Nano Research

DOI 10.1007/s12274-016-1087-9

Photocatalytic reduction of CO2 with H2O over modified

TiO2 nanofibers: Understanding the reduction pathway
Anjana Sarkar1 (), Eduardo Gracia-Espino2, Thomas Wågberg2, Andrey Shchukarev1, Melinda Mohl3,
Anne-Riikka Rautio3, Olli Pitkänen3, Tiva Sharifi2, Krisztian Kordas3, and Jyri-Pekka Mikkola1,4 ()

1
Technical Chemistry, Department of Chemistry, Chemical-Biological Centre, Umeå University, SE-901 87 Umeå, Sweden
2
Department of Physics, Umeå University, SE-901 87 Umeå, Sweden
3
Microelectronics and Materials Physics Laboratories, Department of Electrical Engineering, University of Oulu, P.O. Box 4500, Oulu
FI-90014, Finland
4
Laboratory of Industrial Chemistry and Reaction Engineering, Johan Gadolin Process Chemistry Centre, Åbo Akademi University,
Biskopsgatan 8, Åbo-Turku FI-20500, Finland

Received: 25 June 2015 ABSTRACT

Revised: 27 March 2016 Nanosized metal (Pt or Pd)-decorated TiO2 nanofibers (NFs) were synthesized
Accepted: 1 April 2016 by a wet impregnation method. CdSe quantum dots (QDs) were then anchored
onto the metal-decorated TiO2 NFs. The photocatalytic performance of these
© Tsinghua University Press catalysts was tested for activation and reduction of CO2 under UV-B light. Gas
and Springer-Verlag Berlin chromatographic analysis indicated the formation of methanol, formic acid,
Heidelberg 2016 and methyl formate as the primary products. In the absence of CdSe QDs,
Pd-decorated TiO2 NFs were found to exhibit enhanced performance compared
KEYWORDS to Pt-decorated TiO2 NFs for methanol production. However, in the presence of
TiO2, CdSe, Pt-decorated TiO2 NFs exhibited higher selectivity for methanol, typically
photocatalysis, producing ~90 ppmg−1·h−1 methanol. The CO2 photoreduction mechanism is
CdSe quantum dots, proposed to take place via a hydrogenation pathway from first principles
CO2 photoreduction calculations, which complement the experimental observations.

1 Introduction reducing CO2 emissions. Increasing industrialization in

After realizing the after effects of the industrial
revolution, increasing atmospheric CO2 concentration
is now considered one of the main reasons for global
climate change. Along with methane (CH4), nitrous
oxide, halogenated compounds, and freons, CO2
constitutes a significant part of the greenhouse gases.
Therefore, a lot of attention has been focused on
developing countries results in large-scale combustion
of fossil fuels, such as coal, oil, and gas, contributing
to further increases in CO2 levels in the atmosphere.
Atmospheric levels of CO2 have increased by more
than 30% since 1700 B.C. [1]. This surge continues
to affect the Earth’s climate. Recently, researchers
predicted that the temperature of major cities across
the world will reach a climate point of no-return over

Address correspondence to Anjana Sarkar, sarkar.anjana@gmail.com; Jyri-Pekka Mikkola, jyri-pekka.mikkola@umu.se

