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Current developments and future trends in

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Cite this: React. Chem. Eng., 2021, 6,

photocatalytic glycerol valorization: process
197 analysis
M. R. Karimi Estahbanati,a Mehrzad Feilizadeh,b Farid Attarb and Maria C. Iliuta *a

Received 26th September 2020,
Accepted 7th December 2020
DOI: 10.1039/d0re00382d
rsc.li/reaction-engineering
The rapid advances in biodiesel technologies in recent years and the generation of huge amounts of
glycerol as a by-product have led to a glycerol glut in the market and a significant drop in its price. The
development of suitable techniques for glycerol valorization has recently attracted considerable attention
and the photocatalytic process emerged as a forefront technology that integrates solar energy with
glycerol conversion at ambient temperature and atmospheric pressure. The present review focusses on the
analysis of this photocatalytic process to address the challenges and opportunities for its implementation.
In this regard, the mechanisms of glycerol photoreforming and photo-oxidation as well as their gaseous
(like hydrogen) and value-added liquid products are first analyzed. The developed kinetic and empirical
models are then discussed to evaluate the prospects in the analysis of this process through a modeling
approach. Finally, a thorough critical assessment is performed on the research related to synthesis
parameters like cocatalyst percentage and calcination conditions, as well as the most critical operating
parameters such as the hydrogen source, reaction time, glycerol concentration, solution pH, photocatalyst
loading, photocatalyst stability, source and intensity of light, and reaction temperature.

1. Introduction
Glycerol is a significant by-product of the biodiesel production
process. It has diverse applications such as in cosmetic, paint,
food, tobacco, pharmaceutical, pulp and paper, leather, and
textile industries.1–3 On the other hand, crude glycerol contains
a
Department of Chemical Engineering, Université Laval, 1065 Av. De la Médecine,
Québec, Québec G1V 0A6, Canada. E-mail: maria-cornelia.iliuta@gch.ulaval.ca
b
School of Chemical and Petroleum Engineering, Shiraz University, Shiraz, Iran
impurities like methanol, soap, salts, oils, and solid organic
materials.4 These impurities restrict the applications of glycerol
in most of the above mentioned industries, because glycerol
purification implies excessive cost.5 Numerous works reviewed
the transformation of glycerol for different applications, such
as in hydrogen production,6–10 fuel additives,2,11–13 and
polymer industries.14–16 Since the glycerol molecule is highly
functionalized in comparison to other hydrocarbons derived
from crude oil, a very vast range of products could be
manufactured from glycerol.17

M. R. Karimi Estahbanati Mehrzad Feilizadeh has been an

obtained his BSc and MSc degrees
in chemical engineering from
Shiraz University (Iran, 2010) and
Sharif University of Technology
(Iran, 2013). In 2019, he received
a PhD degree from Université
Laval (Quebec, Canada) under the
guidance of Prof. Maria C. Iliuta.
After graduation, he joined the
National Institute of Scientific
Research (INRS) as a postdoctoral
M. R. Karimi Estahbanati fellow. His current research
focuses on the electrochemical
treatment of microplastics and nanoplastics in water.
assistant professor at the
Department of Chemical
Engineering, Shiraz University
(Iran), since 2016. He achieved
his PhD degree from Sharif
University of Technology (Iran)
under the supervision of Prof.
Vossoughi and Prof. Alemzadeh.
He leads a research group of
environmental and chemical
engineering students and
Mehrzad Feilizadeh researchers. His research
interests focus on photocatalysis,
desalination, water treatment, and solar energy.

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The most common methods for glycerol valorization to
gaseous (like hydrogen) or liquid value-added products are
steam reforming, partial oxidation, auto-thermal reforming,
pyrolysis, aqueous phase reforming, biological conversion, and
photocatalytic conversion (see Fig. 1).18,19 In the catalytic steam
reforming process, glycerol reacts with water at high
temperatures of 600–800 K.20,21 In the partial oxidation
method, glycerol reacts with oxygen in sub-stoichiometric
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ratios at even higher temperatures of around 1000–1100 K.22
Auto-thermal reforming is a combination of partial oxidation
and steam reforming, during which a defined ratio of glycerol,
water, and air is fed into the reactor simultaneously.23 Pyrolysis
is thermal decomposition of glycerol in the absence of oxygen
to produce bio-oils for subsequent conversion to other
feedstocks as intermediates. Aqueous phase reforming is a new
and non-conventional approach which operates at moderate
temperatures (200–250 °C) and pressures (2–2.5 MPa).24,25
Biological26,27 and photocatalytic28–31 methods are novel
approaches that operate under ambient temperature and
pressure conditions; as a result, significantly lower energy
consumption and operational cost are expected. The use of
photocatalysts in glycerol conversion not only increases the rate
of gas and liquid product generation, but can also enhance the
selectivity to desirable products. From the environmental point
of view, photocatalytic valorization of glycerol is an
environmentally friendly process. However, from the
technological point of view, there are several restrictions as a
consequence of its low reaction rate and the presence of
impurities in crude glycerol.32 As a result, more intensive
research is compulsory to overcome these limitations and
improve the efficiency towards an economically viable process.
In this work, the current developments and future trends of
process analysis as well as a parametric study of photocatalytic
glycerol valorization to hydrogen and value-added liquid
products are presented.
Farid Attar earned his BSc and
MSc degrees in chemical
engineering from Shiraz
University (Iran, 2016) and
Sharif University of Technology
(Iran, 2018). He then moved to
Shiraz University to work as a
research assistant and laboratory
supervisor under the supervision
of Dr. Feilizadeh. His current
research interests focus on energy
generation, photocatalysis,
Farid Attar electrocatalysis, and water
treatment.
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2. Reaction mechanism
Studying the mechanism of glycerol valorization to hydrogen
and value-added liquid products is essential for kinetic
modeling of the process as well as enhancing the selectivity
to products. The glycerol valorization process is favorable in
aqueous solutions, as water is a green solvent. In such a
medium, the H2O molecule not only participates in glycerol
conversion reactions, but also can independently split
especially at low glycerol concentrations.
The mechanism of hydrogen production from the
generated H+ during glycerol valorization is similar to that of
water splitting. It is shown that the addition of glycerol to
water can significantly increase the rate of reaction by
changing the dominant reaction path from water splitting to
glycerol conversion. When the glycerol is totally consumed,
the rate of hydrogen production approaches the rate of water
splitting (see Fig. 2).33 As can be seen, at low concentrations
of 0.10 and 0.18 nM, the rate of hydrogen production from
glycerol decreased and reached the rate of water splitting
after around 800 min. The fact that the rate of hydrogen
production from glycerol is higher than water splitting comes
from the higher tendency of glycerol to consume the
photogenerated protons which reduces the rate of electron–
hole recombination.
The photocatalytic valorization of glycerol can be
performed in either the presence (photo-oxidation) or
absence (photoreforming) of O2. Table 1 compares water
splitting, glycerol photoreforming, and glycerol photo-
oxidation reactions. Accordingly, in the glycerol photo-
oxidation and photoreforming processes, O2 and H2O play
the role of an oxidant, respectively. As H2O is not an effective
oxidant in comparison to O2, the rate of glycerol photo-
oxidation is around 5 times higher than glycerol
photoreforming.34 In addition, as glycerol can be valorized
Maria C. Iliuta has been a
professor in the Department of
Chemical Engineering at
Université Laval (Quebec, Canada)
since 2006. She received her PhD
in chemical engineering from
Université Catholique de Louvain
(Belgium) and performed
postdoctoral fellowships in phase
equilibria thermodynamics,
separation technologies, and
heterogeneous catalysis at the
Maria C. Iliuta Technical University of Denmark
and Université Laval. Her research
interests are especially directed towards process intensification,
catalysis (heterogeneous, enzymatic, and photocatalysis), separation,
capture and catalytic valorization of CO2, waste valorization,
alternative fuel/hydrogen production, and process modeling.
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Fig. 1 Summary of the most common methods for glycerol valorization along with gas and liquid products.

into hydrogen only in the absence of O2, in glycerol photo-
oxidation H+ ions are oxidized to H2O. It is worth
emphasizing that glycerol can be valorized to value-added
liquid chemicals by both photo-oxidation and
photoreforming processes, however, the rate of the former is
higher.34 Panagiotopoulou et al.34 analyzed the intermediates
and final products in glycerol photoreforming and photo-
oxidation and showed that both photoreforming and photo-
oxidation may proceed through similar reaction mechanisms.
However, it may not be always correct because more oxygen
reactive species are formed during the photo-oxidation.
A photocatalytic reactor works like a photoelectrochemical
cell where the anode and cathode are combined in the
photocatalyst particles. Therefore, in photocatalysis, the
generated O2 molecules are present both in the vicinity of the
photogenerated electrons and H+ ions. Consequently, the O2
molecules not only hinder the reaction of H+ ions with the
photogenerated electrons, but they also react with the H+
ions and obstruct the generation of hydrogen molecules. As a
result, it can be concluded that the generation of O2 may be
a significant reason for the very low efficiency of overall water
splitting which explains the importance of the presence of
carbon sources (like glycerol) in the solution to transform O2
in water to carbon dioxide (CO2).
The photocatalytic valorization of glycerol into hydrogen
and value-added liquid products can be performed through
its direct reaction with the photogenerated holes (hole-
mediated mechanism) or indirect reaction with the
photogenerated hydroxyl groups (radical-mediated
mechanism).35 The direct photocatalysis occurs on the
surface of the catalyst and therefore, the substrate should
first be adsorbed on the surface. The indirect photocatalysis,
however, can take place either on the surface of the catalyst
or in the liquid bulk. Apart from the mechanism of reaction,
the deep oxidation of glycerol ultimately leads to the
generation of hydrogen and CO2 (eqn (1)) or water and CO2
(eqn (2)), which represent the photoreforming and photo-
oxidation of glycerol, respectively:
C3H8O3 + 3H2O → 3CO2 + 7H2 (1)

C3H8O3 + (7/2)O2 → 3CO2 + 4H2O (2)

In glycerol valorization, an important question was regarding

the hydrogen source (glycerol and/or water). According to the
stoichiometry of eqn (1), during the photoreforming of
glycerol, hydrogen molecules are produced from both glycerol
and H2O, but to a higher extent from glycerol. The

