Journal of Alloys and Compounds 918 (2022) 165533

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Review

Recent development on titania-based nanomaterial for photocatalytic

CO2 reduction: A review ]]
]]]]]]
]]

⁎
Ipsita Som a, Mouni Roy b,
a
Department of Chemistry, National Institute of Technology, Durgapur 713209, West Bengal, India
b
Department of Chemistry, Banasthali Vidyapith, Rajasthan 304022, India

a r t i cl e i nfo a bstr ac t

Article history: Since the past few decades, nanomaterials proved to be an interesting candidate towards several applicative
Received 4 February 2022 purposes. The oxide-based semiconductor nanomaterials provide added benefit for their capability in the
Received in revised form 15 May 2022 utilization of renewable sources of energy, i.e., light energy. In this context, TiO2-based nanomaterials are
Accepted 17 May 2022
extremely promising candidate and has been widely studied. As per the current global scenario humankind
Available online 26 May 2022
is majorly dependent on fossil fuels as the prime energy asset. This created two key challenges: (i) crisis of
fossil fuel and (ii) global warming owing to increased level of atmospheric carbon dioxide (CO2). In con­
Keywords:
Photocatalysis sideration of this, photocatalytic CO2 reduction to fuels and value-added-chemicals, is one of the revolu­
Titania-based materials tionary approaches to resolve both problems efficaciously. To address this concern efficiently, modified TiO2
Heterojunction photocatalyst based photocatalyst has been explored by several research groups worldwide, owing to their interesting
CO2 Reduction physicochemical properties. This review summarizes fundamental aspects (principle, thermodynamics,
Conversion efficiency kinetics), structural and compositional engineering of TiO2 based photocatalyst to achieve efficient pho­
tocatalytic CO2 reduction. Moreover, this article provides an elaborate study on several factors associated;
along with the documentation of their efficiency and selectivity to assess the benchmark towards CO2
photoreduction reactions. Furthermore, an overview has been presented regarding photocatalytic CO2 re­
duction mechanism for different types of TiO2 based photocatalyst supported by computational studies.
Finally, perspective related to probable modification approaches and opportunities in this vital area of
research, has been discussed.
© 2022 Published by Elsevier B.V.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 2

2. Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 3
3. Thermodynamics and total pathway for major products formation related to CO2 photoreduction . . . . ..... . ..... . ..... . ..... . ..... . ..... . 3
4. Kinetics of CO2 photoreduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 4
4.1. Microkinetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 4
4.2. Langmuir−Hinshelwood (L-H) model . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 4
5. CO2 reduction with TiO2-based semiconductor photocatalysts . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 5
5.1. Doped photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 5
5.1.1. Transition Metal doped . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 6
5.1.2. Noble metal doped photocatalyst . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 6
5.1.3. Rare earth element doped TiO2 . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 6
5.1.4. Co-metal doped photocatalyst . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 7
5.1.5. Oxygen Vacancy Self-doped photocatalyst . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 7
5.1.6. Non-metal doped . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 7
5.2. Sensitized Photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...................... . ..... . ..... . ..... . ..... . ..... . ..... . 8

⁎
Corresponding author.
E-mail address: mouni.roy0722@gmail.com (M. Roy).

https://doi.org/10.1016/j.jallcom.2022.165533
0925-8388/© 2022 Published by Elsevier B.V.
I. Som and M. Roy Journal of Alloys and Compounds 918 (2022) 165533

5.2.1. Organic Dye molecules as photosensitizer . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 9
5.2.2. Quantum dots (QDs) as sensitizer. . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 9
5.2.3. Conducting carbon based material as sensitizer . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 9
5.3. Composite photocatalyst with carbon based materials . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 9
5.4. TiO2 based heterojunction photocatalyst . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 10
5.4.1. Traditional Heterojunction . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 10
5.4.2. p-n Heterojunction . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 11
5.4.3. Schottky Junction . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 11
5.4.4. Z‐scheme Heterojunction. . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 12
5.4.5. Step‐Scheme (S- scheme) Heterojunction. . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 12
6. Factors associated with photocatalytic CO2 reduction . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 13
6.1. Role of Photoreactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 13
6.2. Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 14
6.3. Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 14
6.4. Influence of TiO2 as photocatalyst . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 14
6.5. Effect of surface functional group. . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 15
6.6. Wavelength effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 15
6.7. Effect of partial pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... . 15
7. Photocatalytic CO2 reduction mechanism . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 15
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 20
9. Future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 21
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 21
Acknowledgement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... . ..... . ..... ..... . ..... . ..... . ..... . ..... . ..... . ..... . ..... 21

1. Introduction depicting photocatalytic CO2 reduction onto TiO2 nanocatalyst surface

In recent few decades, nanomaterials proved to be quite inter­
esting to scientists and engineers because of several marvellous
physicochemical properties (such as unique opto-electronic prop­
erties, chemical and thermal stability, low cost, high surface area and
biological activity) [1]. Thus, nanomaterials find applications in di­
verse areas such as optical [2], magnetic recording media [3], energy
storage [4], biomedical [5], contrast agent in magnetic resonance
imaging (MRI) [6], cancer therapy [7] and catalysis [8]. Moreover,
nanomaterials are useful for photocatalytic applications due to their
characteristic features. In this context various metal oxide as well as
non-oxide semiconductors receive huge attention. Furthermore,
metal sulphide, metal phosphide, metal-based composites, etc. can
also act as superior photocatalyst for utilizing solar energy effi­
ciently. Specifically, it has been considered that band gap energy of a
photocatalyst is an important factor for effective absorption of solar
light as well as generation of charge carriers (electron and hole).
In this context, TiO2 has been proved to be an efficient nanoma­
terial with alluring properties like favourable surface area, chemically
and biologically non-toxic nature, easy availability, cost effective and
highly stable [9–11]. Akira Fujishima, a Japanese Chemist, for the first
time observed the photocatalytic activity of TiO2 powders under UV
light irradiation in the year 1942. Later, in 1972 Fujishima and Honda
investigated the photoelectrochemical water splitting in presence of
TiO2 as photocatalyst [12]. This attracted the attention of scientific
community towards the use of TiO2 as photocatalyst for different
photocatalytic processes [13]. Thereafter, there are several literature
reports on photocatalytic activities of TiO2, reported till date. Fur­
thermore, several studies suggest that reduction of CO2 can also be
successfully achieved onto TiO2 photocatalyst surface. This is because
of the acidic CO2 molecule has higher affinity towards basic TiO2 metal
centre when subjected to reduction of the former. Spectroscopic data
reveals that under light illumination the Ti3+, present at the surface of
TiO2 catalyst, adsorbs CO2 and transfers an electron to produce bent
CO2•–. In this process Ti3+ oxidises back to Ti4+. The surface adsorbed H
atom further assist the reduction of CO2•–. It is very interesting to note
that the LUMO of the formed CO2•–species is observed to be much
lower in compared to that of gaseous CO2 molecule. Hence, enjoying
the opportunity to be easily reduced by the electrons obtained from
excited state of the semiconductors [14]. Some of the literature studies
has been discussed here. Lv et al. studied the photodegradation of
Brilliant Red X3B, an anionic azo dye using stable anatase TiO2 pho­
tocatalyst. The specific photocatalytic activity (per surface area unit) of
0.0050 min−1m−2 was achieved at 1 g/L catalyst loading within
120 min of reaction under UV light irradiation [15]. Kočí et al. reported
the photocatalytic reduction of CO2 using pure TiO2. A substantial in­
crease of methane yield was observed after 8 h of irradiation [16].
Wang et al. studied the photocatalytic CO2 reduction using rutile TiO2
nanoparticle modified anatase TiO2. The total yield of CH4 obtained in
the experiment after 8 h of continuous irradiation was 18.9 μmol g-
1
[17].
Inspite of having several advantages of TiO2 nanomaterial, the
high band gap (3.2 eV) of anatase phase of TiO2 restrict the solar
light absorption. Generally, TiO2 naturally occurs as three poly­
morphs: anatase, brookite and rutile. Among them, the anatase
phase of TiO2, rutile or anatase-rutile mixed phase (e.g., Evonik-
Degussa P25) responds under UV light irradiation for CO2 photo­
reduction purposes [18]. However, the brookite phase is much less
studied as a photocatalyst. Thus, the amendment of TiO2 by suitable
processes is necessary to harvest solar energy of visible range.
Moreover, sensitization and doping on TiO2 semiconductor, are most
effective methods for encompassing the absorption range to visible
radiation. Besides, Z scheme photocatalyst, heterojunction, S-
scheme, cocatalyst, defect formation has emerged as an efficacious
strategy for effective photocatalytic transformations. Liu et al. in­
vestigated the photocatalytic CO2 reduction with water vapor by La-
modified TiO2 nanoparticles. The La-modified TiO2 showed high CH4
yield of 3.457 μmol under 20 h light irradiation. [19]. Tan et al.
synthesized reduced graphene oxide-TiO2 nanocomposite (rGO-
TiO2) and examined its photocatalytic CO2 reduction activity. The
prepared rGO-TiO2 nanocomposites exhibited almost 0.135 μmol g−1
h−1 superior photocatalytic activity [20].
Among the other application perspective regarding TiO2-based
semiconductors, transformation related to photocatalytic reduction of
a major green-house gas, carbon-di-oxide (CO2), emerged out to be an
important field of research. Presently, almost 80 % of the energy re­
source of the world is based on fossil fuels leading to consumption of
fossil fuel as-well-as large-scale emission of atmospheric CO2 [21]. This
causes significant global warming effect, which is a context of hyper­
critical problems, requiring urgent attention. In this regard conversion