2 Nano Res.
the next 20–30 years, or even sooner in tropical
countries [2]. The sooner we act, the better the climatic
legacy inherited by future generations. Nature has
established its own ways of recycling CO2 via the
carbon cycle. It converts CO2 into various compounds
that support the entire biological system on Earth. It
is extremely important to maintain a balance of the
amount of CO2 in the atmosphere in order to sustain
the eco-geo system. Thus, a permanent solution to the
CO2 problem must involve the transformation of CO2
into other useful or non-toxic compounds. Upgrading
CO2 to reusable hydrocarbon resources would benefit
humans and the environment.
One promising route is artificial photosynthesis,
which can be implemented via photoreduction of CO2
to produce hydrocarbons [3]. During the past few
decades, the capture of CO2 by photocatalytic processes
has attracted attention [4, 8–10]. Since CO2 is a rather
inert and stable compound and its chemical reduction
is challenging, the capture and conversion of CO2
requires high energy input as high temperature and
pressure conditions are typically employed. However,
the photocatalytic process occurs under comparatively
mild conditions with lower energy input, as the reaction
is induced by either solar energy or other light
sources. CO2 does not absorb in either the visible or
ultraviolet (UV) light regions ( = 200–900 nm), hence,
the process requires appropriate photosensitizers.
Several studies have indicated the importance of
photocatalysts in enhancing the efficiency and
selectivity of the photoreaction. Semiconductors such
as titanium dioxide (TiO2), zinc oxide (ZnO), zinc sulfide
(ZnS), hematite (-Fe2O3), tungsten oxide (WO3),
strontium titanate (SrTiO3), cadmium selenide (CdSe),
gallium oxide (Ga2O3), and zirconium dioxide (ZrO2)
are usually used as photocatalysts [4–11]. TiO2 has been
extensively studied with several reports stating that
it is one of the most efficient photocatalysts when
considering cost, stability, and performance, and it
has been frequently applied in CO2 utilization [12–14].
Many studies have shown that CO2 can be reduced
with water vapor or other solvents by photocatalysts
[3–30]. Improvement of activity by nanoscale co-catalyst
materials has also attracted much attention [31–34].
Nanosized semiconductor co-catalysts with different
band structures in reference to TiO2 form hetero-
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junctions with improved optical absorption and
photocharge transfer/separation [35–38]. Anchoring
noble metal nanoparticles on TiO2 photocatalysts also
enhances their activity by trapping electrons on the
metal surface, thus decreasing the recombination
rate of electron–hole pairs [6, 39–44]. Deposition of
semiconductor quantum dots (QDs) onto TiO2 for
photoinduced applications has also proved to be a
good strategy [6]. The conduction band (CB) of QDs,
such as CdSe, aligned on TiO2 becomes more negative
due to electron confinement. This enables the injection
of photo-excited electrons from the QDs into TiO2,
which can subsequently be collected by an electrode
or used to initiate a photocatalytic reaction. Recently,
Wang et al. demonstrated CO2 photoreduction with
water using a CdSe QD-sensitized TiO2 heterostructured
catalyst using Pt as a co-catalyst under visible light
[6]. They suggested that the combination of Pt and
CdSe QDs is required for CO2 photoreduction into
methane under their experimental setup.
In the present study, we report the photoreduction
of CO2 with water using TiO2 nanofiber (NF)-based
photocatalysts under UV light. The effect of metal
nanoparticle (Pt or Pd) and CdSe QD co-catalysts on
the photocatalytic activity of TiO2 NFs is discussed.
Ab initio calculations are also performed, giving an
insight into the photoreduction mechanisms, which
support the experimental results.
2 Results and discussion
The TiO2 NFs were first loaded with 1 wt.% metal
nanoparticles (Pt and Pd) using a wet impregnation
method. These catalysts are referred to as 1%Pt–TiO2
NFs and 1%Pd–TiO2 NFs, respectively. Finally, anchor-
ing of CdSe QDs on the TiO2-based catalysts (pristine
TiO2 NFs, 1%Pt–TiO2 NFs, and 1%Pd–TiO2 NFs) was
achieved. These catalysts are denoted as 1%CdSe–TiO2
NFs, 1%CdSe–1%Pt–TiO2 NFs, and 1%CdSe–1%Pd–
TiO2 NFs.
2.1 Characterization of catalysts
The amount of Pt, Pd, Cd, and Se in the catalysts was
determined by inductively coupled plasma-optical
emission spectrometry (ICP-OES). The results are listed
in Table 1.
Nano Res. 3

The surface chemical composition of the catalysts
was analyzed by X-ray photoelectron spectroscopy
(XPS). The XPS results are summarized in Table 2.
The binding energies (BEs) for both Pt 4f7/2 and Pd 3d5/2
correspond to Pt(0) and Pd(0), respectively, showing
slightly lower values than previously reported, probably
due to the smaller size or elevated electron density on
the metal nanoparticles [45]. In catalysts sensitized
with CdSe QDs, the Cd 3d spectra showed typical
splitting of the Cd 3d core levels into 3d5/2 (404.7 ±
0.4 eV) and 3d3/2 (~411.5 eV) components by spin-orbital
coupling with a splitting magnitude of ~6.7 eV [46].
Interestingly, the Cd 3d spectra are different in
the presence of Pt and Pd nanoparticles. For the
1%CdSe–1%Pt–TiO2 NF catalyst, the Cd 3d5/2 core level
shows the presence of an additional low intensity
peak at 403.3 eV, which most probably corresponds
to (CdOx) [47]. It could be also attributed to the
decomposition of CdSe QDs in the presence of Pt
nanoparticles. Similarly, the Cd 3d spectrum for
1%CdSe–1%Pd–TiO2 NFs shows an additional peak.
However, in the 1%CdSe–1%Pd–TiO2 NF catalyst, the
Cd 3d5/2 peak at ~405 eV almost disappeared and a
corresponding low binding energy peak at 403.6 eV
was more pronounced, as is clearly depicted in Fig. 1.
A similar phenomenon is observed for the Cd 3d3/2
peaks for both catalysts. These results indicate that
CdSe QDs are more stable in the presence of Pt than
Pd nanoparticles.
The size and morphology of the modified TiO2 NFs
were analyzed using transmission electron microscopy
(TEM), high-resolution TEM (HRTEM), scanning
TEM (STEM), and field emission scanning electron
microscopy (FESEM). TEM analysis revealed the size