Table 1 An overview on water splitting, glycerol photoreforming, and

glycerol photo-oxidation reactions

Water Glycerol Glycerol

splitting photoreforming photo-oxidation
Presence of O2 × × ✓
Oxidant — H2O O2
Reaction rate Very Low High
low
Fig. 2 Comparison of the hydrogen production rate from solutions Hydrogen production ✓ ✓ ×
containing low concentrations of glycerol with that from water Value-added liquid × ✓ ✓
splitting33 (reproduced with permission from Elsevier). chemical production

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production of hydrogen following this stoichiometry was
confirmed by measuring the amounts of hydrogen and CO2
(H2 : CO2 = 7 : 3) using dilute glycerol solutions.7,33,36 In
another work, the analysis of hydrogen production from
glycerol solution in D2O showed that almost 97% of hydrogen
was produced from glycerol.37,38 However, it is difficult to
draw a conclusion about hydrogen production from glycerol
in H2O based on this result, as the same work showed that
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D2O affected the process and even the rate of hydrogen
production was reduced around 4 times compared to using
H2O as a solvent.
The mechanisms of glycerol photoreforming and photo-
oxidation are presented in Fig. 3. As can be seen, a
photocatalytic reaction is triggered by absorption of a photon
of light by a photocatalyst to generate a pair of electron and
hole. The photogenerated charges can initiate a series of
reactions in the two above-mentioned cases. For example, in
the photoreforming of glycerol, the photogenerated electrons
react with either H+ or H2O to produce a H˙. A hydrogen
molecule can then be generated by the reaction of two H˙.34
On the other hand, the photogenerated holes can react
directly with glycerol (hole-mediated mechanism) to generate
products and intermediates or with water on the surface of
the catalyst to generate hydroxyl radicals. The generated
hydroxyl radicals can then react with glycerol or
intermediates (radical-mediated mechanism) to generate
products and intermediates in the solution bulk. In addition,
the generated hydroxyl radicals can react with themselves to
generate a hydrogen peroxide (H2O2) molecule which can
ultimately produce products and intermediates from glycerol
and intermediates.35 Accordingly, the generated
intermediates by photogenerated holes, hydroxyl groups, or
Fig. 3 Schematic representation of photocatalytic glycerol valorization under photoreforming and photo-oxidation35 (adapted with permission
from Elsevier).
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hydrogen peroxide can be further oxidized to generate
products. The complete photoreforming of glycerol leads to
the generation of hydrogen and carbon dioxide (as shown in
eqn (1)).34
In the photo-oxidation of glycerol, as can be seen in Fig. 3
the oxygen molecule reacts with a photogenerated electron to
form a superoxide radical. The formed superoxide radical
receives a hydrogen atom from either a direct reaction with
H+ or H2O to generate a hydroperoxyl radical and then
hydrogen peroxide can form by the reaction of the
hydroperoxyl radical with an electron and H+. Finally,
hydrogen peroxide reacts with an electron or superoxide
radical to generate a hydroxyl radical.39 The formed activated
oxygen species, i.e., superoxide radical, hydroperoxyl radical,
hydroxyl radical, and hydrogen peroxide have great potential
to react with glycerol or intermediates.34 On the other hand,
the photogenerated hole reacts with glycerol or intermediates
directly or indirectly (using hydroxyl radicals), like the case of
photoreforming, to generate oxidized products or
intermediates. Meanwhile, the generated activated oxygen
species contribute to the further oxidation of intermediates
and convert them into final products.35 The deep oxidation
of glycerol produces water and carbon dioxide (see eqn (2)).34
A proposed mechanism for photocatalytic glycerol
valorization to value-added chemicals is presented in Fig. 4.
The glycerol transformation starts with dehydrogenation to
glyceraldehyde (or dihydroxyacetone) as well as
hydrogenolysis (dehydration followed by hydrogenation) to
propylene glycol. Further dehydration (C–O cleavage),
dehydrogenation (O–H cleavage) and decarbonylation (C–C
cleavage) can yield other value-added liquid chemicals
containing 1, 2 or 3 carbons and ultimately CO2 (under both
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Fig. 4 A proposed reaction mechanism for photocatalytic glycerol transformation34 (reproduced with permission from Elsevier).
photoreforming and photo-oxidation conditions) and H2
(under photoreforming conditions). According to this
schema, different products such as acetol, 2-oxopropanal,
acetone, ethylene glycol, acetaldehyde, acetic acid,
glycolaldehyde, ethanol, and methanol can also be produced.
The mechanism of photocatalytic glycerol valorization can
be different under various photocatalysts. It was observed
that using the AEROXIDE TiO2 P25 photocatalyst (hereinafter
referred to as P25), the glycerol conversion rate as a function
of glycerol concentration hits a sharp peak, however, for
Merck anatase TiO2 the rate increases linearly (Fig. 5).40 This
observation suggests that the photocatalytic reaction using
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P25 is the combination of two different types of mechanisms:
(i) direct reaction with photogenerated holes and (ii) indirect
reaction with hydroxyl radicals generated by photogenerated
holes. The adsorption of glycerol on the surface of the
catalyst is necessary for the hole-mediated route, unlike the
radical-mediated one. Therefore, as fluorination occupies the
reaction sites of the photocatalyst, only the radical-mediated
route is performed under the fluorinated photocatalysts. To
assess the reaction mechanism of anatase TiO2 and P25, the
reaction rates for the pristine photocatalysts were compared
with those corresponding to the fluorinated catalysts
(inhibiting the adsorption of glycerol through the addition of
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Fig. 5 Influence of inhibition of glycerol adsorption by photocatalyst
fluorination on the glycerol conversion rate40 (reproduced with
permission from Elsevier). Merck: Merck anatase TiO2, P25/F:
fluorinated P25, Merck/F: fluorinated Merck anatase TiO2.
fluoride on their surface). The fluorination had no effect on
the mechanism of reaction in the presence of anatase TiO2,
but it altered the mechanism under P25 (Fig. 5).40 It was
therefore confirmed that both mechanisms (hole- and
radical-mediated) govern the glycerol valorization by P25,
while the radical-mediated one is predominant over anatase
TiO2. Under the Bi2WO6 photocatalyst, conversion of glycerol
was found to be based on the direct mechanism, because the
removal of hydroxyl radicals which are responsible for the
indirect mechanism did not affect the glycerol conversion
and product selectivity.41 It can be attributed to the fact that
the standard redox potential of H2O/OH˙ (+2.3 eV) is more
positive than that of photogenerated holes of Bi2WO6 (+1.77
eV) and as a result, OH˙ cannot be generated by the
photogenerated holes of this photocatalyst.42
The addition of H2O2 at the beginning of the reaction as
an electron acceptor changes the mechanism of the glycerol
transformation reactions by producing different reactive
oxygen species. Hydroxyl radicals are generated during a
photocatalytic transformation by reaction with either
photogenerated electrons or holes, while superoxide radicals
are formed in the presence of an electron acceptor like H2O2
or O2.43 The electron acceptors can increase the
concentration of the hydroxyl radical and single oxygen,
which normally tends to attack the primary carbon atom of
glycerol.44 It was shown that the type of generated value-
added liquid product was not affected by the type of formed
reactive oxygen species, but was changed by their
concentration.44 As H2O2 can be converted into two hydroxyl
radicals under UV radiation, or be reduced/oxidized by the
photogenerated species to produce highly reactive radicals
like hydroxyl, its presence in the reaction can increase the
rate of the radical-mediated mechanism. Accordingly, the
addition of H2O2 can increase the rate of photocatalytic
glycerol conversion especially at the beginning of the
reaction, and influence the products' selectivity as well.45 For
example, H2O2 addition enhanced the selectivity to
glyceraldehyde, glyceric acid, and glycolic acid, but decreased
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the selectivity to dihydroxyacetone because of its conversion
to glyceraldehyde by the hydroxyl radical. Jedsukontorn
et al.45 studied the effect of H2O2 in photocatalytic glycerol
transformation and concluded that the radical-mediated
mechanism was dominant in comparison to the hole-
mediated one for the conversion of glycerol to
dihydroxyacetone, glyceric acid, glycolic acid, and formic
acid. In addition, the addition of H2O2 led to the increase in
glycerol conversion from 19% to 73% because of the
enhancement of the reaction rate by hydroxyl radicals.
3. Process modeling
The majority of the research published on glycerol
valorization concerns experimental works. However, a couple
of efforts have also been made on modeling of photocatalytic
glycerol conversion to hydrogen that focused on the
development of kinetic and empirical models. The kinetic
modeling of the glycerol conversion process is based on a
well-established mechanism of the reactions to determine
the rate of product generation as a function of operating
parameters. On the other hand, empirical modeling does not
require understanding of the mechanism of reactions, the
whole process being considered as a “black box”. Therefore,
empirical modeling is less limited to the complexity of the
process. On the other hand, a few mechanistic studies were
conducted on the conversion of glycerol to value-added liquid
products.46 However, no work was found on the kinetic
modeling of the generation of value-added liquid products as
well as the optimization of the simultaneous generation of
gas and liquid phase products to minimize the complete
oxidation of glycerol to CO2.
Design of experiments is a practical tool to define the
experiments for the modeling of the process. It not only
ensures a uniform distribution of the experimental data in
the defined range of operating parameters, but also
optimizes the number of required experimental data. The
number of required data can be much lower when the
“design of experiments” is applied in comparison to the
conventional ‘one-variable-at-a-time’ approach. The designed
experiments for the available works on glycerol conversion
were defined based on fractional factorial (in two levels)45,47
and Box–Behnken (in three levels)48,49 designs. The reduction
of the number of experiments is essential especially when the
number of independent variables is more than three in order
to decrease the time and cost of experiments.
3.1. Kinetic modeling
A few works developed a kinetic model to predict the rate of
hydrogen production from glycerol as a function of operating
parameters.49–51 It was shown that the rate of hydrogen
production can be modelled as a function of glycerol
concentration using the Langmuir–Hinshelwood (LH)
equation:52
rH2 = k1KaC0/(1 + KaC0) (3)
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where rH2, C0, k1, and Ka represent, respectively, the hydrogen
production rate, initial glycerol concentration, reaction rate
constant, and equilibrium constant of glycerol adsorption/
desorption.37 As LH is supposed to predict the rate of glycerol
conversion as a function of the initial concentration, it can
be concluded that in this reaction, the trend of hydrogen
production is similar to that of glycerol conversion. This
observation confirms that glycerol is the source of hydrogen
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production or at least has an important contribution to the
production of hydrogen from the H2O and glycerol mixture.
Although LH is a simple and practical equation to model the
glycerol conversion, it is only a function of the initial glycerol
concentration and cannot predict the effect of other
operating parameters like pH, light intensity, catalyst load,
and time on the rate of hydrogen production. Clarizia et al.50
developed a kinetic model to predict the rate of hydrogen
production as a function of photocatalyst load, cocatalyst
percentage, and alcohol concentration (glycerol and
methanol) by solving a set of differential equations. They
used the experimental data to find the kinetic parameters
which helped in estimating the values of the rate of hole-
capture, adsorption equilibrium constants, primary quantum
yield, and rate constant for electron–hole recombination.
Analysis of these parameters showed that the deposition of a
cocatalyst decreased the rate of recombination reaction
which indicates that an important role of the cocatalyst is
trapping photogenerated electrons. In addition, the
equilibrium adsorption constant of glycerol was one order of
magnitude higher than that of methanol, which presents a
reason for the higher rate of hydrogen production from
glycerol than methanol. In another work,49 an intrinsic
kinetic rate equation was developed that can easily predict
the rate of hydrogen production as a power function of
catalyst loading and light intensity, a hyperbolic function
with respect to alcohol concentration, and an exponential
function of reaction time. Comparison of this intrinsic
model with the LH model showed that the intrinsic model
was more powerful as the LH model is only a function of
time. In addition, the kinetic model parameters were
calculated using the experimental data which showed that
the deactivation of the catalyst was faster for glycerol than
ethanol because of intermediate formation. It was also
illustrated that this model is valid for different substrates
and photocatalysts, which shows that the mechanisms of
photocatalytic reactions are generally similar. Another
kinetic model was developed to predict the effect of
hydrogen production from alcohols like glycerol as a
function of pH, which is a parameter that affects the
process from different aspects such as glycerol adsorption
and catalyst agglomeration.51 The authors showed that the
rate of hydrogen production depends on the adsorption of
substrates (a hyperbolic function) and agglomeration of the
catalyst (an exponential function). In addition, the analysis
of kinetic model parameters showed that the highest
amount of glycerol could be adsorbed on the catalyst
surface at a pH of around 9.1.
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3.2. Empirical modeling
The empirical models developed for glycerol conversion were
mainly based on response surface methodology (RSM) and
artificial neural networks (ANN). An empirical model that
contains the terms with the multiplication of operating
parameters takes advantage of being capable of considering
the interaction effect of the parameters. Using a first order
regression model that was developed based on the factorial
design, Jedsukontorn et al.44 showed that irradiation time
has the highest effect on the rate of glycerol conversion and
selectivity to value-added liquid products. Bastos et al.47 first
used a simple two-level fractional factorial design to screen
the factors having the most significant effect in hydrogen
production and then utilized the Box–Behnken experimental
design to develop an RSM model that is a function of glycerol
concentration, pH, and salt concentration. However, they
were not successful in optimizing the process as the
calculated critical point of the function was found to produce
the least amount of hydrogen. In another work,48 a
comparison of RSM and ANN models showed that the latter
fitted better the experimental data of photocatalytic hydrogen
production. Using the genetic algorithm method, the
optimum catalyst loading, cocatalyst %, pH, and glycerol %
were obtained at 3.9 g L−1, 3.1%, 4.5, and 50% (for
comparison purposes, glycerol concentrations are expressed
as volumetric percentage in this review paper), respectively.
In addition, analysis of the interaction effect of the operating
parameters showed that the operating parameters can
significantly affect the optimum value of the other three
operating parameters.
4. Parametric study of photocatalytic
glycerol valorization
This section is devoted to the effect of synthesis and
operating parameters in photocatalytic glycerol conversion to
hydrogen and value-added liquid chemicals. The effects of
synthesis parameters, i.e., cocatalyst percentage and
calcination conditions are first explained. Afterward, the
discussion focuses on the effects of the most effective
operating parameter such as the hydrogen source, time
duration of reaction, glycerol concentration, solution pH,
photocatalyst loading, photocatalyst stability, source and
intensity of light, and reaction temperature. Tables 2 and 3
summarize the range and optimum values of the operating
parameters investigated in different studies on glycerol
valorization to hydrogen and value-added liquid chemicals.
4.1. Synthesis parameters
4.1.1. Cocatalyst percentage. The rate of photoreforming
of glycerol can be significantly enhanced with the
incorporation of a cocatalyst. However, it may not increase
the rate of photo-oxidation reaction, because a main role of
the cocatalyst is the generation of hydrogen molecules which
are not produced in photo-oxidation. By increasing the
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Table 2 Summary of the range and optimum values (in the parenthesis) of various parameters investigated in different studies on glycerol valorization
to hydrogen

