traction or showing potential for breakthroughs.

b.Emphasis on Photochemical and Photoelectrochemical Methods:

Solar energy’s integration into CDR aligns with green chemistry principles and sustainable
development goals. A growing focus on photochemical and photoelectrochemical methods
should continue, with efforts to improve efficiency, stability, and scalability. Future research may
explore novel semiconductors and sensitizers that can harness sunlight more effectively or
initiate CO2 reduction under milder conditions, reducing energy costs.

c.Development and Optimization of Metal and Metal Oxide Catalysts:

Metal and metal oxide catalysts, essential for CDR processes, are expected to receive continued
attention, especially in the study of oxygen vacancies (OV) on metal oxides and their role in
enhancing catalytic activity. Investigating how OV affect the CO2 adsorption and conversion
could reveal pathways for designing catalysts with tailored properties.

d.Role of Organic Molecules in Catalysis:

The interaction between organic molecules and metals can improve catalyst performance by
stabilizing active sites or promoting selective reduction pathways. Research should focus on
identifying organic molecules that enhance the efficiency and selectivity of metal-based catalysts
in converting CO2 to high-value products. New ligands or organic frameworks that support
sustainable and selective reduction reactions may play a significant role here.

18
e.Exploration of Metal-Organic Frameworks (MOFs), Carbon Materials, and
Single-Atom Catalysts (SACs):
These materials are promising for CO2 capture and conversion due to their high surface area and
tunable catalytic properties. Metal-Organic Frameworks (MOFs) could offer new possibilities for
selective CO2 capture and reduction in a single step. Single-Atom Catalysts (SACs), which use
minimal metal content, represent a greener and more economical approach. Future research
could focus on improving the stability of SACs and exploring their potential in scalable CDR
applications.

f.Advanced Theoretical Simulations:

Theoretical modeling and simulations will likely be central to developing the next generation of
catalysts. Using machine learning and computational chemistry, researchers can predict catalyst
behavior, optimize material properties, and reduce the experimental time required for finding
efficient catalysts. This computational approach will help identify potential materials and
optimize processes, especially for scaling up to industrial levels.

g.Green and Cost-Effective Synthesis of Nontoxic Catalysts:

The future development of CDR catalysts will emphasize green synthesis methods that minimize
waste and toxicity. Catalysts should be cost-effective, involve lower metal content, and meet
purity standards that ensure efficiency in producing target products. Research should prioritize
sustainable methods and explore how recycling or renewable feedstocks can be incorporated into
catalyst production.

h.Enhanced Production of Valuable C>1 Fuel Molecules:

There is an increasing demand to produce valuable multi-carbon (C>1) fuel molecules, such as
ethanol or ethylene, from CO2 reduction. Future research could focus on finding ways to
enhance the selectivity and yield of C>1 products. This might involve novel catalysts, reaction
conditions, or engineered pathways that facilitate multi-electron transfers for efficient
conversion.

i.Scaling and Commercialization Pathways:

Translating laboratory-scale successes to industrial applications remains a challenge. To make
significant strides toward commercial viability, research should address challenges in scaling,
including stability, reproducibility, and cost. Emphasis on creating scalable prototypes and
engaging in partnerships with industries could accelerate the transition of CDR technologies
from research to practice. In summary, the future of CDR research lies in advancing sustainable,
efficient catalysts that are economically viable and environmentally friendly, leveraging
theoretical modeling, innovative materials, and green synthetic methods.

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11.CONFLICT OF INTEREST STATEMENT:
"The authors declare that they have no conflict of interest regarding the publication of this
review article on the kinetics and mechanism of catalytic reduction of CO2. This review is an
independent academic work, and no financial support or sponsorship has been received from any
organization or individual that could influence the content or outcome of this publication.
Furthermore, the authors confirm that:
1. They have no affiliation or financial relationship with any company, organization, or
institution that could benefit from this research.
2. They have no personal or professional relationships that could compromise their objectivity or
impartiality.
3. They have not received any honoraria, reimbursement, or benefits from any entity that could
influence this work.
4. They have no patent applications, licenses, or intellectual property rights related to the topic.
The authors assert that this review is a genuine and unbiased academic effort, aiming to
contribute to the scientific understanding of CO2 reduction kinetics and mechanisms."

12.ACKNOWLEDGEMENTS:
The authors gratefully acknowledge the financial support provided by the Natural Science Funds
(no. 2008021015) of China Shanxi Province. We would also like to extend our sincere gratitude
to other members of the research team for their invaluable technical support, as well as to the
editor and referees for their valuable suggestions, which greatly improved the quality of this
work.

13.CONCLUSION:
This study explores the catalytic reduction of carbon dioxide (CO2) to hydrocarbons such as
methane (CH4) using titanium dioxide (TiO2) pellets illuminated by ultraviolet (UV) light,
demonstrating TiO2’s effectiveness as a photocatalyst for CO2 transformation in the presence of
water vapor. Experimental results confirm that TiO2 pellets can facilitate the conversion of CO2
into hydrocarbons, primarily producing methane and carbon monoxide (CO). Findings reveal
that the efficiency of this process is strongly influenced by the wavelength of UV light, with both
UVA and UVC irradiation impacting product yields significantly. Additionally, TiO2's capacity to
produce hydrogen gas (H2) through water splitting highlights its dual potential for CO2
reduction and sustainable energy applications.
The study further shows that introducing cobalt phthalocyanine (CoPc) onto TiO2 particles
enhances photocatalytic efficiency by stabilizing electron-hole pairs under visible light. TiO2
acts as an electron trapper, preventing the recombination of electrons and holes, while CoPc
rapidly transfers excited electrons to TiO2, improving the separation of charge carriers and
significantly boosting photo-efficiency. Moreover, CO2 can accept electrons on the TiO2 surface
and be reduced to formic acid (HCOOH), formaldehyde (HCHO), and methanol (CH3OH). The

20
distribution of CoPc on TiO2 nanoparticles is crucial for maximizing reduction yields. Overall,
these findings underscore TiO2’s promise as a clean and versatile material for CO2 management
and renewable energy production, establishing a strong foundation for future advancements in
optimizing TiO2-based photocatalysts.