Table 1 The actual amount of Pd, Pt, Cd, and Se in the samples from ICP-OES analysis
Photocatalyst Pd (mg·g–1) Pt (mg·g–1) Cd (mg·g–1) Se (mg·g–1)
1%Pd–TiO2 NFs 7.7
1%Pt–TiO2 NFs 6.6
1%CdSe–TiO2 NFs 1.4 <1
1%CdSe–1%Pd–TiO2 NFs 7.7 1.4 <1
1%CdSe–1%Pt–TiO2 NFs 6.6 1.4 <1

Table 2 Binding energies and atomic concentrations (at.%) of the TiO2-based catalysts from XPS analysis
1%Pd–TiO2 1%CdSe–TiO2 1%CdSe–1%Pt– 1%CdSe–1%Pd– Peak
TiO2 NFs 1%Pt–TiO2 NFs
NFs NFs TiO2 NFs TiO2 NFs assignment
458.5 eV; 458.8 eV; 458.9 eV; 458.6 eV; 458.5 eV; 458.6 eV; TiO2
Ti 2p3/2
24.98 at.% 20.17 at.% 24.21 at.% 21.35 at.% 18.17 at.% 19.22 at.%
334.5 eV; Pd (0)
335.0 eV; 0.33 at.%
0.63 at.% 335.1 eV;
0.18 at.%
Pd3d5/2 Not detected Not detected Not detected Not detected
336.1 eV; 335.9 eV; Pd (II)
0.25 at.% 0.05 at.%
337.5 eV; 337.1 eV; Pd (II)
0.22 at.% 0.03 at.%
70.7 eV; 0.17 70.5 eV; 0.15
Pt(0)
at.% at.%
Pt4f7/2 Not detected Not detected Not detected Not detected
71.9 eV; 0.05
Pt(II)
at.%
403.6 eV; 403.3 eV;
CdOx
0.02 at.% 0.09 at.%
Cd 3d5/2 Not detected Not detected Not detected
404.4 eV; 405.0 eV; 404.7 eV;
CdSe
0.06 at.% 0.14 at.% 0.03 at.%

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4 Nano Res.

distribution of spherical Pt and Pd nanoparticles to

be highly monodispersed, centered at 2.0 ± 0.5 and
5.0 ± 1.1 nm, respectively (see Fig. S2 in the Electronic
Supplementary Material (ESM)). After anchoring of
the CdSe QDs (2.1–2.3 nm and full width half maximum
(FWHM) = 32 nm (max = 459 nm)), we did not observe
any significant change in the cluster size of the noble
metals. Unfortunately, due to their small size the CdSe
QDs did not exhibit proper contrast in the TEM
images, complicating their characterization. HRTEM
and STEM analyses of these samples gave a better
understanding of their morphology (Fig. 2). HRTEM Figure 1 XPS spectra of the Cd 3d core level for (a) 1%CdSe–
and STEM images clearly show that in the 1%CdSe– TiO2, (b) 1%CdSe–1%Pt–TiO2 NFs, and (c) 1%CdSe –1%Pd–
1%Pd–TiO2 NFs, particles were formed in two different TiO2 NFs.
size ranges; the smaller nanoparticles are less than
1.5 nm in diameter and most of them are ~0.7 nm,
while the larger are in the range of ~5 nm. Due to the
strong background of crystalline TiO2 in the HRTEM
images, which makes it difficult to recognize the
borders of the nanoparticles (especially the smaller
ones), it is more reliable to use the STEM images for
actual size measurements. For 1%CdSe–1%Pt–TiO2,
a more homogeneous particle size distribution was
observed. Here, particles are slightly bigger and those
with diameters of below 1 nm are rarely observed.
Although it is not possible to distinguish different types
of nanoparticles based solely on electron microscopy,
it seems plausible to suggest that CdSe QDs are
represented by the small nanoparticles in the range
of 0.7–1.5 nm, while the larger nanoparticles in the
1%CdSe–1%Pd–TiO2 NF samples are Pd. The fact that
some particles with the same size display differences
in contrast in the STEM image of the 1%CdSe–1%Pt– Figure 2 HRTEM images of (a) 1%CdSe–1%Pd–TiO2 NFs and
TiO2 NFs clearly supports co-existence of different (c) 1%CdSe–1%Pt–TiO2 NFs, and STEM images of (b) 1%CdSe–
types of nanoparticles, where a higher contrast is 1%Pd–TiO2 NFs and (d) 1% CdSe–1%Pt–TiO2 NFs.
expected for Pt particles due to their significantly higher
mass. Nevertheless, the small size of the particles and which correspond to the characteristic anatase phase
the charging effect in the TiO2 rods make it very of TiO2 NFs.
difficult to perform chemical mapping, which renders
2.2 Photocatalytic reduction of CO2
unambiguous assignment impossible. It is not there-
fore possible to identify particular nanoparticles. The photocatalytic reduction of CO2 with water into
Topographical images of the samples obtained by hydrocarbons using TiO2-based photocatalysts has
FESEM are displayed in Fig. S5 in the ESM. been widely studied [7], revealing that the reduction
The Raman spectra (see Fig. S2 in the ESM) of the mechanism is mainly initiated by the formation
samples showed four distinct peaks detected at 147 of two important radicals: •H (hydrogen radical)
−
(Eg), 399 (B1g), 517 (A1g + B1g), and 639 cm−1 (Eg), and •CO2 (carbon dioxide anion radical). Researchers