Glycerol% Comparison Reaction

Cocatalyst% Calcination in water Photocatalyst Duration with other No. of temp.
Photocatalyst (wt%) temp. (°C) (vol/vol) pH loading (g L−1) (h) substrates cycles (°C) Ref.
TiO2 — 300–500 — — — 10 — — 54
(400)
TiO2 nanorods — 200–400 — — — — — 5 — 79
(250)
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TiO2 nanorods, TiO2 — — — — 0.06–0.2 (0.1) — — 5 — 121

nanotubes
Pt/TiO2 0.05–5 (2) — 0.00073–7.9 3–10 0–2.66 (2.66) — — — 40–80 33
(7.9) (8) (60)
Pt/TiO2 — — — 2–12 4 — — 51
(8)
Pt/TiO2 0.02–5 (3.1) — 0.5–50 (50) 2–12 0.05–5 (3.9) 4 — — — 48
(4.5)
Pt/TiO2 0–2 (0.5) — — 1–4.5 — — — — — 114
(1)
Pt/TiO2 — — 0–20 (20) 0–13 — 5 — — — 52
(6.4)
Pt/TiO2 — — 0–0.01 — — 70 — — — 103
(0.01)
Pt/TiO2 — — — — — 14 GLY > PPG > — — 76
IPA
Pt/TiO2 — — 8.9–73.9 — — 3.5 — 5 — 107
(62.3)
Pt/TiO2 — 200–500 0.006–9.7 — — 5 — 4 — 36
(400) (9.7)
Au/TiO2 — — — — — 3 GLY > MEG > — — 91
MEOH >
ETOH
Au/TiO2 nanorods 0.5–2 (1.5) 200–1000 — — — — Triol (GLY) > — — 81
(600) diol (MEG ≈
PPG) > ETOH
> NPA
Pd/TiO2 — — — — — — GLY > DALC > — — 92
SUC > CyOH >
BA
Bi/TiO2 0–5 (2) — — — — 5 — — — 63
Bi/TiO2 nanotubes 0–5 (2) — — — — 5 — 5 — 63
Bi2O3/TiO2 0.3–0.6 (0.4) — — — — 4 — 5 — 74
Bi2O3-QD/TiO2 0–62 (9.6) — — — — — — — — 56
Co/TiO2 0.2–5 (2) — 0–20 (5) 2–12 — 10 GLY > MEG > 7 — 61
(6) MEOH >
ETOH > IPA
La/TiO2 0–7 (5) — — — — 4 — — — 88
Ag/TiO2 nanotubes 0.3–2.0 (1.5) — — — — 4 — — — 134
Ag2O/TiO2 0.75–6.75 400–700 0–30.24 — — — — — — 62
(2.82) (700) (21.28)
Ag2O/TiO2 0.5–5 (0.3) — — — 0.1–1 (0.2) 10 — 7 — 54
Ag2O/TiO2 0.5–10 (1) — 0–10 (5) — 2.5–10 (5) 24 — 5 — 57
Cu/TiO2 0.2–5 (0.5) — 0–20 (5) — — — — 6, 8 — 69
Cu/TiO2 1, 2.5 (2.5) — — — — — — — — 129
Cu/TiO2 — — 0.75–18 (18) — — — — — — 50
Cu/TiO2 nanosheets 0–2.65 (1) 200–450 — — — 3 — 5 — 68
(350)
Cu/TiO2 nanotubes 0.1–2 (1.5) — — — 0.06–2 (0.1) — — — — 67
Cu/TiO2 nanorods 0.5–2 (1.5) 400–550 — — — — — 3 — 59
(500)
Cu2O/TiO2 — — — — — 8 — 2 — 130
CuOx/TiO2 0.01–2.8 — 0.0027–7.3 — — 16.7 — — — 83
(2.8) (7.3)
CuO1−x/TiO2 0–10 (1) — — — — 8 — — — 65
CuFe2O4/TiO2 10–40 (20) — — — — 4 — — — 132
NiIJOH)2/TiO2 nanotubes 0.5–4 (2) — — — — 2 — — — 95
NiO/TiO2 0–5 (2) — 0–25 (25) 2–11 — — — — — 37
(6.6)
NiOx/TiO2 — 250–650 — — — 12 — — — 82
(450)

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Table 2 (continued)