2
I. Som and M. Roy
of carbon dioxide into fuel imparts one step solution triggering both of
the emerging problems (global warming effect and fast diminution of
fossil fuels) simultaneously. Researchers are, therefore, striving to
develop suitable efficient photocatalysts for the purpose of reducing
CO2 to fuels (H2, CO, HCOOH, HCHO, CH3OH, CH4) and valuable che­
micals exploiting solar energy. In this regard, several research groups
worldwide have prepared various types of TiO2 based photocatalyst to
explore the application perspective of photocatalytic CO2 reduction.
Still deeper insight and understanding of this topic in terms of struc­
tural characteristics of photocatalyst surface, mechanistic as well as
kinetic aspect of the reaction, and appropriate knowledge of product
selectivity, is limited. The objective of this review is to summarize
fundamental aspects like principles, thermodynamics etc. Intense
importance has been devoted on the design considerations related to
the improvement of TiO2 photocatalyst. In this context current studies
related to the compositional and structural engineering of TiO2 has
been documented elaborately. Apart from that special emphasis has
been given on the discussion of TiO2 based heterojunction photo­
catalyst which shows enhanced photocatalytic activity due to its im­
proved structural characteristics. The knowledge of tuning several
reaction parameters (pH, reaction temperature, photoreactor type,
wavelength of irradiated light, surface functional group, CO2 partial
pressure) in order to improve photocatalytic CO2 reduction reaction
selectivity and efficiency, is very crucial. Thus, literature studies related
to the above topic is documented intricately to provide a detailed
guide for the same. Moreover, an overview on the photocatalytic CO2
reduction mechanism for different types of TiO2 based photocatalyst
has been presented mostly in-view of computational studies. Cur­
rently, there are several excellent reviews covering the topics related
to fabrication of different semiconductor photocatalyst, influence of
reaction conditions and CO2 reduction pathway. Compared to this our
recent review article assimilates to provide emphasis on (i) kinetics of
photocatalytic CO2 reduction process (ii) influence of various phases of
TiO2 and their structural or compositional modifications upon CO2
photoreduction rate (iii) study of structural engineering on TiO2 based
heterojunction photocatalyst (traditional, p-n junction, schottky
junction, Z-scheme, S-scheme) (iv) photocatalytic CO2 reduction me­
chanism on different types of TiO2 based nanomaterial (doped, carbon
based TiO2 nanomaterial, TiO2 based heterojunction, etc.) mostly
supported by the computational studies.
2. Principle
In a natural photosynthesis process CO2 and H2O are being
converted to oxygen and carbohydrates in the presence of solar light.
Thus, alteration (reduction) and storage of adsorbed atmospheric
CO2 occurs in the form of carbohydrate occurs under natural solar
energy [22].
Sunlight + nH2O + nCO2 → (CH2O)n+ nO2
Scientist worldwide is trying to mimic the natural photo­
synthetic process to convert CO2 into useful chemicals mainly using
a semiconductor or modified semiconductor. The mechanistic re­
view of semiconductor-based CO2 photoreduction process is de­
monstrated in Fig. 1.
The process consists of three steps [23,24,26].
(i) Absorption of light (hν > Eg) by the semiconductor
(ii) Separation of charge transporters (electron−hole)
(iii) Redox reactions at the surface
At first the photocatalyst absorbs light resulting excitation of
electrons in the conduction band (CB) from the valence band (VB). As
a result, holes in the VB are left behind. Therefore, CB and VB of the
photocatalyst should overlap both the reduction potential of CO2 and
3
Journal of Alloys and Compounds 918 (2022) 165533
Fig. 1. Schematic representation of photocatalytic reduction of CO2 mechanism on a
semiconductor photocatalyst.
the oxidation potential of water, respectively (Fig. 1). The transfer of
electrons from the CB is facilitated by the negative CB edge relative
to the reduction potential CO2. Similarly, the transfer of holes from
the VB to water molecules gets accelerated by the more positive VB
edge relative to the water oxidation potential. Hence, transfer of
electrons from the CB to CO2 as well as from water to the VB of the
semiconductor photocatalyst are thermodynamically feasible under
the illumination of light, whereas, uphill reaction is regarded as the
direct reduction of CO2 using water. Hence, from the reduction po­
tential values it may be concluded that the high negative reduction
potential (E (CO2/ CO2•−) = −1.85 V vs SHE) value leads to the one-
electron reduction reactions for CO2, i.e., formation of CO2•−. This
highly negative reduction potential in case of CO2 to CO2•− trans­
formation can be ascribed by the change in hybridization of C from
sp2 to sp3. Reduction potential for the formation of HCOOH, HCHO,
CH3OH, and CH4 are small (−0.665, −0.485, −0.399, and−0.246 V) and
more positive relative to CB edges of some of the semiconductors. In
this cases water molecules are also involved along with CO2 for the
formation of the reduced products. Hence, in this regards proton
coupled electron transfer (PCET) process has been predicted wherein
electron transfer to CO2 is accompanied with proton transfer. The
details regarding the CO2 photoreduction process and the generation
of major products, has been discussed elaborately in the next
section.
3. Thermodynamics and total pathway for major products
formation related to CO2 photoreduction
The linear conformation of CO2 (with two double bonds between
carbon and oxygen atoms) with higher stability (ΔG0 = −400 kJ mol-1).
Hence, its conversion into valuable chemicals without the presence of
any catalyst is non-spontaneous. The large energy gap between LUMO
(lowest unoccupied molecular orbital) and HOMO (highest un­
occupied molecular orbital) (13.7 eV) and high electron affinity of CO2
(−0.6 ± 0.2 eV) makes CO2 very less reactive molecule [24–26]. The
energy barrier diminishes while adsorption of CO2 onto a catalyst/
photocatalyst surface, modifying the linear structure of CO2 to bent
structure. Therefore, the bent structure of CO2 leads to the lowering of
LUMO, imparting to their high reactivity. This activated photocatalyst
surface-bound CO2 commences several consecutive chemical reac­
tions which includes the transfer of an electron or a proton, breaking
C−O bonds, and creating new C−H bonds. The distribution of the final
products can be varied depending on the availability of charge carriers
to take part in the chemical reaction, operating conditions, and the CB
and VB edge position of the concerned photocatalyst [27,28].
In the photoreduction process of CO2 the first step is the generation
of·CO2- anion radical by arresting an electron from the CB of a
I. Som and M. Roy
photocatalyst [29,30]. The acidic nature of CO2 molecule exhibits
strong affinity towards any nanomaterial surface of alkaline nature.
Rather than other acidic metal oxides, TiO2 (a basic metal oxide)
[31,32] facilitates the interaction between CO2 and the photocatalyst
surface resulting in the generation of anionic radical·CO2- [Eq. (1)] [33].
CO2 + e− → CO2•− (−1·85 V vs·SHE)
The existence of ample Ti3+ sites on the TiO2 surface produces a
low-coordinated oxygen species, which enhances the number of
basic sites on titania [34]. Several experimental investigations re­
garding chemisorption of CO2 onto the other basic metal oxide
surfaces like ZrO2 [35], MgO [36], and Ga2O3 [37] have also revealed
the generation of·CO2-. This step is followed by protonation and
subsequent disproportionation reactions which leads to produce CO
in the first step of photoreduction process. Besides, CO can also be
obtained via dissociation of·CO2- at the oxygen vacancy sites in case
of acidic TiO2 surface. In this context it is to be mentioned that, two
fundamental mechanisms have been anticipated for photocatalysis
of CO2 in presence of H2O. The prior mechanism proposed by Sub­
rahmanyam involves the formation of methane and methanol
from·CO2- via a series of reactions;·CO2-→ HCOOH→ HCHO→
CH3OH→ CH4 [38]. Another mechanism proposed by Sasirekha is
based on the assumption that methane and methanol were pro­
duced in parallel reactions through formation of carbon mon­
oxide,·CO2-→ CO→ CH4, CH3OH [39]. The formation of other major
products (HCOOH, HCHO, CH3OH, CH4, and C2H5OH) [40–42] ob­
tained from CO2 can be understood from Scheme 1. Herein the
number of reducing CB electrons and protons (H+) required for the
production of major products from CO2 has been depicted.
4. Kinetics of CO2 photoreduction
Recently understanding and establishment of accurate kinetic
model at the surface of the photocatalyst is the key factor to enhance
the efficiency of the photocatalytic CO2 reduction process. Among
the different kinetics model microkinetic approach and
Langmuir−Hinshelwood model generally fits well with the experi­
mental data obtained in such photoreduction process.
4.1. Microkinetic model
The microkinetic model was based on the fundamental intrinsic
processes occurring at a molecular level of the photocatalysts sur­
face. In this model only the formation of CH4, CO and H2 were as­
sumed whereas the hydrocarbons produced were neglected owing
to its negligible amount. All the reactions in this model were con­
sidered to follow first order kinetics [43–45]. The rate of adsorption
for gaseous species has been expressed as.
rG G
ads = kfwd θempty GRgasT
where kG
fwd is the fitting parameter for the forward rate coefficient of
gaseous species, θempty is the surface coverage of empty sites, G is the
Scheme 1. Representation of the different pathways for production of the major
products while photoreduction of CO2.
Journal of Alloys and Compounds 918 (2022) 165533
gas fraction, Rgas is the gas constant and T is the temperature.
the rate of desorption for gaseous species has been articulated as
below.
rG G
des = krev θgas (3)
where kG is the fitting parameter for the reverse rate coefficient of
(1) rev
gaseous species, and θgas is the gas surface coverage.
The evolution of gaseous species has been depicted by following
the generalized differential [Eq. (4)]
G Vg
= ( r G ads + r G des) f + (G in G) x
t Vr (4)
where f depicts the factor of available surface sites for gas interac­
tion, Gin is the gas inflow where G = CO2, H2O, O2, H2, CO, and CH4).
It is worthy to note that in this model the rate constant value of
reactions (i.e. k) cannot be used directly to estimate the activation
energy as the pre-exponential factors were considered approximate.
The rate constant value can be absolutely over or under-determined
by many orders of magnitude. Fundamentally, the measurement
does not necessarily follow the fitted curve over total time span of
the experiment because the photocatalyst can be both activated and
deactivated on such a long time-scale. While proceeding during the
entire span of the reduction reaction, the number of active sites
change. Here the catalyst poisoning phenomenon was quite obvious
where the concerned photocatalyst surface gets poisoned with in­
termediates, resulting in significant decrease in the number of active
sites. This phenomenon was not taken into consideration in this
model. Thus, this explains the reason for the nature of all the fitted
curves which exhibited a steady graph after the initial hike. Bjelajac
et al. used micro-kinetic modelling parameters for fitting their ob­
tained experimental results. In this case the rate constant value (k1)
of the water dissociation process, which was considered to be rate
limiting step for N-doped TiO2 photocatalyst, was obtained to be
highest. This can be explained owing to the fact that the water
dissociation depends not only on the amount of absorbable photons
but also on the materials composition [46].
4.2. Langmuir−Hinshelwood (L-H) model
Langmuir–Hinshelwood kinetics is the most frequently used ki­
netic expression which explain the kinetics of the heterogeneous
catalytic processes. The empirically derived LH-based kinetic model
[Eq. (5)] provide an alternative approach to microkinetic modelling
approaches. Here rate expression has been depicted as.
Rate = kθAθB = k·KAPAKBPB/ (1+KAPA+KBPB)2 (5)
where θA and θB represent the fractional surface coverage of each
(2)
reactant while PA and PB are the partial pressures of each species, k is
the rate constant, KA and KB are the adsorption equilibrium constant
parameters, which are temperature dependent.
The advantage of using this approach is that it includes the im­
pact of partial pressure on the kinetic data. However, the dis­
advantages include requirement of ample time and experimental
effort to collect CO2 photoreduction kinetic data [47,48]. Tan et al.
studied the kinetic of the photocatalytic CO2 reduction reaction over
synthesized graphene oxide supported oxygen-rich TiO2 nano­
composite (5GO-OTiO2) by Langmuir-Hinshelwood surface reaction
mechanism [49]. CH4 and CO were the main products in this
photocatalytic conversion which was performed in presence of H2O
[Eq. (6)].
3CO2 + 2 H2O → CH4 + 2CO + 3 O2 (6)
4
I. Som and M. Roy Journal of Alloys and Compounds 918 (2022) 165533

the photocatalytic process involves the desorption of the products.

[Eqs. (7–11)] mentioned below, depicts all plausible reaction steps
which take place during the photocatalytic reduction of CO2
with H2O.
+ e ,H2O
H2 O + H+ OH + H 4H + O2 (7)

H
CO2 +e CO2 CO + OH (8)

H
CO + e CO C + OH (9)

H H H
C+H CH CH2 CH3 CH4 (10)

H
nCH2 + mCH3 C2H4 + C2H6 (11)

5. CO2 reduction with TiO2-based semiconductor photocatalysts

To a get deeper insight about the photocatalytic CO2 transfor­

Fig. 2. Conceptual diagram depicting the reaction mechanism of CO2 photoreduction
process based on the Langmuir-Hinshelwood mechanism.
Adapted from ref [49] Copyright 2016 Elsevier.
Herein, the value of H2O adsorption equilibrium (KH2O) was ob­
tained to be 8.07 bar-1, which was significantly higher than that of
CO2 (KCO2 = 0.02 bar-1). This result indicated that water molecule
adsorbed strongly onto 5GO-OTiO2 photocatalyst surface while there
occurred very weak adsorption of CO2 molecules onto the same
photocatalyst surface. This may be due to the superior hydrophilic
nature of TiO2 as well as graphene oxide. A proposed CO2 photo­
reduction mechanism based on the L-H model has been represented
in Fig. 2.
Formerly, the adsorption of reactant, i.e. CO2 and H2O molecules
onto the surface of 5GO-OTiO2 takes place. In the second step (sur­
face reaction),·CO2- radicals were produced owing to the transfer of
photogenerated electrons to the adsorbed CO2 molecule.
Furthermore, the holes react with adsorbed H2O molecules resulting
in the formation of H+ ions and·OH radicals (from which H·radicals
and O2 gas were produced) [50]. Thenceforth, several intermediate
radicals and the hydrocarbon products were produced by the reac­
tion between H·radicals (formed through the reduction of H+) and
carbon radical (formed after the reduction of CO). The final step in
mations, several investigations has been dedicated on different
photocatalysts, especially on well-known TiO2-based photocatalyst.
Synthesis and proper tuning of such TiO2-based photocatalysts has
been studied for achieving better CO2 transformation efficiency.
Fig. 3 represents the different types of photocatalyst studied so far
for the same transformation. The following section provides a de­
tailed discussion regarding each of the mentioned topics.
5.1. Doped photocatalyst
TiO2 photocatalysts have been employed as the leading material
for the photocatalytic reduction of CO2. TiO2 semiconductor photo­
catalyst (d0 metal oxide system) possess CB band and VB energy
levels at 2.7 V and − 0.50 V versus NHE, respectively. Nevertheless,
the wider band gap (3.2 eV) of TiO2 generates very few charge car­
riers which leads to injection of lesser number of electrons into CB,
proving it as less efficient material for reduction processes.
Therefore, numerous efforts have been made to modify pure TiO2
which can effectively harvest visible spectrum of solar light. Among
these the most suitable and widely accepted methods are doping
and co-doping of TiO2 with various metals, and/or non-metals.
Serval types of doping has been illustrated below.

Fig. 3. Classification of different types of photocatalyst utilized for CO2 reduction.