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Nano Res.
have reported a diverse range of products formed upon
photoreduction of CO2, such as methane, methanol,
carbon monoxide, hydrogen, methyl formate, formic
acid, ethylene, ethanol, and formaldehyde [48].
The CO2 photoreduction performance of our TiO2-
based catalysts (i.e. pristine TiO2 NFs, 1%Pt–TiO2 NFs,
1%Pd–TiO2 NFs, 1%CdSe–TiO2 NFs, 1%CdSe–1%Pt–
TiO2 NFs, 1%CdSe–1%Pd–TiO2 NFs) was tested under
UV-B light. It has been reported that metal clusters
decorated on TiO2 act as electron trapping centers,
leading to charge separation due to newly formed
Schottky barriers at the metal/semiconductor interface
[49]. Upon light irradiation, electrons and holes are
generated. The electrons formed migrate to the metal
surface and their back injection is inhibited by the
Schottky barriers, thus limiting recombination. The
electron rich metal surface acts as a reduction site,
while oxidation takes place at the photogenerated
holes. Consequently, introducing Pt or Pd can influence
the CO2 reduction reaction rate. In addition, anchoring
CdSe QDs affects the electron distribution on the TiO2
surface [38]. The CB of bulk CdSe exhibits a slightly
negative potential compared to TiO2. However, due
to quantum confinement, the conduction band of CdSe
QDs shifts to a more negative potential, enabling
electron injection into TiO2 [38]. The electron transfer
rate is size-dependent and is enhanced as the size of
the QDs decreases. The time scale for electron transfer
from excited CdSe QDs to TiO2 has been reported to be
around 2–50 ps, which facilitates the photocatalytic
activity of TiO2 for reduction reactions [6]. Additionally,
CdSe–TiO2 heterostructures are known to harvest
visible light energy and facilitate photon-induced
Figure 3 Products formed for each catalyst (A = methanol, B = methyl formate, C = formic acid, D = other low yield products).
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5
reactions at lower energies [38, 50]. Due to the low
energy of UV-B lamps, it is possible to monitor the
formation of initial products during the reaction. In
all cases, under our experimental conditions, liquid
products condensed in the cold trap revealed the for-
mation of methanol, formic acid, and methyl formate
as the major products, as well as other hydrocarbons
in low yields. Figure 3 shows the products (normalized
area%) produced for each catalyst system. Formic
acid was the major product with 1%Pt–TiO2 NFs, and
low yields of methanol and methyl formate were also
obtained. On the other hand, 1%Pd–TiO2 NFs formed
methanol, formic acid, and methyl formate as the
major products. In the case of methanol formation,
our results agree with those previously reported in
the literature; namely, Pd-decorated TiO2 nanoparticles
are preferred over Pt, as suggested by Ishitani et al. [51].
For 1%CdSe–1%Pt–TiO2 NFs, the presence of CdSe
QDs drastically enhances not only the formation of
methanol, but also improves overall product formation.
The rate of reaction increases, thus increasing methanol
formation. Formation of acetic acid and ethanol in
very low yields was also observed. Meanwhile, in the
case of 1%CdSe–1%Pd–TiO2 NFs, the formation of
methanol decreased and yield of formic acid increased
approximately 3-fold. The decrease in photoactivity
towards methanol formation can be attributed to the
instability of CdSe QDs in the presence of Pd metal, as
mentioned earlier. Under our experimental conditions,
the combination of Pt and CdSe QDs was found to be
the most efficient for methanol formation. Table 3
summarizes the yields of methanol and methyl formate
for each catalyst.
Research
6 Nano Res.