Glycerol% Comparison Reaction

Cocatalyst% Calcination in water Photocatalyst Duration with other No. of temp.
Photocatalyst (wt%) temp. (°C) (vol/vol) pH loading (g L−1) (h) substrates cycles (°C) Ref.
CP-1/TiO2a 2.5–7.5 (5) — — — — — — — — 72
CP-1/TiO2a 0.5–1.5 (1) 420–520 — — — 4 — 4 — 73
(470)
M/TiO2 (M = Au, Pt, Pd) 0.5–3 (3) for — — — — 16.7 — — — 102
Au and Pt
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M/TiO2 (M = Au, Pt, Pd) 0.1–0.5 (0.1) — — — 0.09–8.75 3.5 GLY > MEOH — — 70
(0.09) > ETOH > IPA
> 1-BOH >
GLC
M/TiO2 (M = Pd, Pt, Au) — — — — — 6 GLY > MEG > — — 85
PPG > MEOH
> ETOH > IPA
> TBA
M/TiO2 (M = Au, Pd, — 500–700 — — — 3 GLY > MEG > — — 87
Au–Pd) (600) ETOH
M/TiO2 (M = Au, Pd) — — — — — 3.3 GLY > MEOH — — 99
M/TiO2 (M = Pt, Cu) 0.03–0.06 — — — — 3 — — — 145
(0.06) for
Cu, 0.1–0.2
(0.2) for Pt
M/TiO2 (M = Pt, CuO) — — — — — — GLY > crude — — 94
GLY
M/TiO2 (M = Cu, Ni) 0–15 (10) for — 0–50 (20) — — — — — — 146
Cu–Ni (Cu :
Ni = 9 : 1)
Pt/N/TiO2 nanotubes — — 0–70 (50) — — 5 — — — 105
Pt/B,N,TiO2 — — 2–10 (10) — — — GLY > GLC ≈ — — 147
SUC
Ni/γ-Al2O3/TiO2 5–25 (25) for — — — — 10 — — — 55
Ni
Cu/Ag/TiO2 nanotubes — — — — — 4 GLY > MEG > 10 — 89
ETOH >
MTOH > crude
GLY
Cu3IJPO4)2/CuO/TiO2 0.5–3 (1) for 500–800 0–20 (5) — 0.05–0.4 (0.2) — — 5 — 80
Cu3IJPO4)2 (500)
CNT/TiO2 — — — — 0.06–2 (0.1) — GLY > MEOH 4 — 90
> ETOH
CNT/TiO2 — 300–450 — — — 4 — — — 84
(350)
CNT/TiO2 0–1 (0.1) 350–500 — — — — — 5 — 66
(450)
CNT/TiO2 — 300–450 — — — 4 — — — 84
(350)
La/CNT/TiO2 3–7 (7) for — 0–20 (10) — — — GLY > MEG > 3 — 88
La MEOH >
ETOH
Ni/γ-Al2O3/CNT/TiO2 5–25 (10) for — — — — 10 — — — 55
Ni
Montmorillonite/CNT/TiO2 3–7 (5) for — 1–10 (5) — — 5 GLY > MEG > 4 — 127
CNT MEOH >
ETOH > PA
Pt/graphene/TiO2 — — — — — 6 GLY > MEG > 4 — 93
MEOH > PPG
> ETOH > PA
Cu2O/GO/TiO2 0–2 (1) for — — — — 2 — 4 — 64
Cu2O, 0–5
(3) for GO
Pt/rGO/TiO2 1.5–3.8 (3.8) — 5–80 (20) 5–11 0.1–1 (0.25) — — 2 30–40 97
for Pt, 1–4 (7) (30)
(3) for rGO
CuFe2O4/rGO/TiO2 1–4 (3) for — — — — 4 — 4 — 132
rGO
g-C3N4/rGO/TiO2 0.5–1.5 (1.5) — — — — 4 GLY > MEOH 4 — 148
for rGO > TETA

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Table 2 (continued)

Glycerol% Comparison Reaction

Cocatalyst% Calcination in water Photocatalyst Duration with other No. of temp.
Photocatalyst (wt%) temp. (°C) (vol/vol) pH loading (g L−1) (h) substrates cycles (°C) Ref.
Fe/g-C3N4/TiO2 — — 0–30 (10) — 0.1–1 (0.2) 10 — — — 77
Pt/CuxTi1−xO2−δ — — — — — 12 MEOH > GLY — — 149
Pt/CdS — — 30–70 4–10 — 3–7 — — — 47
Ni/CdS — — 0.15–55 (33) 3–13 — 10 — — — 101
(6)
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Cd–SnO2/CdS — 600–700 — — — — — — — 150

(600)
Cd0.5Zn0.5S — — 0–11 (7) 2–14 — — — 3 — 108
(14)
Pt/Cd1−xZnxS — — — — — 5 — 3 — 100
Pt/Cd1−xZnxS/ZnO/ZnIJOH)2 — — 0.365–7.3 — — 2 — — — 109
(2.2)
ZnO/ZnS — — — — 0.2–4 (1) — — 4 5–25 122
(25)
ZnO/ZnS — — — — — — — — 40–80 139
(80)
Graphene/ZnO/ZnS 0.01–0.1 — 1–50 (40) — — 3 — 3 — 131
(0.05) for
graphene
PdS–ZnO/ZnS 0–0.48 (0.24) — — — — — — — 40–80 71
for PdS (80)
Ni/γ-Al2O3 5–25 (10) — — — 0.1–2 (0.2) 10 — — — 55
Ni/CNT/γ-Al2O3 5–25 (10) for — — — — 10 — — — 55
Ni
Bi4NbO8Br — — — — — 4 GLY > MEG > — — 86
MEOH >
ETOH > IPA
a
CP-1: ([[CuIIIJ4,4′-dipy)2]ijNiIJCN)4]]n0.7IJC2H6O2)1.6IJH2O) polymer). GLY (glycerol), MEOH (methanol), ETOH (ethanol), PA (propanol), IPA
(isopropanol), NPA (propyl alcohol), PPG (1,2-propanediol), MEG (ethylene glycol), TBA (tert-butanol), 1-BOH (1-butanol), BA (benzyl alcohol),
CyOH (cyclohexanol), GLC (glucose), DALC (D-glucose), SUC (sucrose), TETA (triethanolamine).

Table 3 Summary of the range and optimum values (in the parenthesis) of various parameters investigated in different studies on glycerol valorization
to value-added liquid chemicals

Cocatalyst Glycerol% Photocatalyst loading Duration No. of Light intensity

Photocatalyst wt% (vol/vol) pH (g L−1) (h) cycles (mW cm−2) Ref.
TiO2 — — — 1–3 8 — 1.1–4.7 45
TiO2 — 0.073–1.3 — 0.1–0.4 0.42 — 0.02–2.63 46
TiO2 — 0.00015–0.8 — 0.005–0.1 1.5 — — 40
TiO2 — 0.00015–0.8 3–13 — 3 — — 151
TiO2 — — — — 20 — — 44
Pt/TiO2 — — — — 2 8 — 98
Pt/TiO2 — 0–22.4 — — 2 — — 152
Cu/TiO2 — — — — 3 — — 129
M/TiO2 (M = Bi, Pd, Pt, Au) — — — — 14 — — 153
M/TiO2 (M = Pd, Pt, Ru, Rh), Pd/C3N4Pd/SiO2 — 0–11.2 (11.2) — — 18 — — 154
TiO2, ZnO — — — — 3 — — 155
Na4W10O32 — — — — 2 — — 156
Bi2WO6 — — — — 10 — — 157
Bi2WO6 — — — — 12 6 — 41
Au/SiO2 0–15 (12.5) — — — 5 — — 158
Cu/Au/SiO2 0–6 (3) for Au — — — 5 — — 158

amount of cocatalyst deposition, the hydrogen production excessive amount of the cocatalyst (more than around 3%48)
rate can increase due to the higher availability of hydrogen can (i) make a barrier against the incidence of photons to the
production reaction sites and decrease in the rate of semiconductor, (ii) impede the access of the substrate to the
electron–hole recombination. On the other hand, an semiconductor surface, and (iii) increase the rate of electron–