5
I. Som and M. Roy
Fig. 4. (A) {left side} Effect of doping amount on photocatalytic reduction of CO2 in 24 h under UV-A. (B) {right side} Effect of light on photocatalytic reduction of CO2 in 24 h in
presence of KOH/H2O medium.
Adapted from ref [53] Copyright 2018 Elsevier.
5.1.1. Transition Metal doped
Doping with transition metal or metal ion (M+ ion: M = V, Cr, Mo,
Mn, Fe, and Ni) is an effective approach to enhance the light ab­
sorption range of pure TiO2 [51]. Feng et al., prepared Mo (cheap
transition metal) doped TiO2 photocatalyst via one-pot hydro­
thermal route at 473 K [52]. Several such photocatalysts with varying
Mo concentrations were prepared to investigate the photoactivity
towards reduction of CO2 into CH4. It was observed that the CH4
selectivity was increased with the increase in the Mo concentration
in the photocatalyst. The optimum Mo concentration was found to
be about 0.3 wt % with an efficiency of 54.1 %. The enhanced pho­
tocatalytic activity in case of 0.3 wt % Mo loaded photocatalyst can
be attributed to the enhanced electron-hole separation owing to Mo
loading.
Olowoyo et al., synthesized a series of Cu doped TiO2 photo­
catalysts by varying the amount of Cu, following a sonothermal-
hydrothermal method [53]. The obtained photocatalysts showed
higher surface area, with Cu species doped on the surface as well as
into the lattice of TiO2. Investigations regarding the photocatalytic
efficiency of these prepared materials revealed that the Cu2-TiO2
photocatalyst performed best at the optimum reaction conditions
under irradiation with UV-A light [Fig. 4 (A)]. Interestingly,
6.6 mmol g-1 of methane, 472.5 mmol g-1 methanol and more re­
markably 743.8 mmol g-1 of acetone, were obtained in case of CO2
reduction in KOH/H2O medium under irradiation for 24 h. While
under visible light irradiation 6.18, 0.53, 74.17 and 22.17 mmol g-1 of
methane, ethylene, methanol and acetone were obtained, respec­
tively. The copper content present in the photocatalyst might be
responsible for their activity under visible light. Furthermore, Cu
doping leads to the presence of ample Ti3+ ions on the surface of Cu2-
TiO2 photocatalyst which promotes excitation under visible light
irradiation. Besides, owing to the higher TiO2 content in the above
mentioned photocatalyst, the products obtained under UV-A irra­
diation was found to be higher compared to that produced under the
visible light irradiation [Fig. 4 (B)].
Ola et al., incorporated Ni2+ ion onto TiO2 photocatalyst and
found that incorporation of an optimal 1.5 wt % Ni2+ into TiO2 matrix
not only extended optical absorption in the visible light range, but
also notably increased CO2 photoreduction property [54].
5.1.2. Noble metal doped photocatalyst
Plasmonic metal nanoparticles like Au and Ag nanoparticles
doped onto semiconductors shows two interesting properties as: (i)
enhancement of electron–hole separation owing to the generation of
Schottky barriers, [55] (ii) extending the light absorption into the
6
Journal of Alloys and Compounds 918 (2022) 165533
visible light range and enhancing the surface electron excitation due
to the surface plasmon resonance phenomenon observed in case of
noble metals [56]. Now-a-days, plasmonic Au, Ag, Pt nanoparticles
doped TiO2 materials has engrossed researchers’ attention for being
applied as photocatalyst for reduction of CO2 under UV or visible
light illumination.
Tahir et al. prepared gold-nanoparticles (Au-NPs) incorporated
TiO2-nanowires (TiO2-NWs) by hydrothermal and chemical reduc­
tion route and investigated the photocatalytic activity of prepared
nanoparticles towards CO2 photoreduction using H2 gas under
visible light irradiations [57]. With the deposition of Au-NPs, the
efficiency of CO2 reduction, to produce CH4 and CH3OH, was greatly
enhanced under visible light irradiations due to surface plasmon
resonance of the doped Au nanoparticles.
5.1.3. Rare earth element doped TiO2
Doping of TiO2 with rare earth metals has captivated research
attention in current years. Studies demonstrate that such doping can
improve the photocatalytic activity of TiO2 [58]. Lanthanide ions,
with general electronic configuration [Xe]4 f0–145d0–1 6 s2, could
easily form complexes with several Lewis bases as for example acids,
aldehydes, and alcohols [59], [60]. Moreover, presence of lanthanide
ions provides high electrical conductivity and thermal stability to
the material [61]. Furthermore, lanthanide ions can also reduce
electron-hole recombination rate for TiO2 photocatalyst, by trapping
the excited electrons. This can significantly lower the recombination
of photogenerated electron-hole pairs [62–65].
Ali et al. synthesized Ce doped TiO2 photocatalyst (0 −2 wt %) via
sol gel method [66]. Ce/La/TiO2, prepared via an optimum Ce doping
of 1.5 wt% in TiO2, exhibited the highest photocatalytic activity under
fluorescent light illumination. In the liquid phase, a maximum yield
of 317.7 μmol g -1 of CH3OH was obtained. Besides, the reaction in gas
phase produced CH4 and CO as the major products, with maximum
yields of 262.8 and 119.4 μmol g-1, respectively. The respective
product yield of CH3OH, CH4 and CO for 1.5 wt% Ce/La/TiO2 was
found to be around 1.8, 1.9 and 2.1 times higher than that of La/TiO2.
[Fig. 5 (a), (b) & (c)] demonstrates the yield of all the obtained
products with respect to time in presence of varying Ce, La dopant
amount onto TiO2 photocatalyst.
Huang et al. prepared Eu-doped TiO2 nanoparticles by a simple
sol-gel method and investigated their photocatalytic performance
towards CO2 reduction under irradiation with a 300 W Xe arc lamp
for 9 h [67]. In case of 0.25% Eu-TiO2 catalyst maximum yields of CH4
(65.53 μmol g-1) and CO (42.91 μmol g-1) were observed. In com­
parison to pure titania photocatalyst the product generation was
I. Som and M. Roy
Fig. 5. Graphical representation regarding yield of (a) CH3OH, (b) CH4 and (c) CO
under UV light irradiation in presence of TiO2 and TiO2 based photocatalysts.
Adapted from ref [66] Copyright 2017 Elsevier.
significantly better in case of 0.25% optimum Eu doped TiO2 pho­
tocatalyst, which can be ascribed as hindered charge carrier re­
combination rate in case of doped photocatalyst. However, it was
also found that increased doping content decreased photocatalytic
reduction activity. Peng et al. synthesized Sm-doped TiO2 nano­
composite via sol-gel method and applied it for photoreduction of
CO2. 0.5 % Sm-TiO2 catalyst showed best photocatalytic activity over
other catalyst [68]. The CO and CH4 yields using 0.5 % Sm-TiO2 cat­
alyst were 55.47 and 3.82 μmol g-1 respectively, which were 5.02 and
2.67 times compared to the yield for TiO2 photocatalyst.
5.1.4. Co-metal doped photocatalyst
The doping of bimetallic elements together on TiO2 semi­
conductor photocatalysts has been endorsed as a prospective ap­
proach for synergistic improvement of the visible light response of
photocatalysts. Therefore, suitable co-dopant combination is essen­
tial to increase the photocatalytic activity of TiO2 semiconductor
[69–72]. Pham et al. prepared Ag and Cu co-doped TiO2 photo­
catalyst system deposited onto polyurethane (PU) substrate for ef­
fective conversion of CO2 into solar fuels under visible light [73]. Ag
and Cu dopants create defects into the TiO2 lattice which result in
7
Journal of Alloys and Compounds 918 (2022) 165533
the formation of Ti3+and oxygen vacancies in the lattice, leading to
the improvement of CO2 adsorption and conversion efficiency.
Hence, Ag and Cu co-doped TiO2 deposited on polyurethane to form
2Ag@ 4Cu-TiO2/PU (where Ag/TiO2 and Cu/TiO2 were deposited in
the ratios of 2 and 4 wt %, respectively) exhibited the highest rate of
photocatalytic reduction of CO2 to CH4 (yield 880 μmol g-1) and CO
(yield 550 μmol g-1) under visible light irradiation. Xiong et al.
synthesized V and W co-doped TiO2, with dopants existing as V4+
and W6+ ions on the internal surface of honeycomb channels while
V5+(V2O5) loaded onto the surface, of TiO2 [74]. On investigation
about the photocatalytic efficiency of such co-doped TiO2 towards
CO2 reduction they found that V4+ doping enhanced the visible light
absorption efficiency of TiO2, by introducing an intermediate state
within the band gap of TiO2. Furthermore, the W6+ ion incorporated
in the TiO2 lattice structure could trap photogenerated electrons and
transfer them to surface adsorbed CO2 and water molecules. The CO,
CH4, and H2 yields for V3W3T (where mass ratio of 3% V2O5/TiO2 and
3% WO3/TiO2 are present) photocatalyst were 1.91, 0.22, and 0.27
μmol g-1 h-1, respectively, which were much higher than those of
single metal doped TiO2 catalysts.
5.1.5. Oxygen Vacancy Self-doped photocatalyst
Recently, designing of oxygen vacancy self- doped TiO2 (surface
engineering) is achieving utmost importance as it has wide ab­
sorption range and a high charge transfer capacity which has been
found to enhance photoreduction capability of the prepared TiO2.
Meanwhile, Ti3+ ions with surface oxygen vacancies can enhance
hole trapping. Thus, the separation of photoexcited electrons and
holes occurs, indicating increase in charge transport and charge
transfer phenomenon [75]. In a nut shell oxygen vacancy self-doping
method enhances three key factors simultaneously- (i) photo­
induced charge generation (ii) charge separation and (iii) charge
transportation. The separation of charge carrier can also be ex­
plained from the perspective of strain engineering. Generally, the
incorporation of oxygen vacancies may disturb or modify the D-
spacing of the lattice, subsequently developing lattice strain.
Therefore, a built-in electric field is generated due to the loss of the
symmetry of the crystal structure. As a result, displacement of po­
sitive and negative charge centres of the unit cells occurs which
ameliorate the photocatalytic activity of TiO2 [76]. Gao et al. fabri­
cated black titania nanotube arrays (B-TiO2 NTAs) by electrochemical
anodic oxidation method for photocatalytic CO2 reduction [77]. The
oxygen vacancies in the synthesized B-TiO2 NTAs developed new
defect energy levels within the band gap of TiO2, which broadened
their visible light absorption by reducing the band gap. Thus, in their
study, they had found that B-TiO2 NTAs samples exhibited better
photocatalytic performance than TiO2 NTAs-450-A under visible
light illumination [shown in Fig. 14 (a) in the later section]. The
corresponding graph comprising of CO yield from CO2 reduction
showed that B-TiO2 NTA-600 sample exhibited best activity [shown
in Fig. 14 (b) in the later section]. Hence, the experiment proved the
importance of the oxygen vacancies which were the catalytic sites
and accelerate surface reactions regarding reduction of CO2 to CO
(CO yield of 185.39 μmol g−1 h-1 was achieved) under visible light
irradiation. The mechanism of CO2 conversion in presence of water
molecule has been discussed in the later section.
5.1.6. Non-metal doped
Apart from doping strategies related to replacement of oxygen in
the lattice by oxygen vacancies (discussed prior) doping with non-
metallic elements e.g., nitrogen, sulphur and carbon, is also well
known [78] In this kind of doping, the energy difference between VB
and CB decreases owing to the introduction of occupied orbitals
above the VB of the semiconductor. Doping with non-metallic ele­
ments makes photocatalysts more durable and stable [79,80].
Doping of titania with nonmetals e.g. nitrogen [81], sulphur [82], and
I. Som and M. Roy
Fig. 6. (a) Effect of the base on photocatalytic reduction of CO2 in 24 h under UV-A light. (b) Effect of catalyst amount on photocatalytic reduction of CO2 in 24 h under UV-A light.
(c) Effect of doping amount in the gas phase on photocatalytic reduction of CO2 in 24 h under UV-A irradiation. (d) Effect of the sacrificial agent TEOA on photocatalytic reduction
of CO2 in ACN and H2O mixture in 24 h under visible light irradiation.
Adapted from ref [85] Copyright 2018 Elsevier.
fluorine is another efficacious approach which could lead to nar­
rowed band gap resulting in bathochromic shift of the absorption
band of TiO2 [83].
Akple et al. utilized hydrothermal approach to synthesize highly
crystalline N‐doped anatase TiO2 nanoparticle (N-TiO2 NP) as-well as
N‐doped anatase TiO2 microsheets (N-TiO2 MS) with 65% and 35% of
exposed (001) and (101) faces, respectively. [84]. The prepared N-
TiO2 NP with large surface area exhibited remarkably higher pho­
tocatalytic activity than its precursors, TiN and commercial TiO2
(P25) under irradiation of visible light. Olowoyo et al. synthesized a
series of sulphur doped TiO2 nanoparticles with varied amount of
sulphur (S-TiO2-1, S-TiO2-2, S-TiO2-3) via sonothermal method [85].
These potential photocatalysts were then utilized to reduce CO2 to
hydrocarbons under illumination by UV-A and visible light sepa­
rately, with or without sacrificial electron donor. It was observed
that the surface conductivity and charge transfer rate of the doped
photocatalysts increases with the hike in sulphur doping, which in-
turn results in the increment of the photocatalytic reaction rate as
compared to pure TiO2. Furthermore, the effect of different bases
and solvent system (acetonitrile-water mixture) were also studied.
The highest photoactivity was seen in case of KOH solution which
exhibited a maximum yield of 6.25 mmol g-1 methane, 2.74 mmol g-1
of ethylene, 0.074 mmol g-1 of propylene and 0.030 mmol g-1 of
propane under UV-A irradiation for 24 h. Besides, the photoreduc­
tion when performed in acetonitrile-H2O mixture, the product se­
lectivity was also observed to be varied upon the absence (with
product yield as: 167.6 mmol g-1 of methane and 12,828.4 mmol g-1
of methanol) or presence (with product yield as: 846.5 mmol g-1 of
methane and 4030 mmol g-1 of methanol) of TEOA as sacrificial
donor. The bar diagrams given below illustrates the amount of dif­
ferent product formed under various conditions [Fig. 6(a): Products
formed in the presence of variation of bases, Fig. 6(b): Products
8
Journal of Alloys and Compounds 918 (2022) 165533
formed with different catalyst dosage, Fig. 6(c): Products formed
with different sulphur dopant amount in TiO2, and Fig. 6(d): Pro­
ducts formed with different solvent systems in the reaction
medium].
Zhang et al. efficaciously synthesized 10 % I-doped TiO2 samples
(mixture of anatase and brookite phases) which revealed high CO2
photoreduction activity when compared to pure TiO2 samples (~2.4
μmol g−1 h−1) under visible light irradiation [86].
One of the effective methods to boost up the photocatalytic
properties of materials is defect engineering including vacancy and
foreign element doping. The physical and chemical properties of
materials can be modulated by the synergistic effect of multiple
defects. Several studies have reported that although the introduction
of defects can broaden the photoactivity range of a catalyst sig­
nificantly, it does not always mean that the photocatalytic activity
will be enhanced [87]. This mismatch can be solved by under­
standing the complex interactions among the multiple steps in­
volved in photocatalytic reaction. Therefore, suitable defect
concentration or site should be constructed on the photocatalytic
material. In this regard some literature survey (black TiO2 nanotube)
depicts dual-defect strategy (surface oxygen vacancies and bulk ni­
trogen doping) for enhancement of thermodynamic and kinetic
perspective of the prepared photocatalyst [88].
5.2. Sensitized Photocatalyst
The wide band gap of TiO2 semiconductor can be narrowed down
by the use of species called photosensitizers. This method proved to
be a relevant alternative to extend the visible light absorbing cap­
ability of TiO2. Photosensitizer can be broadly categorized into two
types: inorganic materials (CdS, CdSe quantum dots etc.) [89–91]
and metal-free organic species like polypyridyl complexes,
I. Som and M. Roy
porphyrins [92], phthalocyanines [93], and corroles [94], etc. Apart
from being less-toxic and better solubility to the host matrix, pho­
tosensitizers that is to be coupled with TiO2 must possess the fol­
lowing properties. (i) The HOMO (in case of molecular
photosensitizer) or VB (in case of inorganic material based sensiti­
zers) of the photosensitizer species must be positioned below the