Table 3 Methanol and methyl formate yields from photoreduction that there is no general consensus on the reaction
of CO2 with water using TiO2-based catalysts mechanism, but most studies have indicated the
Methanol Methyl formate existence of two reaction pathways, depending upon
Photocatalyst concentration concentration
the rates of CO2 hydrogenation and deoxygenation
(ppm·g–1·h–1) (ppm·g–1·h–1)
[7]. If CO2 hydrogenation is prevalent, the formation
1%Pt–TiO2 NFs 1.61 ± 0.05 11.62 ± 0.5
of formic acid, formaldehyde, and finally methanol
1%CdSe–1%Pt–
90.22 ± 0.7 225.4 ± 1.0 will be observed. Alternately, carbon monoxide and
TiO2 NFs
methane are formed when deoxygenation is faster
1%Pd–TiO2 NFs 14.21 ± 0.04 14.79 ± 0.01
than hydrogen addition. On the basis of this infor-
1%CdSe–1%Pd–
4.63 ± 0.04 13.11 ± 0.3 mation, we propose that under our experimental
TiO2 NFs
conditions CO2 photoreduction with water over TiO2
1%TiO2 NFs 3.07 ± 0.05 53.42 ± 0.01
NFs mainly occurs via hydrogenation reactions, as
the intermediates and products are consistent with
Sensitizing TiO2 NFs with semiconductor CdSe QDs
those species observed experimentally (methanol,
not only enhances the yield, but can also influence the
formic acid, and methyl formate). The proposed reaction
selectivity of the reaction. It is important to mention
pathways are stated in Eqs. (1)–(12), which have been
that CdSe–TiO2 NFs did not show any influence on
previously observed in similar studies over a diverse
product yield compared to pristine TiO2 NFs. These
range of surfaces [52, 53].
series of experiments clearly suggest a synergy between
the metal (Pt or Pd) nanoparticles and CdSe QDs over TiO2 + he– (CB) + h+ (VB) (1)
TiO2 nanofibers and demonstrated their enhanced
H2O+ h  OH + H
+ +
(2)
photocatalytic activity towards CO2 reduction. Blank
experiments were also carried out to ensure that the H + e  H
+ –
(3)
products formed are solely due to photoreduction of CO2(g)  CO2 (4)
CO2. Under similar experimental conditions, blank
filter paper without catalyst was illuminated, and CO2 + H HCOO* (5)
experiments in the dark with catalyst were also carried HCOO + H HCOOH (formic acid) (6)
out. Furthermore, an additional blank test was
HCOOH + H H2COOH (7)
performed using nitrogen gas instead of CO2. Hydro-
carbons were not detected in any of these cases, and H2COOH  CH2O+OH (8)
only water was condensed in the cold trap. Under
CH2O + OH + H CH2O + H2O(g) (9)
our experimental conditions, no detectable amount of
gaseous products was observed. CH2O + H CH3O (10)
CH3O+ H  CH3OH(g) (methanol) (11)
2.3 Theoretical description of CO2 reduction reaction
on TiO2 HCOOH + CH3OH  H2O + HCOOCH3 (12)
(methyl formate)
In the previous sections, we described our experimental
observations for the CO2 photoreduction process over where  indicates adsorbed species, and hrepresents
TiO2 NFs, however, the influence of Pt and Pd is still a photon of appropriate wavelength. Here the first
unclear. We complemented our experimental observa- three reactions (Eqs. (1)–(3)) involve the absorption
−
tions with theoretical studies using DFT. Thus, we of a photon, creating an electron (e )–hole (h+) pair
performed diverse calculations to study the reaction in the CB and valence band (VB), respectively. This
mechanism and increase understanding of the observed electron–hole pair will further react with previously
results. As previously mentioned, CO2 reduction is a adsorbed water molecules, producing OH and H
complex reaction, and a vast number of mechanisms intermediates (Eqs. (2) and (3)). The following reactions
have been proposed [7]. It should be mentioned in Eqs. (4)–(12) are based on a fast hydrogenation

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Nano Res. 7

model of the CO2 molecule over the TiO2 surface,
where the consecutive addition of 6 H atoms (H
intermediates) generates a diverse range of organic
compounds, similar to those observed experimentally.
We have only calculated reaction energy (ΔER) during
CO2 reduction, as shown in Eqs. (4)–(11), since these
reactions are specifically involved in the hydrogenation
of the CO2 molecule. The results are depicted in Fig. 4.
Figure 4(a) illustrates the reaction pathway on the
anatase TiO2 (101) surface based on a fast hydro-
genation mechanism. As indicated in Eq. (4), the
reaction is initiated by the adsorption of a CO2
molecule over a 5-fold coordinated Ti atom (Ti5f, see
also Fig. S4.1(a) in the ESM). It is possible to observe
that the CO2 molecule is preferentially adsorbed on a
tilted configuration, facing one O atom directly to the
Ti5f with a CO2–Ti5f distance equal to 2.6 Å. These
results are in good agreement with those reported in
previous studies [53]. The following steps involve
hydrogenation reactions, except for that shown in
Eq. (8), where the reaction involves the dissociation of
a H2COOH intermediate into formaldehyde (CH2O)
and hydroxyl (OH). Then, by further addition of H
intermediates, the reaction proceeds until methanol
is obtained (CH3OH). Finally, Eq. (12) shows the
condensation reaction of methanol and formic acid to
produce methyl formate. Since it does not involve a
hydrogenation step, it is not included in Fig. 4(b). It is
important to point out that here we consider the
photochemical reactions (Eqs. (1)–(3)) as the source of
adsorbed hydrogen (H), thus accumulating OH
intermediates at the TiO2 surface that could deactivate
the catalyst, as observed experimentally.
The calculated reaction energy for CO2 reduction is
depicted in Fig. 4(b). As observed, CO2 adsorption at
a Ti5f site on the anatase TiO2 (101) surface exhibits a
stable configuration with absorption energy (ΔEads)
equal to −0.17 eV, in good agreement with previous
reports [54, 55]. The first hydrogenation step (Eq. (5))
results in a transition state of relatively high energy
(ΔER5 = 2.1 eV) that most probably rapidly reacts to
form the first stable intermediate, formic acid (Eq. (6)).
As observed in Fig. 4(b), the hydrogenation of formic
acid (Eq. (7)) exhibits the largest ΔER, equal to 2.4 eV,
and is thus considered the rate-limiting step. It is
important to note that, due to the large amount of
energy required for formic acid hydrogenation to
proceed, formic acid could actually desorb as a by-
product. However, if the larger adsorption energy of
formic acid is observed, the opportunity of continuing
CO2 reduction is increased substantially. These results
are in excellent agreement with our experimental
observations, where a considerable amount of formic
acid is observed during CO2 reduction.
The driving force for CO2 photoreduction over TiO2
is assumed to be the difference between the redox
potential corresponding to the VB of TiO2 at the
surface under irradiation (~3.2 eV) [56]. According to
our calculations, illumination with light provides the
potential needed for the reaction to proceed and,
therefore, photoreduction of CO2 over anatase TiO2
(101) is thermodynamically favored. Once the hydro-
genation of formic acid has been achieved, the
following chemical reactions (Eqs. (8)–(11)) proceed