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Reaction Chemistry & Engineering
hole recombination.53–57 Moreover, it leads to not only the
decrease in the accessible active sites, but also the prevention
of appropriate dispersion of particles on the photocatalyst
surface as a consequence of their agglomeration.58,59 This
phenomenon negatively affects the rate of reaction, as it
reduces the number of active sites.58
It was shown that just 1% Pt (for comparison purposes,
the cocatalyst percentages are expressed as wt% in this review
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paper) can enhance the rate of hydrogen production by TiO2
around 13 times.60 As can be seen from Table 2, generally 1–
3% of cocatalyst produced the optimal amount of hydrogen.
Deposition of around 2% Pt,33 Co,61 Ag2O,62 Bi,63 and NiO
(ref. 37) as a cocatalyst on TiO2 was found to produce the
highest amount of hydrogen. For Cu, Babu et al.64 reported
that the incorporation of 1% Cu on reduced graphene oxide
supported TiO2 is optimal, while with the incorporation of
1.5% and 0.5% Cu, the rate of hydrogen production
decreased more than three times (Fig. 6). Similarly, Lin
et al.65 concluded that more than 1% Cu content in CuO1−x/
TiO2 decreased the hydrogen production rate because of the
(i) disappearance of the effect of interfacial charge transfer
and a higher resistance of CuIJII) to Cu(0) transformation, and
(ii) hindering of the effective access of the semiconductor's
active sites to the photons of light. Carbon nanotube (CNT)
decorated TiO2 takes advantage of an effective charge transfer
between CNT and TiO2 because of the formation of Ti–O–C
bonds in the boundary of TiO2 and CNT. Reddy et al.66 found
0.1% CNT as the optimum amount of cocatalyst for TiO2 and
reported that CNT could not effectively be dispersed when its
content is less than 0.1%. As CNT can play other roles than
being the cocatalyst, such as a template and adsorbent,60 this
optimum value can be the outcome of different phenomena.
The morphology of TiO2 and dispersion of the cocatalyst
play an important role in the photocatalytic performance and
can change the optimum amount of cocatalyst. For example,
Fig. 6 The effect of Cu deposition as a cocatalyst on the rate of
hydrogen production by reduced graphene oxide supported TiO2 (ref.
64) (reproduced with permission from Royal Society of Chemistry).
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1.5, 1, 1 and 1.5% of Cu were found as optimum values for
TiO2 nanorods,59 TiO2 nanotubes,67 TiO2 nanoparticles,65
and TiO2 nanosheets,68 respectively. It is shown that the
optimum amount of cocatalyst can decrease when it is highly
dispersed because of its higher surface area.69 For example,
1% Cu was optimum when deposited on TiO2
nanoparticles,65 while 0.5% of finely dispersed Cu was
optimum.69 In another work, deposition of 0.1% of Pd and Pt
on TiO2 produced more hydrogen than 0.5%, which was
attributed to the smaller size of cocatalyst nanoparticles. For
the case of Au, however, almost no difference was observed
with the fine dispersion of particles which shows that Au
may be active enough to work effectively even in non-
dispersed form.70
Previous works71,72 showed that light wavelength (i.e. UV
and visible) has no effect on the optimum amount of
cocatalyst. This can be attributed to the fact that light
wavelength affects light absorption by the semiconductor and
the cocatalyst has no role in the absorption of light. For
example, addition of 0.24% Pd on the surface of ZnO/ZnS
nanorods was found as optimum to produce the maximum
amount of hydrogen under both UV and solar irradiation.71
Similarly, the deposition of 5% and 1% of a Cu/Ni based
polymer ([[CuIIIJ4,4′-dipy)2]ijNiIJCN)4]]n0.7IJC2H6O2)1.6IJH2O)IJCP-
1)) as a cocatalyst on P25 and hydrothermally synthesized
TiO2 was optimum for hydrogen generation under both UV
and visible light irradiation.72,73
4.1.2. Calcination conditions. The main aim of calcination
of photocatalyst materials is to (i) produce or change a
crystalline phase during semiconductor preparation,74,75 (ii)
form metallic particles or reduce them after impregnation of
the cocatalyst on the semiconductor surface,76 or (iii) dope
the formed cocatalyst on the surface with the semiconductor
bulk.77,78 The temperature and duration of calcination can
change the crystal phase structure of the photocatalyst by
affecting the type of formed stable crystal and proximity to
the stability, respectively.35 Calcination at temperatures less
than 400 °C can lead to poor crystallinity. As a result, less
active sites would be accessible for photocatalytic reactions.
On the contrary, calcination at temperatures higher than 600
°C can cause particle agglomeration (decrease of the number
of surface active sites),54,73,79,80 phase transformation,80 and
formation of inactive phases through mixing with other
phases or impurities.66 The duration of calcination can have
a synergistic effect with calcination temperature; therefore, at
400–600 °C a higher duration may have almost the same
effect of a higher temperature.
Calcination of highly stable Ag2O-loaded TiO2 at around
400 °C was found to be optimum because of lower
recombination of electrons/holes compared to 300 and 500
°C.54 For titanate nanorods, 250 °C was obtained as the
optimum calcination temperature while lower and higher
temperatures caused a decrease in the number of active sites
and inadequate accessibility of charge carriers at the surface,
respectively.79 Kumar et al.59 showed that Cu decorated
titanate nanorods calcined at 500 °C produced the highest
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amount of hydrogen. They attributed the less hydrogen
production using samples calcined at lower temperatures to
the generation of the single-crystalline TiO2 (B) phase which
increases the rate of recombination of photogenerated charge
carriers. However, the sample calcined at 500 °C was a
combination of bicrystalline TiO2 (B) and anatase phases
with approximately equal ratios. As the level of the
conduction band edge of TiO2 (B) is higher, the excited
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electrons are transferred to the anatase phase and this
phenomenon can reduce the rate of electron–hole
recombination.59 As seen in Fig. 7, both non-calcined Au/
TiO2 titanate nanorods and the ones calcined at 1000 °C
exhibited almost no hydrogen production, and the highest
amount of hydrogen was produced when the sample was
calcined at 600 °C which was attributed to the generation of
the smallest average Au particle size.81 The optimum
calcination temperature for non-uniformly shaped TiO2 and
titanate nanosheets was found to be 400 °C (ref. 36) and 350
°C,68 respectively, which indicates that the morphology of the
photocatalyst could affect the optimum calcination
temperature. For both TiO2 and NiOx/TiO2, 450 °C was
obtained as the optimum calcination temperature for
maximizing the hydrogen production rate, which suggests
that the deposition of a cocatalyst could have no effect on the
optimum calcination temperature.82 Moreover, Petala et al.83
showed that calcination temperature had no effect on the
photocatalytic activity of CuOx/TiO2 in glycerol conversion to
hydrogen. It was reported that the oxidation state of copper
was +2 and +1 when calcined at 350 and 450 °C, respectively,
which shows that the calcination conditions may change the
path of reaction through formation of different active sites
on the semiconductor.69 It is shown that the calcination
Fig. 7 The effect of calcination temperature on hydrogen production
by Au decorated titanate nanorods81 (reproduced with permission
from Elsevier).
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temperature also affects the formation of products other than
hydrogen. For example, calcined NiOx/TiO2 at 450 °C
produced the lowest amount of CO, and just under the
sample that was calcined at 600 °C, production of CH4 was
observed.82
The time duration of the calcination also affects the
structure of the photocatalyst and the rate of hydrogen
production. Reddy et al.79 showed that the time duration of
calcination might be more effective than the calcination
temperature. Titanate nanorods calcined at 250 °C for 2 h
produced around 2.5 and 7 times more hydrogen in
comparison to those calcined at the same temperature for 1
and 3 h, respectively.79 This was attributed to the insufficient
transformation of nanorods at lower time and agglomeration
of nanostructures at higher time. The time duration of
calcination can also affect the bonding between different
components of a composite photocatalyst. Reddy et al.84
indicated that 2 h is the optimum for the calcination of CNT/
TiO2 because of the formation of more effective carbon and
titanium oxide bonds, which enhances the charge transfer
between TiO2 and CNT.
4.2. Operating parameters
4.2.1. Type of substrate. We consider that the effect of the
substrate is of interest for this review because the
comparison of the potential of glycerol conversion with other
substrates is essential to highlight the advantages and
disadvantages of glycerol conversion. In water splitting, H2O
molecules are the sole source of the produced hydrogen. On
the other hand, no photocatalyst has been yet found to
generate an acceptable amount of hydrogen from pure
H2O.35,55 Utilization of alcohols (dissolved in water) as a
secondary source of hydrogen can increase the rate of
hydrogen production by 1 to 2 orders of magnitude.85 This
can be attributed to the fact that the oxidation potential of
alcohols is lower than that of H2O.86 Different factors such as
the substrate polarity (which can impact the adsorption and
electron donation properties), number of α-H, number of OH
bonds, position of OH in the molecule, number of carbon
atoms in the alcohol, and oxidation potential of the substrate
can affect their photocatalytic transformation.86–89 The lower
oxidation potential of an alcoholic substrate generally leads
to better hole scavenging and therefore a higher rate of
photocatalytic alcohol conversion.87
It can be seen in Table 2 that the rate of hydrogen
production from glycerol is higher than other alcohols. As
the most well-known trihydric alcohol, glycerol has three OH
groups. Some studies claimed that the number of OH groups
can be a significant factor for the rate of hydrogen
production among different substrates. Fu et al.76 compared
the amount of produced hydrogen from C3-polyols (glycerol,
propylene glycol and isopropanol) over Pt/TiO2 and found
that the ratios of hydrogen production are approximately
proportional to the alcohols' number of OH groups, i.e. 3, 2,
and 1, respectively. Moreover, by increasing the number of
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OH groups of C3-polyols, the quantity of generated CH4 and
C2H6 significantly reduced,76 which reveals that this increase
tends to valorize the alcohols in the form of an alkane.
Glycerol also produced a higher amount of hydrogen using
Au/titanate nanotubes than some diols and monols: glycerol
> 1,2-ethanediol ≈ 1,2-propanediol > ethanol > 1-propanol.81
These results not only confirm the order of triols > diols, but
also suggest that a lower number of carbon atoms in the
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chain may lead to a higher rate of hydrogen production in
monols. Almost the same result was obtained by using Pt
and Pd as a cocatalyst, where by applying M/TiO2
photocatalysts (M = Pd, Pt, Au), the hydrogen production rate
increased as: glycerol > 1,2-ethanediol > 1,2-propanediol >
methanol > ethanol > 2-propanol > tert-butanol.85 One
reason for the enhancement of the rate of hydrogen
production by increasing the number of OH groups can be
ascribed to the adsorption of alcohols on the surface of the
photocatalyst from their OH groups which serve as an anchor
for hydrogen bonding.76 Analysis of the rate of hydrogen
production using a CNT/TiO2 composite that contains much
more surface OH groups than pure TiO2 revealed that
glycerol produced 10 and 14 times more hydrogen in
comparison to methanol and ethanol, respectively.90 This
discussion clarifies the reason for the very high rate of
hydrogen production from glycerol, because the main
glycerol byproducts (like glyceraldehyde and
dihydroxyacetone) also have a higher number of OH groups
than primary alcohols.40
Other studies suggested that the attached hydrogen atoms
to hydroxyl carbon (α-H) can easily be converted to hydrogen,
and this hydroxyl carbon would be converted to CO2.91 For