14.REFERENCES:

1. C. Swanson Rollin 5516742 Catalytic conversion of water and carbon dioxide to low cost
energy, hydrogen, carbon monoxide, oxygen and hydrocarbons Journal of Cleaner Production, 4
(3–4) (1996), pp. 232-233.
2. T. I-Hsiang, C.S.W. Jeffrey Chemical states of metal-loaded titania in the photoreduction of
CO2.
3. G.R. Dey, A.D. Belapurkar, K. Kishore Photo-catalytic reduction of carbon dioxide to methane
using TiO2 as suspension in water Journal of Photochemistry and Photobiology A: Chemistry,
163 (3) (2004), pp. 503-508.
4. N. Thevinh, C.S.W. Jeffrey Photoreduction of CO2 in an optical-fiber photoreactor: effects of
metals addition and catalyst carrier Applied Catalysis A: General, 335 (1) (2008), pp. 112-120.
5. T. I-Hsiang, C. Wanchem, C.S.W. Jeffrey Photoreduction of CO2 using sol–gel derived titania
and titania-supported copper catalysts Applied Catalysis B: Environmental, 37 (1) (2002), pp.
37-48.
6. W. Ling, C.Y. Jimmy, F. Xianzhi Characterization and photocatalytic mechanism of nanosized
CdS coupled TiO2 nanocrystals under visible light irradiation Journal of Molecular Catalysis A:
Chemical, 244 (1–2) (2006), pp. 25-32.
7. Y. Jiaguo, Y. Huogen, C.H. Ao, S.C. Lee, C.Y. Jimmy, H. Wingkei Preparation,
characterization and photocatalytic activity of in situ Fe-doped TiO2 thin films Thin Solid Films,
496 (2) (2006), pp. 273-280.
8. R. Seoudi, G.S. Elbahy, Z.A.E. Sayed Ultraviolet and visible spectroscopic studies of
phthalocyanine and its complexes thin films Optical Materials, 29 (2–3) (2006), pp. 304-312.
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doped inorganic glasses Journal of Materials Science, 35 (2000), pp. 2539-2542.
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 15. LIST OF ABBREVIATIONS:
1,2-dicyanobenzene Metal–organic frameworks)
(C6H4(CN)2)...................................................................7 (MOFs)...........................................................................2
Black light blue fluorescent lamps methanol
(FL8BL-B)........................................................................9 (CH3OH).........................................................................3
Carbon dioxide Methanol
(CO2)..........................................................................2, 3 (CH3OH).........................................................................3
Carbon dioxide reduction Molybdenum disulfide
(CDR)...........................................................................18 (MoS2)...........................................................................2
Carbon radicals Nickel
(C•)................................................................................9 (Ni).................................................................................7
Cobalt Nickel phthalocyanine
(Co)................................................................................7 (NiPc).............................................................................7
Cobalt-phthalocyanine nitrogen
(CoPc)............................................................................3 (N2)................................................................................5
conduction band Nitrogen
(CB)................................................................................6 (N2)................................................................................5
Conduction band Oxygen vacancies
(CB)................................................................................6 (OV).............................................................................18
Copper Phthalocyanines
(Cu)..............................................................................10 (Pc-s)..............................................................................3
Differential Thermal Analysis Platinum
(DTA)............................................................................13 (Pt)...............................................................................10
Formaldehyde Silver
(HCHO)...........................................................................3 (Ag)..............................................................................10
formic acid Single-Atom Catalysts
(HCOOH)........................................................................3 (SACs)..........................................................................19
Formic acid sodium hydroxide
(HCOOH)........................................................................3 (NaOH)...........................................................................4
Fourier Transform Infrared Sodium hydroxide
(FT-IR)..........................................................................11 (NaOH)...........................................................................4
Germicidal lamps Specific surface area
(GL8)..............................................................................8 (SBET)..........................................................................13
Graphitic carbon nitride Thermogravimetric Analysis
(C3N4)...........................................................................2 (TG)..............................................................................13
Hydrochloric acid tin oxide
(HCl).............................................................................14 (SnO2)............................................................................3
Hydrogen ions Tin oxide
(H+)................................................................................9 (SnO2)............................................................................3
Hydroxyl radicals Titanium
(•OH).............................................................................9 (Ti).................................................................................6
Metal Phthalocyanine Titanium dioxide
(MPc)...........................................................................11 (TiO2).............................................................................2
Metal-Organic Frameworks total organic carbon
(MOFs).........................................................................19 (TOC)..............................................................................5

22
Total organic carbon (WCT-2)........................................................................15
(TOC)..............................................................................5 X-Ray Diffraction spectrum
Ultraviolet radiations (XRD)............................................................................12
(UV)...............................................................................2 zinc oxide
ultraviolet-visible (ZnO)..............................................................................3
(UV–vis).........................................................................3 Zinc oxide
Ultraviolet-visible (ZnO)..............................................................................3
(UV–vis).........................................................................3 zinc-phthalocyanine
water (ZnPc).............................................................................3
(H2O).............................................................................3 (Zn-Pc)...........................................................................3
Water Zinc-phthalocyanine
(H2O).............................................................................3 (ZnPc).............................................................................3
Wet Capping Test-2

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