Figure 4 (a) Geometrically optimized structures of the diverse range of intermediates along the CO2 reduction pathway performed over
the anatase TiO2 (101) surface. The molecules and intermediates inside the circles indicate additions to the system. (b) ΔER during CO2
reduction, as described in Eqs. (4)–(11). In this case, the limiting step is the hydrogenation of formic acid (Eq. (7)). * indicates adsorbed
species. Color code in (a): blue (H), yellow (C), red (O), and gray (Ti).

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8 Nano Res.
smoothly due their smaller ΔER. Similarly, the relatively
low ΔER for the reaction in Eq. (10) could explain
why formaldehyde is not observed experimentally,
since its low hydrogenation energy (ΔER10 = 1.1 eV)
facilitates methanol production. Finally, the condensa-
tion reaction of methanol and formic acid (Eq. (12))
exhibits ΔER12 = −0.14 eV, indicating that this reaction
is also favored.
Identification of the rate-limiting step permits
deeper investigation into the effect of Pt and Pd nano-
particles on the CO2 photoreduction process. As stated
previously, metals such as Pt or Pd act as electron
traps, modifying the net charge of TiO2. Considering
the current limitations and computational costs of
actual ab initio approaches, we implicitly included the
effect of Pt and Pd on the TiO2 surface by varying the
total charge of the system. The net charge on anatase
TiO2 (101) was modified from −0.4 to + 0.4 e–, as
suggested in previous publications [57]. We then
calculated the change in adsorption energy of formic
FA
acid (ΔEads ). Our results show that the adsorption
energy changes linearly with the net charge of the
system (see Fig. S4.3 in the ESM), where a positively
FA
charged surface exhibits a stronger ΔEads by ~0.12 eV
at +0.4 e– when compared with neutral systems. Thus,
improving the interaction of formic acid may benefit
hydrogenation. On the other hand, a negatively
FA
charged system exhibits a weaker ΔEads (a decrease of
~0.12 eV at −0.4 e–), indicating faster desorption of
formic acid and inhibition of further reduction reactions.
Similar results were observed when the rutile TiO2
(110) surface was used as the catalyst, see Fig. S4.3 in
the ESM. These results agree qualitatively with our
experimental observations, where the presence of
metal nanoparticles generates a slightly positive TiO2
surface, therefore increasing the adsorption energy of
formic acid and improving CO2 reduction. We also
FA
observed a larger ΔEads on anatase TiO2 (101) (−0.87 eV)
than on rutile TiO2 (101) (−0.63 eV), which suggests
that anatase TiO2 (101) might act as a better catalyst for
formic acid hydrogenation and subsequent production
of methanol and other related products.
3 Conclusions
In summary, photocatalytic reduction of CO2 using
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modified TiO2 NFs was demonstrated under a low
energy UV-B light source. TiO2 NFs decorated with
Pt and Pd nanoparticles lead to the formation of similar
products, but exhibited selectivity towards different
products. Decorating TiO2 NFs with Pd metal is
preferred over Pt for methanol formation. Anchoring
CdSe QDs on Pt-decorated TiO2 NFs results in a drastic
enhancement in methanol formation and also enhances
the overall yield of products. Nevertheless, CdSe
QDs anchored on Pd-decorated TiO2 NFs exhibited
selectivity towards formic acid and decreased the
yield of methanol due to decomposition of CdSe QDs
in the presence of Pd nanoparticles. The synergistic
effect of CdSe QDs and Pt was found to be optimal
for methanol formation under our experimental con-
ditions. The photoreduction of CO2 is proposed to take
place via a hydrogenation pathway, forming various
products. Modified TiO2 displayed enhanced activity
towards CO2 photoreduction, which was demonstrated
experimentally and using DFT calculations.
4 Experimental
4.1 Materials
Titanium dioxide (Sigma-Aldrich, <25 nm anatase,
99.7%) powder was utilized as received. Water purified
through a Millipore system was used. Precursors Pt-
and Pd-acetylacetonate were also received from Sigma
Aldrich, as well as CdSe QDs 2.1–2.3 nm in size.
4.2 Catalyst synthesis