energy level of the redox couple such that the oxidized photo­
sensitizer species obtained after electron injection into the CB of the
semiconductor could be regenerated easily (by transferring the holes
to TiO2 nanomaterials) (ii) In order to diminish the energy loss as
much as possible the CB of TiO2 must be matched well with the
excited state energy level of photosensitizer. The photosensitizer
based TiO2 is being effectively used nowadays, for photocatalytic CO2
reduction. The section below illustrates different types of TiO2 based
sensitized photocatalyst and their application towards CO2 photo­
reduction reaction.
5.2.1. Organic Dye molecules as photosensitizer
The dye sensitized photocatalysts have been found to be very
effective in exploiting maximum natural source of light irradiation.
Hence, photochemical transformation with such dye molecules as
sensitizers is a quite convenient way. In this case, the photo­
genarated electron produced under visible light irradiation, transfers
from the dye molecule to the CB of the photocatalyst [95]. It is to be
noted that the charge separation can be efficiently attained by
adding a co-catalyst to trap this photogenarated electrons. Nguyen
et al. reported metal (Cu and Fe) doped TiO2 sensitized with N3 dye
[RuII(2,20-bipyridyl-4,40-dicarboxylate)2(NCS)2] and exploited the
photocatalyst to photoreduce CO2 to fuel (CH4) in presence of H2O
and natural sunlight [96]. It was reported that methane production
rate was 0.617 and 0.847 μmol g-1 h-1 under concentrated natural
sunlight and artificial light respectively using Cu(0.5 wt %)–Fe(0.5 wt
%)/TiO2/optical fiber sensitized with N3-dye.
5.2.2. Quantum dots (QDs) as sensitizer
Recently, majority of the research works is dedicated on quantum
dot (QD)-sensitized photocatalyst for photochemical conversion of
CO2, because of their desirable optical and electronic properties
[97–100]. The band gap of QD can simply be adjusted by controlling
the size of the QDs, for achieving better visible light absorption from
the solar spectrum [101–104]. Basically, metal chalcogenide (in­
cluding CdSe or ZnS) QDs when coupled with suitable semi­
conductors facilitates the photon-based transformation of CO2 into
hydrocarbon fuels. Furthermore, the tunable electronic structure of
the QDs enables excellent redox chemistry as-well-as good charge-
separation efficiency, in case of the prepared QDs based photo­
sensitizer photocatalyst [105]. Cheng et al. designed Cu2+ ions in­
corporated CdS QD which were deposited onto the TiO2 nanorod
array films. The synthesised QD sensitized TiO2 were utilized as a
photocatalyst for the reduction of CO2 under visible light irradiation
[106]. The presence of Cu2+ ion in this case functioned as dual role:
(a) inhibition regarding the recombination of the electron hole pairs
and (b) broadening of the visible-light response of the sensitized
photocatalyst. The CdS-Cu2+/TiO2 nanorod array films exhibited
much better activity than conventional catalysts with maximum
ethanol yield of 109.12 μmol g-1 h-1. Wang et al. investigated PbS
quantum dots (PbS-QDs) sensitized Cu/TiO2 catalysts for photo­
catalytic reduction of CO2 [107]. It was reported that 4 nm PbS-QD
present in the synthesized Cu/TiO2 catalyst exhibited the highest
CO2 conversion yield of 1.71 mmol g-1 h-1 (0.82 mmol g-1 h-1 CO,
0.58 mmol g-1 h-1 CH4, and 0.31 mmol g-1 h-1C2H6). The yield was
found to be almost 5 times higher than that of Cu/TiO2 without any
photosensitizers. In addition, 4 nm PbS-QD sensitized Cu/TiO2 pho­
tocatalyst exhibited higher product yield as compared to 3 and
5 nm size.
9
Journal of Alloys and Compounds 918 (2022) 165533
5.2.3. Conducting carbon based material as sensitizer
Porphyrins are a group of heterocyclic macrocycle, composed of
four modified pyrrole subunits interconnected at their α-carbon
atoms via methine bridges(=CH−). These types of porphyrin based
macrocycle, possesses high absorption capability of visible light with
high quantum yield. Metalloporphyrin type complexes can also act
as visible light active sensitizers. TiO2 when coupled with such
porphyrin-based materials proved to be an effective photocatalyst
towards photoreduction of CO2 [108,109]. Furthermore, in case of
porphyrin sensitized ligand-assisted modified-TiO2, electron and
energy transfer occur smoothly between porphyrin and ligand mo­
lecules due to their similar energy levels. Wang et al. synthesized
supramolecules containing zinc(II)/copper(II)/cobalt(II) porphyrins
and ruthenium(II) polypyridyl complexes along with TiO2 nanotubes
to form corresponding conducting carbon modified TiO2 nanotube-
based photocatalysts [110]. It was investigated that the above sen­
sitizers with various molecular structures, such as coordinated me­
tals in porphyrin and peripheral polypyridyl ligands, exhibited
different efficiency. ZnPyP-RuBiDipy-TNT (TiO2 nanotubes–modified
with functionalized supramolecular sensitizers: zinc(II) porphyrin-
ruthenium(II) polypyridyl complexes) shows the best efficiency in
photoreduction of CO2 in the aqueous medium to form methanol
(746 μmol L−1g−1). In this regard it is worth to mention that Metallo-
phthalocyanines (MPc) are also a class of effective photosensitizers
which have superior semiconductivity and chemical stability
[111,112]. They intensely absorb blue-green region of the spectrum
which make it an efficient species to collect upto 50 % of the energy
available in the solar spectrum [113]. Yazdanpour et al. reported
photoconversion of CO2 under visible light by copper phthalocyanine
(CuPc) modified titanium-dioxide (CuPc/TiO2). It was observed that
15 % photocatalytic conversion of CO2 was achieved with 0.05 g
concentration of CuPc/TiO2 photocatalyst [114]. Bian et al. synthe­
sized ultrathin zinc phthalocyanine/BiVO4 nanosheet (ZnPc/BVNS)
composite, and used as wide range-visible-light harvesting photo­
catalyst for photoreduction of CO2 to CO and CH4 [115].
5.3. Composite photocatalyst with carbon based materials
In modern era, carbon based photocatalyst with exceptionally
economical, environmental friendly, non-toxic substance, has moti­
vated the researchers worldwide. The extensive π- π conjugated
system in carbon-based materials improves the circulation of pho­
toexcited electrons, resulting in separation of excitons. Moreover, the
high surface area leads to better dispersion of the photocatalyst on
carbon matrix and hence provides easy access for the reactant mo­
lecules to be adsorbed on the catalyst surface [116]. The synergetic
interaction between the photocatalyst and the carbon material in­
creases the yield of product, significantly. Therefore, any photo­
catalyst combined with carbon-based materials meets the demand
of efficient photocatalyst for reduction of CO2. In this regard, gra­
phene, carbon nanotube, conducting polymers and graphitic carbon
nitride have been found reliable to solve many practical issues.
Especially, in the last few years there occurred a huge surge in the
investigation regarding graphene-based composite photocatalysts
[117]. The large specific surface area, high work function, better
optical transmittance, and superb electrical conductivity of graphene
make it an efficient candidate with improved catalyst support and an
efficient electron acceptor/trapper [118,119]. Liang et al. compared
the photocatalytic reduction of CO2 utilizing solvent-exfoliated gra­
phene (SEG)-TiO2 nanocomposites and reduced graphene oxide
(RGO)-TiO2 nanocomposites as photocatalyst [120]. It was observed
that less defect-containing SEG-TiO2 was found to possess higher
photocatalytic activity towards the reduction of CO2 to CH4 than
RGO-TiO2 photocatalyst. SEG-TiO2 nanocomposites even showed
upto 7-fold improvement in efficiency as compared to pure TiO2,
under visible light illumination. This enhanced CO2 reduction
I. Som and M. Roy
capability of SEG-TiO2 nanocomposites can be attributed to the im­
proved mobility and diffusion of photoexcited electrons to the re­
active sites allowing easy electron availability for the reaction to
occur effectively. Zhang et al. reported photocatalytic CO2 reduction
in presence of graphene-TiO2 composite, with 8.5% graphene
loading, yielding 160 mmol g-1 methanol and 150 mmol g-1 formic
acid [121]. It was observed that the enhancement in graphene
loading can hike the photocatalytic performance rate.
Another widely studied carbon-based material with outstanding
optical properties and electron transferability is Carbon nanotubes
(CNTs). Thus, composite of CNT with suitable semiconductors like
TiO2, have also been reported to investigate the efficiency of the
formed TiO2-based photocatalyst [122]. Basically, CNTs in compo­
sites plays two crucial roles: firstly as photosensitizer which makes
room for the photoactivation of TiO2 under illumination of visible
light and secondly as electron sink which helps to transfer the
electrons to the adsorbed reactant molecules for reduction. The ex­
citons may consequently elicit the photoreaction by generating re­
active radicals like superoxide radical ions (O2·-) and hydroxyl
radicals (HO·) [123,124]. While performing photocatalytic CO2 re­
duction, Gui et al. reported methane yield of about 0.17 μmol g-1 h-1
in 6 hrs using laboratory synthesized multi-walled CNT/TiO2
core–shell nanocomposites under visible light [125]. In another
work, Gui et al. reported both methane (6.34 μmol g-1) and ethylene
(0.68 μmol g-1 h-1) production while using silver (2 wt % Ag)-doped
multi-walled carbon nanotubes@titanium dioxide nanocomposites
with core–shell structure [126].
Recently metal-free polymeric graphitic carbon with interesting
band structure, alluring physicochemical properties, chemically and
thermally stabile as-well-as being cost-effective, are known to be
broadly investigated [127]. Moreover, owing to adequate negative
potential of CB of g-C3N4, it can be suitably fitted for the purpose of
hydrocarbon fuel production from CO2 [128]. Dehkordi et al. in­
vestigated the CO2 photoreduction efficiency of the hollow carbon
nitride sphere (HCNS)@TiO2 composite nanostructure and revealed
that the composite showed product yield of 11.3 μmol g-1 h-1. The
hence obtained yield was around fivefold higher than pristine g-
C3N4 and ten-fold more effective than P-25 TiO2 photocatalyst [129].
Wang et al. obtained highest yield of CH4 and CO of about 72.2 and
56.2 μmol g-1, respectively, after 4 h irradiation during photocatalytic
reduction of CO2 under optimized condition in presence of g-C3N4
modified TiO2 [130].
In last few years, chitosan (CS), a biodegradable cationic poly­
saccharide, has gained immense attention as bio-sorbent, owing to
the presence of high contents of amino and hydroxyl functional
groups. Recently, several research groups focus on TiO2-chitosan
composite synthesis for their application as potential photocatalyst.
It has also been observed that immobilization of CS onto TiO2 solid
support can successfully achieve CO2 capturing and photoreduction
capability [131,132]. CS provide the features of steady spatial struc­
ture, superior spatial effects, robust coordination complexing cap­
ability and effective separation of photogenerated electron-hole
pairs [133]. She et al. reported the synthesis of Cu:TiO2-CS composite
and utilized the photocatalyst for CO2 reduction yielding 4.48 μmol
g-1 of CO and 5.34 μmol g-1 CH4 [134]. The activity of the composite
was found to be 10 times higher than that of pure TiO2.
Furthermore, some linear conjugated polymers such as polyani­
line (PANI) have also been utilized to form conjugate with any in­
organic semiconductors. Liu et al. reported a polyaniline/TiO2 hybrid
which showed a noteworthy improvement towards the photo­
catalytic reduction of CO2 in presence of H2O [135]. It is observed
that in comparison to pure TiO2 photocatalyst, 0.85% PANI–TiO2
hybrid photocatalyst showed CO, CH4 and H2 formation rates of 2.8,
3.8 and 2.7 times higher, respectively. This result indicated sy­
nergistic effect between TiO2 and PANI which provided such im­
proved activity. Additionally, the loading of these composite with Pt
10
Journal of Alloys and Compounds 918 (2022) 165533
nanoparticles resulted in the formation of Pt–0.85% PANI–TiO2
photocatalyst. On comparison with the Pt–TiO2 catalyst, the above
Pt-0.85% PANI- TiO2 photocatalyst produced 3.3 and 2.8 times higher
H2 (̴ 320 mmol g-1 h-1) and CH4 (̴ 50 mmol g-1 h-1) yield, respectively.
Another important category of carbon- based nanostructures, the
yolk–shell (YS) structure possesses interesting physical and chemical
features [136]. Typically, the YS structure consists of an inner core
and a hollow shell, which can stimulate the light scattering in hollow
areas and also provide a large surface to produce ample active sites
[137]. In this regard, Liang et al. showed enhanced photocatalytic
CO2 reduction by employing hollow heterostructure g-C3N4@CeO2
photocatalysts. The highest yields of CH4, CH3OH and CO was ob­
tained as 3.5 μmol g−1, 5.2 μmol g−1, 16.8 μmol g−1, respectively [138].
5.4. TiO2 based heterojunction photocatalyst
Apart from the photocatalyst that has been discussed above,
several different heterojunction based photocatalytic systems in­
cluding traditional heterojunction, p-n heterojunction, Schottky
junction, Z-scheme structure, S-scheme structure, etc. has been
known. Research groups worldwide are devoting their enthusiasm to
investigate the photocatalytic efficiency regarding such heterojunc­
tion based photocatalytic systems. Heterojunctions have long been
proposed with the research of semiconductors, and are generally
considered as the composites constructed by two or more different
semiconductors with intimate contacting interface, different band
energy levels, matched crystal lattice and similar thermal expansion
coefficient [139]. Different known heterojunction semiconductor can
be sub-classified as into traditional heterojunctions (type-I, type-Ⅱ,
type-Ⅲ), p-n junction, Schottky junction, Z scheme heterojunction
and S scheme heterojunction.
5.4.1. Traditional Heterojunction
The concept of traditional heterojunctions is deduced on the
basis of distinct band alignment between semiconductors. Thus,
they are classified as into three types (i) type-I heterojunction with a
straddling gap (ii) type-II with a staggered gap and (iii) type-III with
a broken gap. In case of type-I heterojunction photocatalyst the
conduction band (CB) and the valence band (VB) of semiconductor A
are respectively higher and lower than the corresponding bands of
semiconductor B. Therefore, under light irradiation, both electrons
and holes accumulate on the CB and VB of same semiconductor i.e.
semiconductor B respectively. Thus, the efficient separation of
electron–hole pairs are inhibited resulting in lower photocatalytic
activity. On the other hand, the CB and the VB levels of semi­
conductor A are placed in higher position than the corresponding
levels of the semiconductor B for the type-II heterojunction photo­
catalyst (Fig. 7). Therefore, under light irradiation feasible transfer of
photogenerated electrons from semiconductor A to semiconductor B
can occur, while movement of photogenerated holes occurs effec­
tively from semiconductor B to semiconductor A. Thus, spatial se­
paration of electron–hole pairs occur [140,141]. Shi et al. reported
yTiO2−x/g-C3N4 type II heterojunction photocatalysts (where, y = 8, 3,
2 and 1) as efficient material for photocatalytic CO2 reduction under
solar irradiation [142]. In this case, VB position of g-C3N4 and TiO2
were observed as 1.21 and 2.27 eV respectively while the CB posi­
tions were found as − 1.49 and − 0.68 eV, respectively. From the
perspective of band gap position, it is evident that photogenerated
electron transfer from CB of g-C3N4 to TiO2 can occur efficiently
while the photogenerated hole can feasibly transfer from VB of TiO2
to g-C3N4; establishing it as a type II heterojunction photocatalyst.
Herein, 2TiO2−x/g-C3N4 showed highest CO evolution rate of 77.8
μmol g−1 h−1, roughly 5 times than that of pristine g-C3N4 (15.1 μmol
g−1 h−1), owing to the large surface area and effective charge se­
paration in case of the synthesized heterojunction photocatalysts. As
revealed from Fig. 7, it is evident that in case of type-III
I. Som and M. Roy Journal of Alloys and Compounds 918 (2022) 165533