example, in the presence of tertiary butanol (as a sacrificial
agent with no α-H), the rate of hydrogen production was
around one order of magnitude lower than the alcohols
containing α-H.91 By plotting the rate of hydrogen production
from glycerol, ethylene glycol, methanol, and ethanol as a
Fig. 8 Increase of the hydrogen production rate versus augmentation of the number of (a) α-H and (b) OH groups91 (reproduced with permission
from Elsevier).
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function of the number of α-H or OH groups, a linear trend
is obtained (Fig. 8). As this figure suggests, the experimental
data of methanol and ethanol (as two alcohols with the same
number of OH groups but different numbers of α-H) better
fit based on the number of α-H. Methanol produced a higher
amount of hydrogen than ethanol as it possesses more α-H.
Fig. 8 also confirms that glycerol with five α-H produced the
highest amount of hydrogen which shows the significance of
glycerol valorization in comparison to other alcohols.
Bahruji et al.92 showed, in addition to the presence of
α-H, that the feasibility of dissociation of the α-C–C bond is
another determinative factor. For example, hydrogen
production from cyclohexanol (a ring alcohol) and benzyl
alcohol (an aromatic alcohol) was not significant in
comparison to glycerol. Chen et al.91 and Wei et al.86 reported
that the rate of hydrogen production was found to be higher
from glycerol than other alcohols with a different number of
carbons and the following order was obtained: glycerol >
ethylene glycol > methanol > ethanol > isopropanol.
Analysis of these alcohols also showed that their polarity and
standard oxidation potential change in the same order.86,93
Therefore, this comparison also suggests glycerol as the most
promising alcohol for valorization purposes.
Crude glycerol generally contains impurities such as salts
and organic molecules, which could significantly affect the
photoconversion of glycerol. Comparison of pure and crude
glycerol as a hydrogen source revealed that pure glycerol
produced 2.5, 4, and 9 times more hydrogen under Pt/TiO2,
CuOx/TiO2, and Ni deposited TiO2 nanotubes, respectively.94
It should be noted that the composition of crude glycerol was
not similar in these works, which resulted in varied amounts
of glycerol conversion under these catalysts. It was reported
that millimolar concentrations of impurities such as NaCl,
Na2SO4 or NaNO3 in crude glycerol could reduce the rate of
hydrogen production by nearly 20%. The presence of
NaH2PO4 had a more negative effect on the reaction rate than
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the above-mentioned impurities (reduction by approximately
60%). These negative effects can be attributed to both
competitive adsorption of the anions and glycerol molecule
on the active catalyst sites and foam generation from the
residual soaps, while defoamers could not be effective as they
are degraded by the photocatalyst. The lower oxidation
potential of pure glycerol compared to the impurities present
in crude glycerol can be another reason for its higher
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conversion rate.95,96
The impurities in crude glycerol can have an interaction
effect with the operating parameters and change the
optimum operating conditions. Ribao et al.97 reported that
the optimum value of catalyst loading (rGO/Pt/TiO2, where
rGO is reduced graphene oxide) for crude and pure glycerol
conversion to hydrogen was 0.5 and 0.25 g L−1, respectively. It
means that more catalyst is required to achieve optimum
hydrogen production for crude glycerol, which can be
attributed to the inactivation of active catalyst sites by
impurities. On the other hand, 1 and 20% solutions were
found as optimum concentrations for crude and pure
glycerol, respectively. Almost no hydrogen was produced
using a high concentration of 20% crude glycerol solution in
water, which suggests that the impurities in crude glycerol
can have a detrimental effect on the photocatalytic activity.97
As hydrogen is produced simultaneously from glycerol and
H2O, the presence of impurities in water can also affect the
rate of reaction. It is reported that using seawater rather than
pure water halved the hydrogen molecule production because
of the agglomeration of catalysts with electrolytes like NaCl,
adsorption-inhibiting effect with formation of electrolytes
and hole scavenging with chloride.98
4.2.2. Time duration of reaction. Most works report an
approximately linear trend for the amount of hydrogen
produced during less than 10 h of reaction.36,81,99,100
However, by extending the reaction time, a plateau would be
observed which shows a decrease in the rate of hydrogen
production.101 Reddy et al.63 reported that although the
accumulative amount of hydrogen production increased, the
rate of hydrogen production could decrease in time, which
can be attributed to the catalyst deactivation or decrease of
glycerol concentration.102 In the case of low concentrations
(less than 0.1 M) of glycerol and prolonged reaction times
(higher than 100 h), two steps of the hydrogen production
rate were usually observed: (i) a very sharp increase of the
rate to a maximum, and (ii) a gentle rate decrease up to the
rate of hydrogen production from pure water (as the process
converts into a water splitting one).103 The lower rate at the
beginning of reaction (before the peak) is attributed to the
unsteady-state stage of the reaction. On the other hand, the
rate decrease after the maximum may be ascribed to catalyst
deactivation and decrease of glycerol concentration.74 In high
concentrations of glycerol (higher than 1%), however, the rate
of hydrogen production did not decrease towards the rate of
hydrogen production from pure water (water splitting) even
after 1000 min.102 During the reaction, CO2 was produced
with approximately the same trend of hydrogen, indicating
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complete oxidation of glycerol to CO2 and hydrogen.103 The
accumulated amount of produced H2 and CO2 was in good
agreement with stoichiometric amounts of eqn (1).34
The conversion of glycerol may not start exactly after
triggering the photocatalytic reaction. Analysis of an in situ
photodeposition of a cocatalyst on a semiconductor showed
that the photogenerated electrons were first consumed for
the cocatalyst formation and then for hydrogen production.
Petala et al.83 showed that for 0.37 mM concentration of
glycerol and in the presence of CuOx/TiO2 as a photocatalyst,
CO2 appeared just after the illumination started; however,
hydrogen was detected after 2 h. The detection of CO2 just
after the illumination shows that the photogenerated holes
were consumed from the beginning of the reaction to convert
glycerol. On the other hand, the delay of hydrogen generation
can be attributed to the alteration of the oxidation state of
copper particles from CuIJII) to CuIJI) or metallic Cu. It is
because of the fact that the reduction of CuIJII) is more
thermodynamically favorable than the reduction of
hydronium ions to produce hydrogen. This assumption can
also be justified by the observation that the augmentation of
Cu load led to the increase in the hydrogen detection delay
(because more electron is required to reduce CuIJII)), in such a
way that by increasing the Cu load from 0.04 to 2.8%, the
hydrogen detection time was also delayed from 25 to 120 min
(see Fig. 9).83
4.2.3. Glycerol concentration. Based on the current
photocatalytic technology, the rate of water splitting is low,
and the presence of glycerol can significantly enhance the
rate of photocatalytic hydrogen production. As the glycerol
content of different crude glycerol sources is substantially
dissimilar, discovering the effect of glycerol concentration is
interesting from a practical point of view.104 By increasing
glycerol concentration from millimolar to molar amounts, its
adsorbed amount on the photocatalyst surface also increases
and therefore, not only the rate of its transformation
enhances, but also the probability of recombination of the
generated charges (as a controlling step) reduces.48
Nevertheless, hydrogen production is reduced after an
optimum point of glycerol concentration (usually in the range
of 5–50% based on the conditions) as a result of hindering
the efficient adsorption of hydronium cations and H2O
molecules on the active sites of the photocatalyst.57,77,80
An addition of only 0.073% glycerol to water enhanced the
rate of hydrogen production around 3 times and its further
increase up to 7.93% improved more the rate of hydrogen
production.33 In another work, it was found that raising
glycerol concentration up to 5.48% enhanced the rate of
hydrogen evolution sharply up to 300 μmol h−1, and reached
a plateau at 29.2%.52 This behavior is similar to the LH
kinetic model and suggests Langmuir type glycerol
adsorption, which causes the hydrogen production rate to
obey eqn (3). The LH reaction mechanism is expected to be
satisfied only in low or medium (less than 50%) glycerol
concentrations, because at high concentrations the rate of
hydrogen production could decrease.
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Fig. 9 Time variation of the production rate of (A) hydrogen and (B) CO2 in different Cu loadings83 (reproduced with permission from Elsevier).
An optimum of glycerol concentration of around 50% was
reported by Slamet et al.105 for P25 (Fig. 10). Interestingly,
this optimum (which is around 3.94 : 1 (glycerol : water) molar
ratio) is near 3 : 1 stoichiometric molar ratio which can be
inferred from eqn (2). For the Pt/TiO2 photocatalyst, the
maximum hydrogen production was obtained at 53.6% in
another study which extended the range of glycerol
concentration,106 while the production decreased
meaningfully by 74.0% because of the hindering of the
adsorption of hydronium cations and H2O molecules.
Another work using the Pt/TiO2 photocatalyst also showed an
optimum for glycerol concentration at 62.3%.107 For the case
of using Cu69 and Co61 as cocatalysts, 5% of glycerol was
found as optimum, suggesting a different mechanism in the
presence of these cocatalysts. This lower optimal glycerol
concentration than the case of platinum can be justified by
the fact that the rate of the hydrogen production half-
reaction was lower on these cocatalysts (which were less
active than platinum) and therefore, a low glycerol
concentration on the surface was sufficient to consume the
photogenerated protons and not control the overall reaction.
Fig. 10 The effect of glycerol concentration and irradiation time on
the amount of hydrogen production using Pt–N–TiO2 (ref. 105)
(reproduced with permission from John Wiley and Sons).
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However, in the presence of Cu and Co as less active
cocatalysts than Pt, a lower optimum glycerol concentration
was obtained because the rate of the hydrogen production
half-reaction is lower.
As suggested by the LH model (eqn (3)) and confirmed by
experimental data of previous works,37,52 the rate of the
photocatalytic reaction is exponentially enhanced by
increasing the glycerol concentration. To overcome this issue,
powerful adsorbents like CNT can be combined with the
photocatalyst to increase the concentration of glycerol on the
surface of the photocatalyst. It is shown that this technique
can enhance the rate of hydrogen production at low (around
1%) glycerol concentration around two times.60 However, this
effect was not observed in high (10% and 50%) glycerol
concentrations because sufficient glycerol molecules were
adsorbed at these concentrations.
The optimum value of glycerol concentration may vary
depending on the type of photocatalyst because the nature of
the photocatalyst affects the rate of reaction and the
equilibrium amount of adsorbed glycerol on the surface. A
glycerol concentration of 55% was suggested as optimum
glycerol content for the CdS photocatalyst.47 Despite this,
around 33% glycerol was reported to be optimal for CdS
quantum dots, which was attributed to their high surface to
volume ratio that helps in the adsorption of more glycerol.101
For Cd0.5Zn0.5S solid solution108 and Pt/Cd0.2Zn0.8S/ZnO/
ZnIJOH)2 multiphase109 photocatalysts, 7 and 2.2% glycerol
were reported as optimal, respectively.
In addition to the overall rate of photocatalytic reaction,
increasing the glycerol concentration can enhance the initial
rate of reaction.40 It was shown that glycerol concentration
has an interaction effect with pH, catalyst loading, and