Synthesis of sodium titanate (Na2TiyO2y+1) NFs was
achieved via hydrothermal treatment of anatase TiO2
in 10 M NaOH aqueous solution for 24 h at 175 °C
[49]. Furthermore, the resulting material was treated
with 0.1 M hydrochloric acid to exchange sodium
ions with protons in the NFs. The product was
washed and dried at 70 °C, followed by calcination at
600 °C in air for 12 h to form TiO2 NFs.
Loading of Pt and Pd nanoparticles on TiO2 nano-
wires was achieved by means of a wet impregnation
method using Pt- and Pd-acetylacetonate precursors,
respectively. In a typical procedure, 1 wt.% precursor
salt was dissolved in 50 mL acetone (VWR) and mixed
with 1.0 g TiO2 NFs. The suspension was sonicated
Nano Res.
for 10 min followed by overnight stirring. Acetone was
evaporated under a constant nitrogen flow at ~80 °C.
The dried samples were calcined in air at 500 °C for
4 h and then reduced in a H2 gas (99.995%, AGA) flow
at 500 °C for 4 h to obtain TiO2 NFs with 1 wt.% metal
loading. The catalysts decorated with 1 wt.% Pt and
Pd are referred to as 1%Pt–TiO2 NFs and 1%Pd–TiO2
NFs, respectively.
Anchoring of 1 wt.% CdSe QDs (2.1–2.3 nm) onto
the TiO2-based catalysts was obtained by first preci-
pitating commercial CdSe QDs twice with methanol.
The CdSe QDs were then dissolved in dichloromethane
and added to the TiO2-based catalysts (i.e. pristine NFs,
1%Pt–TiO2 NFs, and 1%Pd–TiO2 NFs). The catalysts
were dried after evaporation of dichloromethane and
further annealed at 600 °C for 30 min under N2 gas
(99.9%, AGA) to desorb the organic capping molecules.
For the TiO2 catalysts decorated with Pt and Pd, the
metal nanoparticles were first loaded and then CdSe
QDs were anchored onto them. These materials are
denoted as 1%CdSe–1%Pt–TiO2 NFs and 1%CdSe–
1%Pd–TiO2 NFs, respectively, while TiO2 NFs anchored
with CdSe QDs are labeled as 1%CdSe–TiO2 NFs.
4.3 Structural characterization
The actual amount of Pd, Pt, Cd, and Se loaded in the
catalysts was quantified on a Perkin Elmer Optima
5300 DV inductively coupled plasma-optical emission
spectrometer, with which either an axial or radial
viewing mode of the plasma is possible. Each sample
was digested using an appropriate procedure (see the
ESM). The surface chemical composition was studied
using XPS (Kratos Axis Ultra DLD electron spectro-
meter, monochromated Al K source operated at
150 W, charge neutralizer, analyzing area 0.3 mm ×
0.7 mm).
The structures of the materials were characterized
using TEM (EFTEM, Leo 912 Omega, 120 kV, LaB6
filament), HRTEM (JEM-2100F at 200 keV), STEM
(JEM-2100F at 200 keV in STEM mode with angular
dark-field detector), and FESEM (Zeiss ULTRA plus
with an acceleration voltage of 5 kV). Raman spectra
were recorded over the range 50–1,200 cm–1 on a
Horiba Jobin Yvon LabRAM HR800 equipped with a
confocal Raman BX41 microscope with an excitation
www.theNanoResearch.com∣www.Springer.com/journal/12274 | Nano
9
laser beam wavelength of 487.99 nm. A proper con-
centration of sample was loaded on the conductive
carbon tape for analysis.
4.4 Photocatalytic reaction
The activity of each catalyst was tested by performing
photocatalytic CO2 reduction experiments under UV
light. Typically, 100–140 mg catalyst was dispersed in
10 mL deionized water and filtered through 90 mm
polycarbonate membranes of 0.2 μm pore size. The
filter paper and catalyst were dried at room tem-
perature overnight before the photocatalytic activity
was tested.
The reaction chamber was set up as follows: The
catalyst on the filter paper was loaded in a stainless
steel reaction chamber containing an inlet and outlet
for gas. A circular stainless steel ring was placed on
the filter paper to hold it in place. Finally, a quartz
window sealed with an O-ring was installed to allow
light to fall on the catalyst. (For a schematic illustration
and photograph of the reactor setup, see the ESM,
Figs. S3(a) and S3(b).)
CO2 gas was passed through a bubbler containing
60 mL MilliQ water (maintained at 25 °C) before
entering the reactor (maintained at 30 °C). The outlet of
the reactor was connected to a cold trap, maintained
at −6 °C, which was further connected to a micro gas
chromatograph equipped with a thermal conductivity