Fig. 7. Schematic illustration of exciton separation for traditional heterojunction photocatalysts: a) type-I, b) type-II, and c) type-III heterojunctions.
Adapted from ref [144] Copyright 2017 Wiley online library.

heterojunction photocatalyst, staggered gap between two partici­

pating semiconductors becomes so extreme that the bandgaps of
two semiconductors do not overlap [143]. Therefore, the efficient
migration and separation of charge carriers between the two semi­
conductors gets suppressed in the said case. Among the above-
mentioned traditional heterojunctions, type-II heterojunction is the
most promising traditional heterojunction to be used for improving
photocatalytic activity owing to its suitable structure for facile se­
paration of electron–hole pairs [144].

5.4.2. p-n Heterojunction

Recently, the combination of TiO2 and other semiconductor na­
nomaterials forming p-n heterojunction structures has been proved
to be very effective and demanding towards photocatalytic CO2 re­
duction. In this case a n type semiconductor (containing excess of
electrons) is kept in contact with p type semiconductor (containing
excess of holes). Thus, this leads to separation of photo-induced
electrons and holes while building a strong inner electric field, upon
light irradiation [145]. Fig. 8 represents the electron-hole transfer
process in p-n heterojunction photocatalyst.
Yang et al. fabricated a TiO2/Cu2O p-n junction nanorod to per­
form photocatalytic CO2 reduction [147]. Herein, the TiO2 /Cu2O-15%
exhibited the highest CH4 yield of 1.35 μmol g-1 h-1 within 4 h of
irradiation, which is much higher than pristine Cu2O and TiO2 when
used separately. The photoreduction capability of the TiO2 /Cu2O-15
% was increased due to the close construction of Cu2O nanoparticles
onto TiO2 nanorods, with formed p-n junction, to accelerate the
separation of photogenerated electron-hole pairs. Marcì et al. ob­
served maximum photocatalytic CO2 reduction by using laboratory
synthesized the GaP/TiO2 heterostructure (with 1:10 GaP:TiO2 mass
ratio) photocatalyst [148]. In this case, CH4 formation rate was ob­
tained to be 2.46 μmol g-1 h-1 . Under the same experimental
Fig. 8. Schematic illustration of the separation of electron–hole pairs in the case of
p–n heterojunction photocatalysts.
Adapted from ref [146] Copyright 2020 Wiley online library.
condition negligible methane production was observed for bare TiO2
Evonik P25 as well as GaP. Thus, this study indicated that GaP/TiO2
p-n heterojunction photocatalyst was efficient than that of bare TiO2
Evonik P25 photocatalyst, which emphasize the importance of p-n
junction photocatalyst.
5.4.3. Schottky Junction
Adding further into the heterojunction based photocatalyst list,
discussion on Schottky junction/barrier containing photocatalysts
are quite interesting. These photocatalyst shows superior photo­
catalytic activities due to the facile electron transfer and electron-
hole separation process occurring in the interfacial region between
metal and p-type semiconductor components [149]. Therefore, facet
engineering at the interface is a suitable and vital technique to fa­
cilitate charge separation in case of the Schottky junction [150].