cocatalyst loading, for production of hydrogen from glycerol,
and higher concentrations increased the optimum value of
these parameters.48 Glycerol concentration can also affect the
stability of the photocatalyst, as was reported for the case of
Pt/hex-CdS.47
4.2.4. Solution pH. Solution acidity or basicity is one of
the most important operating parameters affecting glycerol
conversion.47,48 A thorough analysis of the relative
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importance of operating parameters showed that pH is the
second most influential parameter after catalyst loading
(among pH, catalyst loading, cocatalyst%, and glycerol%) and
can affect the rate of hydrogen production by around 29%.48
This determinative role is attributed to the significant
influence of pH on photocatalyst agglomeration and glycerol
adsorption.51 pH can change different characteristics of the
photocatalyst such as functional groups and surface charge
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which causes the alteration of the catalyst particle size
distribution. It can also change the band gap of the
photocatalyst and therefore the absorption of light. The pH
of solution alone cannot influence glycerol dissociation
because the dissociation constant is high (pKa = 14.4).
However, it can affect the adsorption of glycerol and
intermediates on the photocatalyst surface, as well as the
desorption of products from the surface.35,110 The
agglomeration of the catalyst occurs at pH around zero point
of charge (pHzpc) where no electrostatic potential exists
because of the lack of surface charge.111,112 The
agglomeration reduces the accessible area of the catalyst for
absorption of light as well as conducting a chemical reaction.
For the case of TiO2 as an example, the agglomeration of
particles occurs at a zeta potential of around ±30 mV and at
values close to zero no agglomeration occurs because of the
low electrical potential at the slipping plane.113 The
agglomeration of the catalyst not only decreases the
accessibility of substrates and light to the active site of the
catalyst, but also increases the tendency of catalyst particles
to sediment. As glycerol adsorbs on the photocatalyst surface
based on hydrogen-bonding, the solution pH affects the
adsorption of glycerol on the surface by changing the number
of surface OH groups. In an acidic or basic solution, the
surface OH groups may dissociate according to eqn (4) and
(5), respectively:
K a1
Cat − OH2 þ ƒ! −OH þ Hþ (4)
Fig. 11 Variation of solution pH during hydrogen production from
glycerol using Pt/TiO2 (ref. 36) (reproduced with permission from
Royal Society of Chemistry).
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K a2
Cat − OH ƒ! −O − þ Hþ (5)
It is suggested that when pKa1 < pH < pKa2, the catalyst
surface is covered with an adequate number of OH groups to
adsorb required glycerol molecules for the photocatalytic
reaction.51
Solution pH is not constant during the reaction because
of continuous generation and consumption of hydronium
and hydroxide ions. Jiang et al.36 reported the reduction of
pH of glycerol solution during photocatalytic transformation
to hydrogen and its tendency to a stable value around 3.5
(Fig. 11). This behavior was attributed to the generation of
intermediate carboxylic acids which reduced the pH towards
the acidic range. In another work, the final pH of the
solution was found to tend towards 8, 6, and 5 for the
conversion of methanol, ethanol, and glycerol to hydrogen,
respectively. For the case of glycerol, it was attributed to the
formation of 1,3-dihydroxyacetone, glyceraldehyde, formic
acid, and formaldehyde or probably glyceric acid, tartronic
acid, hydroxypyruvic acid, mesoxalic acid, and oxalic acid as
intermediates.51
A comprehensive analysis of the effect of solution pH on the
rate of hydrogen production from glycerol using TiO2 showed
that the maximum amount of hydrogen was produced around
pH of 8. This pH is sufficiently far from the pHzpc of TiO2
(which causes catalyst agglomeration), i.e., around 6.0, and
close enough to neutral pH (at which glycerol efficiently
adsorbs on the catalyst surface). In addition, a local minimum
around pHzpc was found which can be attributed to extensive
catalyst agglomeration at this pH.51 A global minimum was
also observed at highly basic pH (around 12), which may be
ascribed to extensive dissociation of surface OH groups (eqn
(5)).51 In the case of using platinum,33,52 cobalt,61 and nickel37
as a cocatalyst for TiO2 as well as nickel-hybrid CdS quantum
dots (pHzpc of around 7.5),101 the initial pH around neutral
was found to be optimal because of the highest amount of
glycerol adsorption on the catalyst. On the contrary, for the
Cd0.5Zn0.5S photocatalyst, hydrogen production in acidic or
neutral solutions (pH of 2–9) was found to be negligible, while
it was improved with increasing alkalinity.108 However, in a
high concentration of 4 mol L−1 of NaOH (around pH of 14),
the production rate was decreased, and hydrogen production
was maximum at an initial pH of 14. This behavior was
ascribed to the relatively high isoelectric point of this
photocatalyst, which is in the pH range of 8.1–11. In the case of
heteropoly blue sensitized Pt/TiO2, it was reported that
hydrogen was produced at pH less than 3 and no hydrogen was
detected at the initial pH of 3–4.5.114 This was explained by the
effect of increasing pH on the degradation of H3PW12O40 to
other heteropoly anions that have lower photocatalytic
activity,115 where H3PW12O40 can be completely decomposed at
pH higher than 2.5.116
4.2.5. Photocatalyst loading. Similar to any catalytic
reaction, photocatalytic conversion of glycerol depends on
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the amount of available photocatalyst to absorb light and
also transform glycerol. Analysis of the relative importance of
operating parameters of photocatalytic hydrogen production
from glycerol using TiO2 showed that the catalyst loading is
the most effective parameter (in comparison to other
parameters such as pH, glycerol concentration (v/v), and Pt
mass percentage as a cocatalyst).48 The rate of photocatalytic
glycerol conversion is expected to reach a maximum value by
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changing the photocatalyst loading to efficiently absorb the
highest amount of light.117,118 On the other hand,
photocatalyst agglomeration increases in very high
photocatalyst loadings; as a result, (i) a part of the
photocatalyst surface could be unavailable for absorption of
photons,119,120 and (ii) the light can scatter because of
solution opaqueness.57,77,121 For example, in the case of Pt/
P25, it is reported that by increasing the photocatalyst
loading up to 2.66 g L−1, the hydrogen production rate
increased.33 However, 0.1 g L−1 of photocatalyst was found to
produce maximum hydrogen from glycerol using TiO2
nanotubes and CNT/TiO2. This was attributed to their high
specific surface area (200 and 100 m2 g−1, respectively) in
comparison to Pt/P25 (48 m2 g−1),121 which leads to a higher
capability to adsorb glycerol. On the other hand, for ZnO/ZnS
heterostructured nanorods with a BET surface area of 32.61
m2 g−1, an optimum photocatalyst loading of 1 g L−1 was
observed.122
4.2.6. Photocatalyst stability. Photocatalyst stability is one
of the most significant barriers against its commercialization.
The deactivation of the photocatalyst normally occurs
because of the adsorption of intermediates on the catalyst
surface. A kinetic study on the deactivation process showed
that the adsorption of poisonous intermediates/products like
CO is almost irreversible if it takes place in the initial stage
of the reaction.123 The produced intermediates can decrease
the rate of photocatalytic reaction because of (i) poisoning of
the active sites with persistent intermediates or
products,124–126 (ii) seriously affecting the adsorption of
glycerol on the surface of the catalyst, and (iii) generating an
opaque solution.127 The number of active surface sites
generally reduces exponentially because of the deactivation,
i.e., the photocatalyst deactivation can be considered as a
first order reaction.49,123 However, the poisoned photocatalyst
can be reactivated by its annealing; for the case of TiO2 for
example, at a maximum temperature of around 450 °C (to
avoid catalyst phase transformation).
One approach to systematically evaluate the recyclability
and durability of a photocatalyst is comparing its
photocatalytic activity in several cycles by repeating the
experiment after purging the reactor with an inert gas. By
purging the reactor, the gaseous intermediates adsorbed on
the catalyst active surface sites (like CO) can be removed to
regenerate the photocatalyst. As normally the glycerol
concentration does not significantly reduce in a limited time
(especially at concentrations higher than 1%), the
photocatalytic activity reduction in the cycles can be
considered due to photocatalyst deactivation. It is worth
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mentioning that an increase in the rate of hydrogen
production in the later cycles may be observed, which can be
attributed to the higher activity of the photocatalyst because
of the change in its structure in the earlier cycles. For
example, TiO2 nanosheets doped with quantum CuIJII)
nanodots showed a higher activity in the second experiment
of the cycle in comparison to the first one for producing
hydrogen from glycerol.68 Less hydrogen production in the
first cycle was attributed to the reduction of CuIJII) by the
photogenerated electrons, as confirmed by the observation of
a higher CO2 generation rate in the first run (which shows
that the photogenerated holes were produced and consumed
for CO2 production). Another approach is the photocatalyst
separation by centrifugation or filtration and then its
employment for another set of experiments. Although in this
method fresh glycerol solution is used to avoid the
differences between the experiments, complete removal of
adsorbed intermediates from the photocatalyst may not be
possible. In addition, the quality of the photocatalyst may be
affected because of its contact with atmospheric oxygen. For
instance, the recovery and reuse of Cd1−xZnxS showed around
90% reduction in the rate of hydrogen production from
glycerol, which was reported to be due to metal sulfide
oxidation by atmospheric oxygen during the recovery.100
A couple of works studied the parameters that affect the
deactivation of the photocatalyst during glycerol
transformation. The stability of the photocatalyst depends on
its chemical structure and can be enhanced by its chemical
modification. For example, Pt/TiO2 (Kronos) exhibited around
25% decrease in the initial rate of hydrogen production from
glycerol after five cycles, while the reduction was around 55%
for Pt/P25 after three cycles.107 The higher rate of
deactivation of P25 can be attributed to its superior surface
area (around five times) which causes higher sensitivity to
poisoning of the active sites. It was shown that the activity of
CNTs/TiO2 (ref. 66) and La/CNT/TiO2 (ref. 88) decreased
because of deactivation of catalyst active sites by
intermediates/products which affected the interaction of
glycerol and the photocatalyst.66 However, employing
montmorillonite to make the montmorillonite/CNT/TiO2
photocatalyst successfully increased its stability.62
Changes in the chemical or physical characteristics of the
photocatalyst, for instance by alteration of its chemical
structure or agglomeration of particles, reduces the number
of active sites and therefore causes photocatalyst
deactivation. For example, it was reported that the hydrogen
production yield decreased by around 22% after recycling
Ag2O/TiO2 5 times; it was attributed to the reduction of Ag+
ions which affected the structure of the photocatalyst by the
aggregation of particles and reduction of the photocatalyst
active surface area.57 It was also reported that the stability of
Cp-1/TiO2 (CP-1: ([[CuIIIJ4,4′-dipy)2]ijNiIJCN)4]]n0.7IJC2H6O2)1.6-
IJH2O) polymer)) to produce hydrogen from glycerol slightly
decreased after four cycles because of the agglomeration of
catalyst particles.73 It is shown that the deactivation of a
photocatalyst may be affected by the operating parameters
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such as radiation wavelength and solution pH. For example,
CuS/Cd0.3Zn0.7S is more stable in basic pH rather than
neutral because the sulfide ion oxidizes to sulfate and sulfite