detector (TCD). Before assembling the reactor, CO2
was first bubbled through the bubbler at a rate of
10 mL·min−1 overnight for saturation. Once the filter
paper containing the catalyst was fixed in the reaction
chamber, the reactor was assembled. The reactor was
closed tightly and flushed with CO2-saturated water
for 1 h at a rate of 50 mL·min−1 to equilibrate the entire
reactor. Then, the flow was reduced to 5 mL·min−1
and allowed to stabilize for 30 min before irradiation.
Throughout the reaction, the flow was maintained
at 5 mL·min−1. Four 6W UV-B lamps (Sankyo Denki
G6T5E, Japan, FWHM = 40 nm (λmax = 306 nm))
corresponding to a total intensity of ~2 mW·cm−2 were
used for irradiation. The reaction was monitored for
5 h. Every hour a gas sample was injected into the
gas chromatograph equipped with TCD. The liquid
product condensed in the cold trap was analyzed
Research
10
after 5 h by a gas chromatograph (Agilent) equipped
with a flame ionization detector (FID). We observed
that beyond 5 h, the activity of the catalyst gradually
declined.
4.5 Theoretical methods
Ab initio calculations were performed by density
functional theory (DFT) [58] using the generalized
gradient approximation and the model of Perdew,
Burke, and Ernzerhof [59] as the exchange-correlation
term. The electronic structure was solved using
Vanderbilt ultrasoft pseudopotentials [60]. The kinetic
energy cutoffs for wave functions were set to 50 and
500 Ry for the charge density. A Marzari–Vanderbilt
[61] smearing of 0.02 Ry was used to aid convergence.
Integration of the Brillouin zone was carried out
using an 8 × 8 × 1 Monkhorst–Pack grid [62]. The DFT
computations were performed using the Quantum
Espresso (QE) code [63].
Non-spin polarized calculations were performed to
describe the CO2 reduction reaction over two different
TiO2 phases (anatase and rutile). The bulk lattice
parameters of anatase TiO2 (space group I41/amd)
obtained by DFT as a = b = 3.793 Å and c = 9.647 Å
were in good agreement with the experimental data
[64]. For rutile TiO2, the obtained lattice parameters
were equal to a = b = 4.5922 Å and c = 2.9574 Å; these
values are also consistent with the experimental lattice
parameters [65]. The resulting electronic band gaps
for the anatase and rutile TiO2 phases were 1.94
and 1.85 eV, respectively, consistent with previously
reported values (1.88 eV) using similar DFT methods
[66]. The electronic properties and lattice parameters
of both bulk anatase and rutile TiO2 were obtained
using an 8 × 8 × 8 Monkhorst–Pack grid for integrating
the Brillouin zone.
An anatase TiO2 (101) surface with a (2 × 1) super
cell containing 6 TiO2 slabs was used as the catalytic
surface. The chemical reaction on anatase TiO2 (101)
was initiated by adsorption of a CO2 molecule on
a 5-fold coordinate Ti atom (Ti5f), followed by the
consecutive addition of diverse photon electron (H+ +
e−) pairs. During geometric optimization, the bottom
three layers were kept frozen at their bulk optimized
positions, while the top three slabs and adsorbents
| www.editorialmanager.com/nare/default.asp
Nano Res.
were allowed to move until all components of the
ionic forces were less than 0.03 eV·Å−1. The ΔEads of
adsorbates is defined as ΔEads = Eadsorbate/TiO2 – Eadsorbate –
ETiO2, and the ΔER of intermediates was computed as
the energy difference of each elementary reaction
during CO2 reduction. The description for rutile TiO2
systems can be found in the ESM.
Acknowledgements
The theoretical simulations were performed on resour-
ces provided by the Swedish National Infrastructure
for Computing (SNIC) at the High Performance
Computing Center North (HPC2N). The Authors also
acknowledge Kempe Foundations, the Bio4Enenrgy
programme and the Artificial Leaf project under
auspices of Knut & Alice Wallenberg Foundation for
funding provided.
Electronic Supplementary Material: Supplementary
material (characterization, TEM images and Raman
spectra of modified TiO2 samples; schematic illustration
and a photograph of the reactor setup; theoretical
description of rutile TiO2 system) is available in the
online version of this article at http://dx.doi.org/
10.1007/s12274-016-1087-9.
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