11
I. Som and M. Roy
Fig. 9. Schematic of charge transfer for metal/TiO2 under UV light irradiation due to
the existence of the Schottky junction.
Fig. 9 shows the charge transfer process for metal/TiO2 under UV
light irradiation owing to the existence of the Schottky junction.
Yuan et al. obtained H2, CO and CH4 evolution rate of 5.5, 4.8 and
2.9 μmol g −1 h−1, respectively when photocatalyst prepared using
1 % molar ratio of Cu grafted onto mesoporous TiO2 (1Cu-mT). The
data revealed better efficiency in-case of the above hybrid photo­
catalyst compared to the bare TiO2 (mTiO2) and xCu-mT (where
x = 0.25, 0.5, 2, 3) [151]. An initial increment of photocatalytic CO2
reduction rate with the increment in the Cu content is observed upto
x = 1. After this decrease in the product evolution rate can be seen
with the hike in loading amount of Cu on the surface of mTiO2.
Herein, gradual reduction of Cu(II) to Cu(I) and ultimately to Cu(0)
takes place efficiently upon atomically dispersed Cu(II) species on
mTiO2. So, Cu(0) can trap the holes to be re-oxidized to Cu(I) and
further to Cu(II). Further, the Cu (I) species uptake the transferred
photogenerated electrons from the CB of TiO2 to convert back to Cu
(0), thus forming Cu(I)/Cu(0) mixture which is considered to be more
effective for photoreduction of CO2. On the other hand, an excessive
amount of Cu may act as recombination centres which suppress
effective photocatalytic CO2 reduction rate. Jiang et al. synthesized a
defective TiO2 nanosheet containing oxygen vacancies which were
further equipped with AuCu alloy co-catalyst to form AuCu-TiO2−x
NSs photocatalyst and examined their photocatalytic performance
towards selective conversion of CO2 to CH4 [152]. In this study, 90.55
% CO2 reduction selectivity and CH4 yield of 22.47 μmol·g−1·h−1 was
achieved. Herein the synergistic effect of AuCu and oxygen vacancies
is the contributing factor for improved CO2 conversion. At first CO
intermediate is probably generated on Au surface, then overflows to
the Cu surface, and undergoes further reduction into CH4. The sur­
face oxygen vacancies in TiO2 endorse the oxidation of H2O and thus
offer rich protons to enhance the reduction of CO2 to CH4. The
Schottky junction between both the AuCu and oxygen vacancies
promote the charge separation and transfer efficiency. Zhu et al.
investigated the photocatalytic CO2 reduction activity for the syn­
thesized Cu/Cu+ fabricated Ti3+/TiO2 (Cu/Cu+@TiO2) photocatalyst
[153]. The CH4 yield increases with the increasing Cu-loading up to
2.5 wt %. The synergistic effect of outside Cu and inside Cu+ in Cu/
Cu+@TiO2 has dramatically increased the electron carrier density. In
addition, Schottky junction developed on the interface Cu and TiO2
leads to facilitation of migration and separation of electron-hole
pairs. More crucially, the photogenerated electrons in Cu/Cu+@TiO2
can be 100 % utilized for CO2 reduction which was further aided by
the hydroxyl group on the surface.
5.4.4. Z‐scheme Heterojunction
Although p-n junction has accelerated charge separation, it sa­
crifices the importance of redox potentials while developing a
photocatalyst. To overcome this problem, various Z‐scheme multi­
component/hybrid systems have been employed recently to make
the photocatalytic redox reactions thermodynamically more
12
Journal of Alloys and Compounds 918 (2022) 165533
feasible. Basically, direct Z-scheme photocatalyst was prepared by
combining two different semiconductors without an electron med­
iator [154]. Herein, photogenerated electrons with higher reduction
potential and holes with higher oxidation potential with are spatially
separated on the semiconductor to form an improved Z-scheme
heterojunction photocatalyst, respectively [155]. Ciocarlan et al.
utilized a Z-scheme based photocatalyst, ZnFe2O4 @TiO2, for pho­
toreduction of CO2 under UVC light irradiation to generate 27 μmol
g-1 h-1 CH4 and 47 μmol g-1 h-1 CO [156]. The yield was found to be
much higher than that obtained in case of P25-TiO2. Wang et al.
reported a Z scheme [(Au/A-TiO2)@g-C3N4] heterojunction photo­
catalyst which lead to a much higher photoreduction rate than
commercial P25-TiO2, with a maximum yield of CO to be 21.7 μmol g-
1 -1
h and CH4 to be 37.4 μmol g-1 h-1 [157]. Wang et al. investigated
the photocatalytic CO2 reduction rate using synthesized Ag-Cu2O/
TiO2 Z-scheme heterostructure photocatalyst [158]. Under simulated
sunlight in presence of 0.5Ag-0.5Cu2O/TiO2 photocatalyst maximum
CO (13.19 μmol g-1 h-1) and CH4 (1.74 μmol g-1 h-1) production rate
were found. The reaction rate was satisfactorily higher as compared
to the reaction when performed with P25-TiO2, 1Cu2O/TiO2 and 1Ag/
TiO2, photocatalysts individually. For 0.5Ag-0.5Cu2O/TiO2 the elec­
trode potential value of conduction band (ECB vs NHE) and valence
band (EVB vs NHE) was obtained to be 2.6662 V and − 0.368 V, re­
spectively, indicating a band gap value of 3.03 eV which was lower
than that of other prepared photocatalysts. In this photocatalyst
apart from the better charge separation characteristics, the presence
of Ag as the co-catalyst aids to trap the electrons of Cu2O; thus leads
to the enhancement in CO2 photoreduction capability. Fig. 10 depicts
the photocatalytic reduction of CO2 on 0.5Ag-0.5Cu2O/TiO2 Z scheme
heterostructure.
5.4.5. Step‐Scheme (S- scheme) Heterojunction
Now-a-days, a novel step-scheme (S-scheme) heterojunction has
gained popularity among scientific community [159]. Reduction
photocatalyst (RP) and oxidation photocatalyst (OP) are two major
components of S-scheme heterojunction, as shown in Fig. 11. RP
possesses more negative CB potential which explains the higher
reducing capability of the photoexcited electrons residing there. On
the other hand, OP has more positive VB potential and in-turn
possess greater oxidizing ability for the photoexcited holes present
there. Typically, RP has higher Femi level (i.e. smaller work function)
than OP. On combining RP and OP, this fermi level difference drives
the electrons from RP to OP. Thus, after contact of RP and OP, the
fermi level of both the photocatalyst becomes the same resulting in
the accumulation of opposite charges on their interface as well as
Fig. 10. Schematic illustration of the photocatalytic reduction of CO2 on 0.5Ag-
0.5Cu2O/TiO2.
Adapted from ref [158] Copyright 2022 Elsevier.
I. Som and M. Roy
Fig. 11. Schematic illustration of an S-scheme heterojunction with staggered band configuration: (A) before contact, (B) after contact and (C) photogenerated charge carrier
transfer process after illumination. Copyright 2020 Elsevier.
Adapted from ref [161].
the formation of an internal electric field (IEF) pointing from RP to
OP. Owing to the IEF and band bending, the useless photogenerated
electrons on the CB of OP will transfer to RP and recombine with the
useless holes on the VB of RP. However, the useful photogenerated
electrons and holes will retain on CB of RP and VB of OP, respectively.
The above fact explains the strong reduction and oxidation ability in
case the formed S-scheme heterojunction photocatalyst [160].
Therefore, construction of TiO2-based S-scheme heterojunction
possess the immense possibility to improves the performance of CO2
photocatalytic reduction reaction.
Wang et al. synthesized TiO2/g-C3N4 S-scheme heterojunction
photocatalyst with hierarchical thin-film to perform photocatalytic
CO2 reduction [162]. Herein, the heterojunction constructed be­
tween g-C3N4 and TiO2 separates excitons efficiently. Furthermore,
higher yield of CO (upto 571.65 μmol h−1 m−2) and CH4 (upto 213.69
μmol h−1 m−2) was achieved in compared to pure TiO2. The following
bar diagram represents the amount of products (CO and CH4) formed
in case of different synthesized photocatalysts (Fig. 12).
Thus, the above section beholds various studies towards proper
tuning of pure crystalline TiO2 to develop materials that had cap­
ability to exploit light energy successfully to generate fuels. The
literature reports depict many TiO2 based photocatalysts with im­
proved photoactivity than that of pure TiO2. However, it is to be
borne in mind that not only material designing is important, the
choice of optimum condition for photocatalytic process is also
evident.
Fig. 12. Graphical representation of CO2 photoreduction performance for pure TiO2
and different TiO2 /g-C3N4 heterojunction photocatalysts.
Adapted from ref [162] Copyright 2022 Elsevier.
13
Journal of Alloys and Compounds 918 (2022) 165533
6. Factors associated with photocatalytic CO2 reduction
Several factors are responsible for efficient photocatalytic CO2
reduction which are driving force of conversion of CO2 into valuable
chemicals. The CO2 photoreduction can be influenced by several
parameters e.g. CO2 adsorption capability, temperature, pH of the
media, partial pressure of CO2, reactor for the reaction, presence of
surface functional groups and surface co-catalysts, etc., which will
be discussed in the following section.
6.1. Role of Photoreactor
Photoreactors are vital in regards to the photocatalysis process
and constitute an important engineering factor. In addition to the
different photocatalysts discussed in the previous section, various
reactor types might also affect the yield and distribution of the
products [163]. While designing an effective photoreactor several
factors like the enhancement in light absorption by minimization of
photon loss, decrement in charge carrier recombination, ease in the
product separation and collection, are taken into consideration.
Along with this some other parameters also determine the types of
photoreactors to be used. The other factors that determine the
choice of the photoreactors, includes types of phases involved
[single phase (gas, liquid), multiphase (gas-liquid, gas-solid, liquid-
solid, gas-liquid-solid)], the mode of hydrodynamic operation
(batch, semi-batch, or continuous), the mixing and flow character­
istics (completely mixed, some back-mixing, plug flow, nonideal
flow characteristics), the geometric configuration (dimensions and
shape), the light source specifications (output power, spectral dis­
tribution, shape, dimensions, operating and maintenance require­
ments) [164,165]. Moreover, photoreactors can be classified into two
types- photothermal reactor and solar driven photoreactor. Photo­
thermal reactors are employed for electronic excitation due to ad­
sorption of visible or ultraviolet radiation or infrared radiations or
even thermal energy from exothermic reactions, in presence of
heterogeneous photocatalysts. In the photoreactor solar energy get
converted into heat energy which is often required to drive the re­
action in the forward direction. Photothermal reactors are categor­
ized into fixed bed reactor, structured reactor, slurry reactor and
membrane reactors. Olivo et al. performed CO2 photoreduction ex­
periment by synthesized CuO-TiO2 and Au-TiO2 in fixed bed photo­
reactor [166]. In this case the yield of CH4 and H2 by CuO-TiO2
photocatalyst was obtained to be 20.00 µmol g-1 and 0.33 µmol g-1,
respectively, with about 100 % selectivity. On the other hand, the
yield of CH4 and H2 by Au-TiO2 photocatalyst was obtained to be
15.00 µmol g-1 and 10.00 µmol g-1, respectively with 60% selectivity.
In addition, the comparison between the photoactivity obtained ei­
ther with the fixed bed reactor or with the thin film reactor is re­
ported. For these tests, a commercial titanium-dioxide materials was
I. Som and M. Roy
used as a model catalyst. As a result, methane formation increases
enormously (from 0.03 µmol g-1 to 14.00 µmol g-1). In this experi­
ment thin film reactor was found to be more effective for photo­
catalytic reduction of CO2 as within the thin film reactor the mass
transport is facilitated compared to the fixed bed reactor. Hence,
desorption of products occurs easily and, as a consequence, their
ease of collection as well.
Several research work on photocatalytic reduction of CO2 to va­
luable fuel had revealed the use of artificial irradiation sources,
whereas some literature studies also contemplated the use of solar
photoreactors where natural sunlight had been used as irradiation
sources. Guan et al. synthesized Pt- loaded K2Ti6O13 photocatalyst
followed by combining with Fe-based photocatalyst supported onto
dealuminated Y-type zeolite. The above hybrid photocatalyst was
then utilized to conduct photoreduction study of CO2 with H2O
under concentrated sunlight. When the reaction solutions were
being subjected to concentrated sunlight considerable heating of the
solution occurred, which assisted the photoreduction process. It was
observed that when the reaction solution was heated to
temperature > 373 K owing to sunlight illumination, improved
photocatalytic water decomposition occurred. It was also noticed
that both hydrogenation and photocatalytic CO2 reduction process
occurred at high temperature (~600 K) originated due to irradiation
by concentrated sunlight. [167]. Thus, it can be concluded that sui­
table study and photoreactor design is evident for photocatalytic CO2
reduction process.
6.2. Effect of pH
The pH of the solvent plays a crucial role towards improved rate
and efficiency of CO2 photoreduction. It was observed that variation
in the proton concentration of the reaction media can lead to the
alteration in the theoretical reduction potential of CO2. In this case,
CO2 can act both as a reactant and as buffer. In spite of having very
low aqueous solubility, the partial hydration of CO2 in aqueous
medium leads to the formation of carbonic acid [168]. The pH value
also governs the solubility of CO2 resulting to furnish CO32-, HCO3- in
the reaction media. At high pH dissociation of CO2 into CO32- or
HCO3- occurs. The dissimilar chemical species (i.e. CO32-, HCO3 or
molecular CO2) possess a variety of standard redox potentials values
which can offer different adsorption characteristics of these species
onto photocatalyst surface, resulting in different product yield and
selectivity. Asi et al. synthesized AgBr/TiO2 nanocomposite and in­
vestigated the effect of pH on photocatalytic reduction of CO2 [169].
It was found that the product yield increased with the pH value to
8.5 and then decreased with further increase in the pH value. The
above fact can be explained on the fact given below (1) It is well
known that the OH− ions in aqueous medium could act as strong
hole scavenger and reduces the recombination of hole-electron pairs
which facilitated the reduction of CO2 [170,171]. On the contrary,
protons in aqueous solution involves in the competition with CO2 for
electrons, required in reduction process (H+ + e−→ H·), giving rise to
much lesser hydrocarbons yield [172]. (2) The electrostatic force of
interaction between CO2 and the catalyst AgBr/TiO2 nanocomposite
seemed to be quite effective. At pH < 5.4, positive surface charge of
the catalyst was generated which enhanced strong electrostatic in­
teraction with CO2 molecules, while the electrostatic repulsive force
existed between CO2 and the catalyst occurs pH > 5.4, owing to
negatively charged surface. Therefore, the optimum pH of photo­
reduction was at weakly alkaline pH where the overall combined
effect of the relatively higher concentration of OH− ions and lower
electrostatic repulsive force are dominant. In another study Pas­
trana-Martínez et al. synthesized copper (I) oxide based TiO2 com­
posites and investigated the effect of pH on photocatalytic reduction
of CO2 onto the synthesized composite surface [173]. Here, CuO from
different copper sources has been adapted to form CuO-TiO2 p-n
14
Journal of Alloys and Compounds 918 (2022) 165533
junction photocatalyst. It was found that the cuprous oxide-titania
composite prepared from copper nitrate source showed the highest
photocatalytic activity at pH 11. In this case MeOH and EtOH was
formed with yield of 45.2 and 86.4 µmol g-1 h-1 respectively.
6.3. Temperature
An optimum temperature should be maintained for feasible
photocatalytic CO2 reduction reaction. Generally, increasing tem­
perature triggers formation of ample electron-hole pairs due to
photon (light energy) activation (discussed above). An increase in
reaction rate had also been reported for high temperatures due to
enhancement of collision frequency and diffusion rate of partici­
pating reactant molecules [174]. The kinetics of CO2 photoreduction
can be explained well in terms of adsorption/desorption equilibrium
of the various species involved in the reaction. Here the rate limiting
step is the product desorption phenomena where the apparent ac­
tivation energy (Ea) is found to be positive. In case of low tem­
perature, the product desorption does not occur easily, even though
the surface coverage tends to maximum. On the other hand, at high
temperature the reactants get easily adsorbed onto as well as pro­
ducts get desorbed from the photocatalyst surface resulting in ne­
gative activation energy (Ea) [175]. Lo et al. reported the influence of
temperature towards the rate of photocatalytic reduction of CO2 in
presence of acidic photocatalyst (TiO2/SO42−) [176]. It was observed
that increased yield of CO (3.3 μmol g-1 h-1) and CH4 (1.2 μmol g-1 h-
1
) could be attained at higher temperature. Slamet et al. [177]
showed the influence of temperature in terms of activation energy
regarding photocatalytic CO2 reduction onto copper-doped titania
photocatalyst. The photoreduction experiment was carried out at
different temperatures (43–100 ⁰C). The maximum methanol yield
was found to be 4500 μmol g-1 at 100 ⁰C, implying the better ad­
sorption capability of CO2 molecules on copper-doped titania pho­
tocatalyst surface, at higher temperature.
6.4. Influence of TiO2 as photocatalyst
The role of photocatalyst is very crucial and determining factor
for photocatalytic CO2 reduction reaction. In case of oxide photo­
catalyst, TiO2 has been studied widely which is known to exists in
three polymorphs: anatase, brookite and rutile [178–181]. Here, the
defect disorder present in the TiO2 photocatalyst greatly influence
their photoactivity. The defects like oxygen vacancies (VO) can serve
as surface reactive sites present at the interface. In this case, the
donation of excess unpaired electrons to Ti was accelerated leading
to form Ti3+ species on the photocatalyst. Thus, these stored elec­
trons may strongly affect the surface chemistry and charge transport
properties of TiO2. Among the three phases of TiO2, brookite exhibit
highest photocatalytic CO2 reduction activity. Probable reasons for
this enhanced activity of brookite with surface defects (VO/Ti3+ de­
fects) include the facilitated formation of oxygen vacancies which
could readily provide reactive sites for the adsorption of reactants.
Besides, the photocatalyst allows effective electron or hole transfer
between CO2/H2O and the TiO2−x surface under photo-illumination.
Liu et al. performed theoretical calculations which reveal that the
formation energies of VO and Ti interstitial for different TiO2 poly­
morphs were as: rutile > anatase > brookite [182]. This calculation
proved that since the formation energies of VO and brookite Ti in­
terstitial was found to be least, brookite with surface defects can be
formed easily. Thus, the rate of reaction involving·CO2- and adsorbed
H2O occurred faster for such brookite polymorph. The vital finding of
this experiment was that defective brookite exhibited highest CH4
and CO yield due to the facile formation of oxygen vacancies
within it.
I. Som and M. Roy
6.5. Effect of surface functional group
The nature of surface functional groups on the photocatalyst
plays a crucial controlling aspect in the reactivity and selectivity of
CO2 reduction. Surface functional groups act in two ways: (i) offer
basic sites for better interaction with acidic oxide, CO2 and (ii) in­
duces surface hydrophobicity to repel water molecules and thus
indirectly favours the adsorption of carbon dioxide molecule [183]. It
is noteworthy to mention that in aqueous solution the product se­
lectivity gets significantly influenced by the availability of surface
hydroxide groups which in-turn is known to be affected by the
surface hydrophilic as well as hydrophobic characteristics of the
photocatalyst. Literally, some of the scientific reports have revealed
hydrophilic-hydrophobic theory which signifies that relative amount
of water in the system coupled with surface hydrophilic-hydro­
phobic properties favours the formation of one of the competitive
products, CH4 or CH3OH, from methyl radical. Dong et al. studied the
influence of NH4F and HF which were separately treated to TiO2/SiO2
photocatalyst [184]. It was found that the replacement of Si-OH bond
with Si-F (hydrophobic group) takes place only when the photo­
catalyst were treated with NH4F. Thus, the studies depicted that CH4
was produced selectively by the TiO2/SiO2 composites which are
hydrophobic in nature (i.e. in case of NH4F treated photocatalyst). In
another studies it was found that the reactivity of the Ti− β zeolites
synthesized using different anions (OH- and F- ion) along with the
structure-directing agents It was observed that the hydrophilic Ti-β
zeolite (containing Tiβ (OH−) species) had higher affinity for water
molecule than hydrophobic Ti-β zeolite (containing Tiβ (F−) group)
with H2O molecules being easily accessible to the tetrahedrally co­
ordinated TiO2 species in the Ti− β(OH) zeolite, the former case. The
differences in the H2O affinity controls the reactivity of the formed
zeolites and selectivity of the products [185].
Hence, the above strategies have been found to be effective to­
wards achieving higher yield as well as good product selectivity for
photocatalytic CO2 reduction reactions.
6.6. Wavelength effect
The photocatalytic CO2 reduction reaction also depends upon the
wavelength of light used for the irradiation of photocatalyst.
Generally, increasing the light irradiation energy (lower wavelength)
results in the enhancement of electron-hole generation rate which
boosts up the photocatalytic reduction rate of CO2 [186,187]. Kočí
et al. examined the CO2 reduction performance in presence of Ag/
TiO2 photocatalyst under the illumination of lamps working at three
different wavelengths (254 nm, 365 nm, and 400 nm) [188]. It was
observed that illumination by 254 nm lamp yielded higher products
(methane and methanol) than under irradiation by 365 nm lamps.
On the other hand, no products were formed in presence of 400 nm
lamp. Thus, it is evident that if the irradiation energy become in­
sufficient to photoexcite an electron, the rate of photocatalysis sig­
nificantly diminishes. In this scenario, the modifications of the
concerned photocatalyst become indispensable to improve the
photoactivity rate.
6.7. Effect of partial pressure
The rate of photoconversion of CO2 is markedly dependent on the
rate of adsorption of CO2 molecule on the surface of the photo­
catalyst. The adsorption of CO2 molecules on the surface of photo­
catalyst depends upon the van der Waal forces of interaction
between the adsorbent (photocatalyst) and the adsorbate (carbon
dioxide gas). It is the adhesive force between the adsorbate-ad­
sorbent system which increases with hike in partial pressure of the
adsorbate. Thus, when CO2 is in gaseous phase, higher partial pres­
sure of CO2 gas attributed to better product yield. The solubility and
15
Journal of Alloys and Compounds 918 (2022) 165533
molar concentration of CO2 in liquid phase is increased due to higher
partial pressure of CO2 (PCO2 ) which indicates increase in product
formation [189]. In case of both gaseous and liquid phase systems,
PCO2 controls their probability of adsorption over the active sites of
photocatalyst ensuring higher yield of solar fuel [190]. Furthermore,
the improvement of mass transfer is achieved due to the fluctuation
of pressure in spite of working at constant high pressure [191]. Anzai
et al. prepared Ag-modified CaTiO3 (Ag-CaTiO3) photocatalyst and
reported the photocatalytic CO2 reduction efficiency with the syn­
thesized photocatalyst [192]. It was observed that high production
rate of CO (54 μmol h−1) as well as outstanding selectivity (94 %) was
achieved by the prepared Ag- CaTiO3. To investigate the effect of the
CO2 gas in the reaction aqueous solution, the group introduced the
gas into the reactor both via bubbling flow and without bubbling. It
was found that bubbling leads to higher gas concentration into the
reaction mixture. Furthermore, it was found that when the reaction
performed at higher temperature (306 K), the production rate of CO
was diminished (albeit H2 production rate was same) as compared to
the reaction performed at lower temperature. Thus, the studies
proved that higher reaction temperature and gas introduction via
bubbling-free mode into the reaction liquid phase leads to lesser CO2
dissolution with decreased CO yield and lower selectivity. So, this
report indicated that for achieving better photocatalytic efficiency
the high concentration of dissolved CO2 was necessary, which in-
turn is directly proportional to PCO2.
Table 1 provides a summarized overview of different TiO2 and
TiO2 based nanomaterials employed for photocatalytic conversion of
CO2 into major products, with documentation of yield, light source
used and reaction conditions promoting photocatalytic performance.
From the current section it is evident that, the study related to
the parameters affecting the photocatalytic CO2 reduction reaction
provides with a conclusion that in order to obtain higher yield with
better product selectivity, all the above-mentioned parameters must
be chosen carefully. Moreover, it is to be kept in mind that tuning of
the product selectivity as per choice, can also be performed with
alteration of reaction conditions. Therefore, to choose the probable
reaction and to tune its selectivity, mechanistic study of the CO2
reduction reaction process is crucial.
7. Photocatalytic CO2 reduction mechanism
Literature study depicts that several experimental works has
been performed over recent years regarding photocatalytic CO2 re­
duction. In spite of that clear insight related to the plausible me­
chanistic pathway and intermediate identification, is still unclear.
The fundamental mechanisms of the processes that occur at dif­
ferent stages of CO2 reduction are not completely understood from
experimental work. Especially, interactions at the photo­
catalyst−substrate interface plays one of the most important role.
This interaction can be well understood from Density Functional
Theory (DFT) [218]. DFT based computational modelling methods
are not only used for the investigation of electronic/chemical prop­
erties but also probe necessary structural engineering that is re­
quired in the photocatalyst for enhancing their efficiency. Also,
saving experimental time and resources is the main advantage of
using this type of approach. In this context various photocatalytic
CO2 reduction mechanism over different types of TiO2 based nano­
material e.g. doped, composite, sensitized etc. has been elucidated in
this section with suitable pictorial diagram.
Tahir et al. proposed a mechanistic pathway over synthesized
gold-nanoparticles (Au-NPs) doped TiO2 nanowires (TiO2-NWs) [57].
Under visible light illumination, the surface plasmon resonance ef­
fect of Au-NPs on the TiO2 surface drags the electrons from the
conductance band of TiO2 leading to separation of electron-hole pair
(Fig. 13).
 I. Som and M. Roy