ions after 3 hours of irradiation.128 Regarding the radiation
wavelength, no decrease in the photocatalytic activity of Co/
TiO2 was observed after 7 cycles under solar irradiation.
However, under UV illumination, around 10% hydrogen
production decrease was observed under the same
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conditions.61 Similarly, in the case of Cu/TiO2, the rate of
hydrogen production decreased by around 25% after 6 h
under UV irradiation, while under solar irradiation it was
almost constant up to 80 h.129 Ag2O/TiO2 indicated no
deactivation and showed a 12% hydrogen production rate
decrease after 7 cycles under solar and UV irradiation,
respectively. This result was attributed to the fact that only
under solar irradiation can Ag2O be transformed to the
Ag2O–Ag phase which has high stability and photocatalytic
sensitivity.54
It was reported that the combination of a photocatalyst
with carbonaceous materials may reduce its stability. Cu2O/
TiO2 (ref. 130) and Cu2O/TiO2 nanorods59 were stable; no
Cu2+ was detected on the surface of TiO2. However, addition
of rGO to make rGO/Cu2O/TiO2 resulted in around 15%
decrease in the stability after 4 cycles.64 Almost the same
result was obtained for addition of graphene to make
graphene/ZnO/ZnS, as it was reported that the amount of
produced hydrogen decreased by around 10% after 3
cycles,131 while ZnO/ZnS heterostructured nanorods were
almost stable after four cycles.122 However, rGO/CuFe2O4/TiO2
was stable in the conversion of glycerol to hydrogen without
leaching and deactivation after four cycles (cycles of 120
min),132 which was attributed to the high stability of
CuFe2O4.133
For the case of Ag2O/TiO2 nanotubes, the amount of
deactivation was found to be the same in pure water and
glycerol solution and no silver was detected in the effluent,134
suggesting that other causes may exist for catalyst
deactivation.135 As can be inferred, analysis of the variation
of photocatalyst activity is very complicated and may be
affected by different parameters such as the type and
structure of photocatalyst, alteration of the photocatalyst
surface area, pH of solution, wavelength of light, and
combination of the photocatalyst with carbonaceous
materials. Despite this, very limited work investigated the
strategies to increase the photocatalytic stability for glycerol
transformation and further study is necessary to reduce the
rate of photocatalyst deactivation.
4.2.7. Source and intensity of light. Solar radiation is a
sustainable, clean, and renewable source of light.
Consequently, it is considered as a promising source for
photocatalysis in the future.136 Around 3–5% of the total
solar energy is in UV spectra (<400 nm) and the rest is in the
range of visible and infrared.35 As the number of photons is
important for a photocatalytic reaction, even a lower
percentage of solar radiation is in the UV range by
considering the number of its photons.137
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Analysis of the light source of previous works shows that
most of them utilized UV lamps to perform the experiments.
Despite this, a few works used natural solar radiation as the
light source to analyze the process under solar energy.59,61 In
solar photocatalytic valorization experiments, the radiation
was provided using a solar simulator, usually using a Xe arc
lamp coupled with light filters.47,83,86 It is worth mentioning
that the generated spectrum of the solar simulator does not
supply the exact range of solar radiation.80
The comparison of the rate of glycerol conversion under
UV and visible radiation is essential to analyze the potential
of a photocatalyst in working with solar energy. The rate of
glycerol conversion under UV irradiation is usually higher
than visible light, because the photocatalysts are generally
more active under UV than visible irradiation. For example,
under Cu/TiO2,129 Co/TiO2,61 Pt/rGO/TiO2,97 TiO2
138 89
nanorods, Cu/Ag/TiO2 nanotube, and ZnO/ZnS–PdS core/
shell nanorods139 around 1.5, 2, 1.95, 3.4, 3, and 9 times
higher hydrogen production rate was observed under UV
irradiation in comparison to solar irradiation, respectively. In
addition,138 Bi4NbO8Br had 5 times more photocatalytic
activity under simulated solar light (λ > 300 nm) than visible
light (λ > 420 nm).86
Regarding the power of the light source, most of the
research utilized 100–500 W lamps. It is challenging to
compare this value with 1000 W m−2 reported by the
American Society for Testing and Materials (ASTM) as the
average solar radiation at the ground level at noon,137
because the intensity of the light received by the reactor is
affected by different parameters such as lamp efficiency and
reactor dimensions. The light intensity is a key parameter in
the rate of glycerol conversion. It is shown that the rate of
hydrogen production from glycerol increases as a power
function with respect to the light intensity with a power value
between 0 and 1.49 It means that by increasing the light
intensity the rate of hydrogen production first increases
almost linearly and then non-linearly. For example, the rate
of glycerol to hydrogen conversion by Pd/P25 under visible
light was found to be almost linear and enhanced by around
25% by a 30% increase in light intensity.140
4.2.8. Reaction temperature. Analysis of the effect of
reaction temperature on the rate of glycerol conversion is
useful not only to investigate the performance of the process
at cold or warm climate, but also to analyze the prospects of
thermo-photocatalytic reactions. As a catalytic reaction, the
rate of photocatalytic reaction is dependent upon the
temperature. Since the band gap of photocatalysts is too large
to undergo thermal excitation around ambient temperature,
usually the influence of temperature is not attributed to
light-driven reaction steps. However, the solution
temperature influences the rate of glycerol conversion by
affecting the individual reaction steps (i.e., conversion of
chemicals), the adsorption/desorption of substrates/products,
and their diffusivity in the solution.141–144
Raising the temperature (especially up to 100 °C) usually
increases the glycerol conversion rate. Using the Pt/TiO2
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photocatalyst, the rate of hydrogen production from glycerol
was found to enhance around twice by increasing the
reaction temperature from 40 °C to 60 °C; however, further
increase up to 80 °C did not affect the rate significantly
which may be attributed to having no effect on the dark
reaction steps.33 Most of the case studies on the effect of
temperature on the rate of photocatalytic glycerol conversions
were conducted on non-TiO2-based photocatalysts. By
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increasing the reaction temperature from 5 to 25 °C, ZnO/
ZnS and ZnS photocatalysts illustrated around two-fold
increase in the hydrogen production rate, while ZnO showed
an increase of about three times.122 Further increasing the
reaction temperature from 40 °C to 60 °C and 80 °C can
double and triple the rate of hydrogen production using ZnO/
ZnS because of dark reaction steps, respectively.139 Moreover,
it was found that increasing the temperature from 40 °C to
80 °C enhanced the rate of hydrogen production from
glycerol using ZnO/ZnS–PdS around two times more than
ZnO nanorods, which can be attributed to the higher
sensitivity of ZnS–PdS to temperature.71
5. Conclusions and perspectives
A large amount of attention has been devoted to photocatalytic
reactions in recent decades. Most of the research has focused
on photocatalytic degradation, but photocatalytic synthesis has
started to attract more attention recently. The photocatalytic
valorization of glycerol to hydrogen and value-added liquid
products is a promising approach from a sustainable
development point of view. A stoichiometric amount of
hydrogen was shown to be generated from glycerol, which
indicates that the maximum possible chemical energy of
glycerol can be converted into this valuable energy carrier. It
must be emphasized that, to investigate the capability of a
photocatalyst for glycerol valorization, its performance has to
be investigated under the optimized conditions of operating
parameters. Therefore, in addition to the synthesis of new
photocatalysts and their enhancement, a variety of research
studies have been performed on the optimization of synthesis
and operating parameters. The most investigated parameters
are the cocatalyst percentage, calcination conditions, type of
substrate, time duration of reaction, glycerol concentration,
solution pH, photocatalyst loading, photocatalyst stability,
source and intensity of light, and reaction temperature. A
detailed review on the effect of these parameters revealed that:
• The presence of a cocatalyst can significantly enhance
the rate of hydrogen production and typically between 1 and
3% cocatalyst is optimal;
• The optimal temperature and time duration of
photocatalyst calcination are around 400 °C and 2 h;
• Glycerol usually produces the highest amount of
hydrogen in comparison to all possible alcohols;
• The rate of photocatalytic reaction typically increases to
a plateau with the passage of time and then decreases due to
the deactivation of the catalyst or reduced glycerol
concentration;
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• A solution with around 50% glycerol concentration
generally produces the highest rate of hydrogen production;
• A neutral or slightly basic solution can produce the
highest amount of hydrogen;
• Depending on the surface area of the catalyst, around
0.2–2 g L−1 of catalyst loading can be optimal;
• The rate of photocatalytic reaction enhances by
increasing the temperature.
In the light of this literature review, we can conclude that
the photocatalytic valorization of glycerol has promising
potential to generate: (i) simultaneously hydrogen and value-
added liquid products under photoreforming conditions (in
the presence of O2), or (ii) only value-added liquid products
under photo-oxidation conditions (in the absence of O2).
Although most of the research focused on the generation of
hydrogen, a few works studied the generation of value-added
liquid products. As a vast range of value-added liquid
products can be generated from glycerol and some of them
are more valuable than hydrogen, further study is essential to
enhance the selectivity to the most valuable liquid products.
The mild atmospheric conditions of the photocatalytic
process are the key to selectively synthesize value-added
liquid products. In addition, no work has been performed on
the optimization of the operating parameters to obtain an
optimal integrated production of desired gaseous and liquid
products. In this context, selective glycerol conversion to
hydrogen and liquid chemicals, and photo-reduction of the
evolved CO2 to fuels are indeed promising prospects towards
value-added chemical generation technology.
To sum up, in order to develop an effective process for
photocatalytic valorization of glycerol, at first, access to the
technology of suitable photocatalyst synthesis with a high
conversion and acceptable selectivity to desired products
under solar irradiation along with optimization of synthesis
parameters like calcination conditions and cocatalyst
percentage is necessary. Afterward, the operating parameters
should be optimized to find the best conditions of the
parameters such as catalyst loading and pH. Finally, the
production of value-added liquid products should be
considered as a promising approach in practice. On the other
hand, as purification of crude glycerol is a costly process,
direct conversion of crude glycerol could shift this process
into a more economically viable one. In the case of hydrogen,
other than its generation, its purification, transportation, and
utilization are important issues that have to be considered in
order to take a step towards a sustainable society reliant on
solar hydrogen.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors are very grateful to the Ministry of Education and
Higher Education of Quebec as well as TELUS and Laval
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University for awarding Ph.D. scholarships entitled “Merit
Scholarship Program for Foreign Student” and “Leadership
and Sustainable Development Scholarship”, respectively. They
would also like to express their gratitude to The Natural
Sciences and Engineering Research Council of Canada
(NSERC) for its financial support.
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