Table 1
Summary of various TiO2 and TiO2 based nanomaterials for photocatalytic CO2 conversion.

Photocatalyst Light source Experimental condition Major products Yield Ref.

2 −1 −1
Au/Cu (2:1) co-doped P25-TiO2 film (with constant total 1000 W Xe lamp (AM 1.5) 1.25 cm thin film (0.6 mg of solid material) deposited on CH4 2200 ± 300 μmol g h [193]
metal amount of 1.5 wt%) quartz plates
−1
0.5 wt%Ag doped Brookite TiO2 300 W Xe lamp Photocatalyst dosage: 150 mg CO 128.8 ppm h [194]
MgO layers deposited on porous TiO2 450 W Xe lamp Photocatalyst dosage: 10 mg CO 54 μmol g−1 h−1 [195]
TiO2/carbon nitride nanocomposites 300 W Xe lamp (> 325 nm) Photocatalyst dosage: 0.2 g CO 1.96 μmol g−1 h−1 [196]
Hypercrosslink polymer grafted TiO2 anchored with Pd 300 W Xe lamp Photocatalyst dosage: 30 mg CH4 237.4 μmol g−1 h−1 [197]
ZnFe2O4/Ag/TiO2 nanorods 200 W Hg lamp Photocatalyst dosage: 150 mg CO 1025 μmol g-1 h-1 [198]
WO3-TiO2/Cu2ZnSnS4 400 W Xe lamp (λ > 420 nm) Photocatalyst dosage: 0.1 g CO 15.37 μmol g−1 h−1 [199]
Ag-quantum dots modified TiO2 300 W Xe lamp Photocatalyst dosage: 50 mg CO 2.3 μmol g-1 h-1 [200]
Yolk@shell TiO2−xHx (HUY@S-TOH)/AuPd 300 W Xe lamp Photocatalyst dosage: 0.125 g CH4 47.0 μmol g-1 h-1 [201]
TiO2−MnOx−Pt hybrid multi-heterojunction Film 350 W xenon lamp Photocatalyst dosage: 15 mg CH3OH 31 μmolm−2 in 6 h [202]
TiO2-Graphene-MoS2 300 W xenon lamp Photocatalyst dosage: 10 mg CH4 93.22 μmol g-1 h-1 [203]
Au nanoparticle-grafted TiO2 nanotubes Solar simulator Photocatalyst dosage: 30 mg CH4 58.47 μmol g-1 h-1 [204]
Au3Cu-SrTiO3/TiO2 300 W Xe lamp 2.5 cm2 catalyst film over CO2-saturated N2H4 and then CH4 421 μmol g−1 h−1 [205]
inject 4 mmol CO2 and 8 mmol He

16
TiO2 nanoflake 300 W Xe lamp Photocatalyst dosage:10 mg PCO2 : 0.2 MPa CH4 1708.1 mmol g-1 h-1 [206]
1 wt% Pt co-catalyst doped LixTiO2 300 W xenon arc lamp Photocatalyst dosage: 100 mg CH4 8.85 mmol g-1 in 8 h [207]
Black phosphorus coupled black titania nanocmposite 300 W Xe lamp Photocatalyst dosage: 50 mg CH4 16.8 mmol g-1 h-1 [208]
Polyaniline-TiO2 nanocomposites 125 W white light Photocatalyst dosage: 0.3 g L-1 HCHO 80.57 mmol g-1 in 8 h [209]
Ti3+ Defective SnS2/TiO2 Heterojunction 300 W Xe lamp Photocatalyst dosage: 30 mg CO 724 mmol g-1 h-1 [210]
Cu@V codoped TiO2/Polyurethane Visible light (Two 20 W Bulbs) Photocatalyst dosage: 2 g CH4 933 mmol g-1 in 6 h [211]
CdS QDs-Cu2+-TiO2 nanorods 300 W solar simulated Xenon lamp Photocatalyst dosage: 0.5 g C2H5OH 109.12 mmol g-1 h-1 [212]
TiO2 nanotubes coated with CoOx nanoclusters 150 W UV lamp Photocatalyst dosage: 20 mg CO 16.40 mmol g-1 h-1 [213]
g-C3N4/N-TiO2 nanosheets 300 W Xenon arc lamp Photocatalyst dosage: 8 mg CO 14.73 mmole g-1 h-1 [214]
Cu–Pt bimetallic shells supported on a double-walled TiO2 Visible light Photocatalyst dosage: 25 mg CH4 50 μmol g−1 h−1 [215]
nanotube
Pt loaded Ti3+ self-doped mixed phase TiO2 nanosheets Solar simulator (300 W Xenon short arc lamp, Photocatalyst dosage: 5 mg 4:1 mol ratio of H2 : CO2 CH4 1.68 μmol g−1 h−1 [216]
equipped with a UV/IR filter)
−1 −1
Carbon nano-layer coated TiO2 nanoparticles 300 W Xe lamp Photocatalyst: 100 mg CO 16.76 μmol g h [217]
Journal of Alloys and Compounds 918 (2022) 165533
I. Som and M. Roy
Fig. 13. Schematic illustration of the proposed mechanism for photocatalytic CO2 reduction with H2 to CO, CH4 and CH3OH over Au-NPs/TiO2 nanowires under visible light
irradiation. Copyright 2015 Elsevier.
Adapted from ref [57].
The energy of the trapped electrons was enhanced via SPR effect
of Au-NPs (Eq. (4)) such that CO2 species react effectively [219]. The
active valance band holes (h+) in TiO2NWs and/or Au can oxidize H2
to produce H+ (Eq. (15)). Then, holes and the active electrons are able
to reduce CO2 to CO, CH3OH and hydrocarbons, as explained in [Eqs.
(16)–(19)]. Therefore, photo-catalytic activity of Au-NPs-decorated
TiO2NWs can be explained based on the charge trapping and charge
transfer ability of Au-NPs as well as visible light harvesting cap­
ability of the concerned photocatalysts.
TNWs + hυ → h+vb + e-cb
e-cb → e-Au
e-Au + hυ (visible)→ e-SPR
H2 + h+vb → H+ + H+
CO2 + 2 H+ + 2e- SPR → CO + H2O
CO2 + 6 H+ + 6e- SPR → CH3OH + H2O
CO2 + 8 H+ + 8e- SPR → CH4 + 2 H2O
nCO2 + nH+ + e- SPR → C2H4 + C2H6 + C3H6 + C3H8 + nH2O
In another study Gao et al. proposed a photocatalytic CO2 re­
duction mechanism on black titania nanotube arrays (B-TiO2NTAs)
[77]. Numerous oxygen vacancies are formed on the surface of the B-
TiO2 NTAs with the production of low-coordinated oxygen species.
The pathway for photocatalytic CO2 on B-TiO2 NTAs was shown in
Fig. 14, which consists of the following four steps: (i) CO2 as well as
H2O were adsorbed on the oxygen vacancy sites present on the
photocatalyst surface (ii) photogenerated electrons dissociate H2O
molecules into hydroxyl groups and hydrogen radical upon visible
light illumination. Furthermore, those photogenerated electrons also
reacted with the adsorbed CO2 molecules to form vo-O-C]O (iii)
Hydrogen radical produced attack and break the C–O bond resulting
in the formation of CO molecules (iv) Hydroxyl groups reacted to
form H2O2 which finally get decomposed under visible light illu­
mination to restore back the oxygen vacancies for further reaction
[Fig. 14 (c) & (d)].
Journal of Alloys and Compounds 918 (2022) 165533
As mentioned earlier (section no 5.2.1) organic dye have widely
been employed as photosensitizer for semiconductor photocatalysis.
In this regard Won et al. showed photocatalytic CO2 reduction me­
chanism related to Zn−porphyrin (ZnP*) dyes anchored onto TiO2
surface (Fig. 15). Here, Zn−porphyrin-|TiO2|-Re(I) hybrid acts as dye-
sensitized photocatalytic system [220]. Upon solar irradiation
ZnP* get excited from ground state (S0) to excited state (S1) and then
an excited electron injects from ZnP* to the CB of TiO2. Then TiO2
transports the electron to the Re(I) based reduction catalyst (ReC)
consequently. At the ReC center, proton-coupled two-electron re­
(12) duction of CO2 occurs to produce CO following the monomeric
mechanism rather than dimer formation (CO2-bridged dimer com­
(13) plex, LReCOOReL). The persistent efficient photocatalytic CO2 re­
duction to CO occurs effectively owing to the on-demand electron
(14) supply from conduction band of TiO2 [TiO2 (e−)] to ReC. Finally, the
overall photocatalytic cycle is completed after the regeneration of
(15) ZnP by subsequent reduction of ZnP•+ with BIH.
The photocatalytic CO2 reduction by Graphene based TiO2 na­
nomaterial is interesting and trending. Zhao et al. performed pho­
(16)
tocatalytic reduction process onto a TiO2 based hybrid photocatalyst,
Pt/TiO2-nanocrystals wrapped by reduced graphene oxide sheets
(17)
[(Pt/TiO2)@rGO] and elucidated a plausible mechanism on the basis
of the obtained experimental result (Fig. 16) [221]. When Pt/TiO2@
(18) rGO is illuminated with sunlight, anatase TiO2 generates photo­
excited electrons and the co-exposed {101} and {001} facets on TiO2
(19) which facilitate the separation of holes and electrons. Thenceforth,
the supported Pt NPs accumulate photogenerated electrons from the
conduction band of anatase TiO2 nanocrystal which is then trans­
ferred to the rGO. Thus, the tiny region of rGO shell wrapping gets
enriched with the photogenerated electrons via the vectorial elec­
tron transfer (TiO2→Pt→rGO). On the other hand, the holes left be­
hind in the valence band of TiO2 nanocrystals reacts with water to
form H+ ion and oxygen. Now, the CO2 adsorbed onto the hybrid
photocatalyst surface accepts these photogenerated electrons along
with the supplied H+ ions to form CH4 selectively. The unique non­
polar nature and ample π electron cloud originated from rGO are
beneficial to the effective adsorption of CO2.
Low et al. performed DFT simulation to find out the intrinsic
cause for the formation of the direct Z-scheme heterojunction be­
tween the TiO2 and CdS [222]. Here, TiO2/CdS composite exhibited
superior photocatalytic activity related to CO2 reduction to solar fuel
(CH4 yield found to be 11.9 mmol h-1 m-2 which is 3.5 and 5.4 times
17
I. Som and M. Roy Journal of Alloys and Compounds 918 (2022) 165533

Fig. 14. Photocatalytic reduction activity of TiO2NTAs-450-A and B-TiO2 NTAs for CO2 conversion yield (a) and CO2 conversion productivity (b) Advantages for CO2 photoreduction
into CO over the oxygen deficient B-TiO2 NTAs atomic layers (c) Representation of CO2 photoreduction into CO over the oxygen deficient B-TiO2 NTAs atomic layers and (d)
schematic representation of the mechanistic approach.
Adapted from ref [77] Copyright 2020 Elsevier.

Fig. 15. Schematic representation of the sequential energy/electron transfer process in a dye-sensitized hybrid system from lower energy porphyrin photosensitizers (ZnPs) to
TiO2 (molecular immobilizer and electron mediator) and Re(I) reduction catalyst (ReC)
Adapted from ref [220] Copyright 2018 American Chemical Society.

18
I. Som and M. Roy
Fig. 16. Schematic of the mechanism for CO2 photoreduction with H2O to CH4 over (Pt/TiO2)@rGO-n catalysts.
Adapted from ref [221] Copyright 2018 Elsevier.
higher than that of TiO2 and CdS, respectively) owing to the for­
mation of Z-scheme heterojunction.
The Fermi levels (EF) of the both exposed TiO2 (101) and CdS (111)
surfaces were calculated from the following equation [Eq. (20)]
mentioned below .
EF = Evac – Φ
where Φ is the work function, Evac is the energy of a stationary
electron at the vacuum level. Thus, the EF of TiO2 (101) surface and
CdS (111) surface can be estimated to be − 6.45 and − 4.48 eV, re­
spectively. Therefore, electrons can easily migrate from the CdS (111)
to the TiO2 (101) surface [as EF of the TiO2 (101) surface is more
negative than that of the CdS (111) surface] when both of the sur­
faces with the above-mentioned exposed faces are in contact with
each other and the equilibrium is reached. Finally, the region close to
the TiO2/CdS interface become charged after achieving Fermi equi­
librium resulting in internal electric field pointing from CdS to TiO2.
Thus, this study along with other studies [223] show that the pho­
togenerated electron–hole migration was accelerated significantly
following the direct Z-scheme mechanism which in turn enhances
the photocatalytic activity of the concerned catalyst (Fig. 17).
Zeng et al. performed DFT studies for getting in-depth insight about
the photocatalytic CO2 reduction mechanism by understanding the
Fig. 17. Representation of charge carrier migration on TiO2/CdS under the influence of
internal electric field.
Adapted from ref [222] Copyright 2018 Wiley Online Library.
Journal of Alloys and Compounds 918 (2022) 165533
optical and electronic properties of the synthesized photocatalyst
system [Au cluster decorated anatase TiO2 with exposed (101) plane
(Au-PMTiNTs)] [224]. In this investigation DFT calculations with Hub­
bard U correction method were done using OpenMx software (an open
source package for Material eXplorer). The projected density of states
(PDOS) revealed in Fig. 18, demonstrated the hidden charge flow me­
(20) chanism from an electronic structure perspective. The calculations were
performed considering pseudoatomic orbitals and relativistic pseudo­
potentials, adopted by LDA. The important filled electronic orbitals
present in this hybrid system were O 2p and Au 3d, as depicted in the
Fig. 18. Herein, O 2p is the main contributor to the VB of TiO2. When the
photocatalyst was illuminated by photons exceeding the bandgap of
TiO2, electrons were excited to the Ti 3d orbital that constitutes the CB
of TiO2. An Au 3d interband transition overlaps with the O 2p → Ti 3d
transition. Henceforth, electrons were excited from + 0.1 eV Au sp or­
bital to + 0.8 eV Au sp orbital which was regarded as intraband transi­
tion. This intraband transition was stimulated following dephasing of
the Au surface plasmons which were excited by visible light illumina­
tion leading to creation of nonequilibrium distribution of electron
Fig. 18. Projected density of states diagram of selected gold atom (red line), titanium
atom (green line), oxygen atom (blue line). The Fermi energy is at 0 eV.
Adapted from ref [224] Copyright 2020 Elsevier.
19
I. Som and M. Roy Journal of Alloys and Compounds 918 (2022) 165533

Fig. 19. (a) Density of states (DOS) plots for {101} and {001} surface of anatase TiO2. O 2p, Ti 3d, and TDOS are partial DOS of O 2p, partial DOS of Ti 3d, and total DOS, respectively.
(b) {001} and {101} surface heterojunction.
Adapted from ref [225] Copyright 2014 American Chemical Society.

carriers. Another interesting characteristic obtained from PDOS was the

next energy level which was found to be higher than the LUMO of the
Au-TiO2 system and existed at + 0.8 eV (sometimes called S2 in a mo­
lecular system), mainly consisting of Ti 3d orbital isoenergetic with the
Au sp orbital. From the HOMO-LUMO interaction (derived by DFT study)
in case of photocatalyst system, it can be inferred that Ti 3d orbital was
strongly coupled with Au sp orbital which served as a shuttle to deliver
the localized surface plasmon resonance electrons to CO2 in photo­
reduction reaction. In this experiment Au-PMTiNTs produced methane
(302 µmol g-1cat.h-1) from CO2 with 89.3 % selectivity.
Yu et al. accomplished DFT calculation to find out the formation
of co-exposed {101} and {001} facets onto the surface of anatase TiO2
heterojunction, within single TiO2 particle [225]. The Fermi level of
{001} facets entered their valence band which can be seen from the
Fig. 19. On the other hand, the Fermi level of {101} facets was still
placed above the valence band of {101} surface. Thus, the {001} and
{101} facets formed surface heterojunction when they were placed Fig. 20. Schematic diagram illustrating the photocatalytic performance of the CsPbBr3
in contact to each other. Thus, the migration of photogenerated @MTB hybrid.
electrons and holes were facilitated to {101} and {001} facets, re­ Adapted from ref [226] Copyright 2018 Elsevier.
spectively during the photocatalytic process.
Recently, a novel step-scheme (S-scheme) heterojunction has 8. Conclusion
gained popularity among scientific community. Dong et al. eluci­
dated the photocatalytic CO2 reduction S-Scheme mechanism by The photocatalytic transformation of CO2 to hydrocarbon fuels
using perovskite CsPbBr3 embedded quantum dots into mesoporous and valuable chemicals is a demanding and needful approach to
TiO2 beads (CsPbBr3@MTB) [226]. Upon simulated solar irradiation, modulate both fuel crisis and global warming. It is to be noted that
the photoexcited electrons in the CB of MTB were transferred to the TiO2-based nanomaterials with defect disorder have achieved an
VB of CsPbBr3 resulting in recombination with the holes within it. eminent reputation as an efficient material which can viably alle­
Thus, strong oxidizing holes in the VB of MTB and high reducing viate photocatalytic activities. The large energy barrier between
electrons in the CB of CsPbBr3 was left behind (Fig. 20). Hence, a S- HOMO and LUMO of CO2 molecule is diminished during its ad­
scheme charge transfer route had been developed which further sorption onto a suitable catalyst surface. The linear structure of CO2
helped to photocatalytically reduce CO2 into CO and CH4. Such un­ is favourably converted to bent structure which not only lowers the
ique S-scheme charge transfer route not only promoted spatial energy gap but also increases its reactivity to suitably convert into
charge separation but also preserved the higher reduction potentials useful chemicals. Here, TiO2 based materials with suitable band gap
for the photogenerated electrons, which was extremely important and existence of ample Ti3+ sites onto the surface leads to the gen­
for the efficient reduction reaction. eration of excitons as well as increased basic sites, respectively,

20
I. Som and M. Roy
imparting its role towards the generation of various products from
the adsorbed CO2 molecules. Mostly two kinetic models
(Microkinetic and Langmuir-Hinshelwood) have been observed to fit
the experimental data related to photocatalytic CO2 reduction re­
action. The microkinetic model depicts the formation of CH4, CO and
H2, assuming negligible amount of hydrocarbon production. As the
pre-exponential factors are approximated here, the rate constant
value cannot be solely used for activation energy determination. In
this model the rate limiting step is found to be affected by the ma­
terial composition. In case of Langmuir-Hinshelwood model the rate
is observed to be proportional to the adsorption of gaseous re­
actants. A competitive adsorption of two reactants, CO2 and H2O
onto the surface of the photocatalyst, yield different products
(generally CH4 and CO are obtained as main products). This kinetic
model suggests the reduction of CO to other products utilizing the
labile photogenerated electrons. The desorption of the products also
occurs efficiently.
In this review, it has also been observed that suitable modifica­
tion and surface engineering of TiO2 via doping onto TiO2 surface,
creation of surface defects (oxygen vacancy defects, Schottky de­
fects), sensitization (with suitable dye, conducting carbon species) as
well as formation of composite, various heterojunctions (i.e., tradi­
tional, p-n junction, Schottky junction, Z scheme, S scheme,) leads to
better CO2 photoreduction efficiency and selectivity compared to
pure titania. In search of the optimum factors that lead to the ef­
fective photoreduction it is found that suitable photoreactor design
can lead to high product yield and selectivity. Furthermore, a variety
of standard redox potentials values of several chemical species (i.e.
CO32-, HCO3- or molecular CO2) formed at different pH, offer dif­
ferent adsorption characteristics on photocatalyst surface which
leads to high yield as well as selectivity. It is also found that surface
hydrophilic-hydrophobic properties have marked influence on the
product selectivity. Generally, increasing temperature triggers for­
mation of ample photogenerated excitons as well as enhances col­
lision frequency and diffusion rate of reactant molecule. The high
partial pressure of CO2 is seen to enhance the Van der Waal forces of
interaction between the photocatalyst and CO2 gas resulting in­
creased product yield. While investigating the mechanistic per­
spective (in terms of DFT study) of such CO2 reduction on different
type of TiO2 based photocatalyst, it is found that surface exposed
facets and oxygen vacancy sites have substantial influence onto the
reduction mechanism in case of anatase TiO2 surface. Furthermore,
fast migration of these photogenerated excitons can also be observed
in TiO2 based composite nanoparticle following Z scheme me­
chanism. Hence, this review clarifies the fact that unique properties
of TiO2 based nanostructured photocatalysts with suitable mod­
ification leads to the improvement in the photocatalytic perfor­
mance which stands out to be a potent domain in the context of
photocatalytic application prospects to serve the humankind.
9. Future perspective
From this review, it is clear that urgent search of suitable TiO2
based photocatalyst which could exploit solar light spectrum effi­
ciently for the purpose of photocatalytic CO2 reduction on large scale
industrial level, is required. One of the polymorphs of TiO2 i.e.,
brookite with band gap (3–3.6 eV) needed to be explored. Suitable
modification of brookite to lower band gap is also a good topic of
investigation. Besides, several other strategies such as designing of
TiO2 with hollow and ultrathin structured materials can be beneficial
routes for achieving improved photocatalytic CO2 reduction. The
advantage of multi-reflection of light through hollow structure as
well as the, accelerated migration rate of photogenerated charge
carriers to the surface with lower recombination rate, provides an
interesting candidate for such photoreduction process. It can also
generate high surface defects which could furnish a better
21
Journal of Alloys and Compounds 918 (2022) 165533
nanomaterial for CO2 activation and conversion. The study of dual
cocatalyst doping onto TiO2 surface is crucial since the greatest
challenge is optimization regarding the loading of dual cocatalyst
onto the photocatalyst surface such that it could improve the effi­
ciency of photoreduction process. Apart from TiO2 other semi­
conductor materials must be exploited in search of suitable
photocatalyst for CO2 reduction that can achieve the practical im­
plication. It has been observed that few noble metal-based photo­
catalysts exhibit the highest rates in visible-light driven
photocatalytic CO2 reduction reaction. This observation can be at­
tributed to the low kinetic reaction barriers and high conductivity of
the photocatalyst used. Besides, few earth abundant semi­
conductors, which includes CdS, Cu-based nanomaterials, etc., are
known to be promising. However, it is often found that tuning the
properties of such highly crystalline semiconductors, are quite
challenging. Therefore, in this context, cheap carbon-based materials
with easily tunable properties may pop-up as an alternative greener
substitute. Furthermore, research should be focused on usage of
single atom photocatalyst for production of valuable chemicals from
CO2 reduction reaction. These type of photocatalysts with unique
electronic structures, unsaturated coordination centres, and re­
quirement of relatively lower catalyst consumption (owing to the
atomic dispersion of catalytic species) could provide interestingly
high selectivity and stability.
Though investigation on photocatalytic CO2 reduction has not
gained a desired outcome for practical enslavement, it is expected
that the fast-paced advancement in this research arena, should bring
the potentiality of this method nearer to realization in recent years.
It is hopeful that this review can contribute towards building a re­
search roadmap to facilitate the search for advanced photocatalyst in
attaining high-performance environmental cleaning and sustainable
energy applications.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgement
I.S. would like to acknowledge Department of Chemistry,
National Institute of Technology, Durgapur. M.R. would like to thank
Banasthali Vidyapith for providing support to furnish this work.
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