Applied Surface Science 536 (2021) 147843

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Applied Surface Science

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

Highlighting the importance of optimal defect density through band T

structure and photocatalytic studies
Dileep Maarisetty , Janaki Komanduru, Saroj Sundar Baral
⁎

Department of Chemical Engineering, BITS Pilani, K K Birla Goa Campus, Goa 403726, India

ARTICLE INFO ABSTRACT

Keywords: Interface energetics plays a substantial role in the efficient charge transfer between semiconductor materials.
Dipoles The concentration of donors or acceptors at the junction determines the direction of charge flow. In this work,
Fermi level CdS was doped to TiO2 progressively to explore the electronic structure modification and its associated effect on
Work function charge dynamics. Results suggest that loss of dipole moment with increasing CdS concentration; causing the
Photocatalytic degradation
work function (WF) values of the composites to increase. The dipole-dipole repulsion occurs as a consequence of
Oxygen reduction reaction
Optoelectronics
a decrease in Cd-Cd distance at higher doping concentrations. When present in optimal concentration, the
surface dipoles besides aiding in efficient charge transfer, accelerate the chemisorption process at corrugated
surfaces. Apart from the optoelectronics, efforts have been made to understand the hindering role of higher
defect concentration in triggering the thermodynamically favored undesired photocatalytic reactions, which
drastically reduce the quantum yield of the process. This work may provide some insights to tune the work
function (WF) values in applications that involve optoelectronic and photocatalytic studies.

1. Introduction modulating the interfacial properties (favoring the dissociative ad-

Reports from photocatalysis research prove the inconsistency in
terms of quantum yield, even when the same composition of photo-
catalysts are compared. A huge number of variables influencing it such
as type of precursors, synthesis method, doping concentration and also
heating treatments lead to varying results. The major contributor con-
undrum continues but emphasizes the importance of looking this pro-
blem at a molecular level. Takanabe et al., reported that defect density,
charge carrier concentration and interfacial properties as three strong
influencing candidates for enhancing the photocatalytic efficiencies [1].
Interestingly, carrier concentration and interfacial properties are con-
trolled by the defects thereby highlighting the key role of surface de-
fects in photocatalytsis. Our previous work served as a complementary
to this, where defect-rich catalyst exhibited higher photocatalytic ac-
tivity compared to the same composite (but with lesser defects), in spite
of having 6–7 times higher surface area than the former [2]. Recently, a
review article elaborately explained the role of defects in boosting the
photocatalytic activity on a fundamental level and readers are en-
couraged to go through it [3]. Although strategies like facet, phase,
morphology control, charge transfer schemes were reported [4], defect
engineering serves as an effective plan of action for enhancing the
photocatalytic efficiency. Defect-engineering displays potential in
sorption), electronic properties and regulating atom coordination
number as understood from theoretical studies [5]. Recently an ex-
tension in photocatalytic applications such as CO2 reduction [6], or-
ganic synthesis [7] and nitrogen fixation [8] have taken a new leap in
defect engineering and achieved tremendous results. So far many re-
searchers have worked on CdS-TiO2 as photocatalysts and confirmed
their superior performance than their individual photocatalytic per-
formance under visible light [9]. Numerous studies have reported the
varying concentration of dopants and its effect on bandgap [10], re-
combination and photocatalytic activity [11] yet the underlying rea-
sons were not fully studied [12]. A systematic approach to this can be
achieved by considering the acceptor or donor levels at the interface/
junction (attributed to doping) between two semiconductors that dic-
tate the electron transfer [13]. The decrease in work function values,
particularly, at the interface between two metal oxides, can be reasoned
by band bending due to the surface dipole moments; induced by de-
fects. However, this is not straight forward as one may think, and
deeper understanding of the relationship between dopant concentra-
tions and work function is required to come to a proper conclusion
[14].
Also, chemical and structural variations can account for the change
in work function values such as transformation from Ti+4 to Ti+3 [15].

⁎
Corresponding author.
E-mail address: dileepnaidu59@gmail.com (D. Maarisetty).

https://doi.org/10.1016/j.apsusc.2020.147843
Received 2 March 2020; Received in revised form 24 August 2020; Accepted 5 September 2020
Available online 11 September 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
D. Maarisetty, et al. Applied Surface Science 536 (2021) 147843

a b

c d
CdS Anatase (101)

TiO2

Fig. 1. (a) XRD patterns of composite catalysts (b) Crystallite size changes in composites after doping CdS (c) TEM image depicting Cd clusters on TiO2 nano particles
(R4) (d) SAED image of R4 confirming crystallinity (no lattice distortion) after CdS doping.

Few reports also claim the underperformance of photocatalysts due to
excessive defect density by creating more recombination centers in the
forbidden gap [3]. An optimized concentration of these surface defects
is very important, which would otherwise favor the undesired back-
ward reactions and account for decreased photocatalytic efficiency
[16]. Recently, multi-component ZnxCd1−xS and ZnIn2S4 have received
considerable attention recently in the field of photocatalysis owing to
moderate bandgaps [17]. An efficient separation of photo-excited
charge carriers by surface dipoles was reported due to the sulfur va-
cancies and interstitials [18], the readers are recommended to go
through it.. Although co-catalysts decrease the energy offset to avoid
recombination, higher dopant concentrations enhance the defect den-
sity. A controlled amount of S-vacancies for optimum photocatalytic
performance was reported where ZnS structures exhibited a better
photo-stability [19]. In this work, dipoles resulted from the defects
were comprehensively studied at the heterojunction; as dipole moment
ensures smooth flow of electrons. With Photocatalysis having numerous
parameters that decide the overall efficiency, Takanabe in his work
emphasized the importance of interface properties along with carrier
concentration, mass transfer and defect density [1]. Interestingly, three
out of four aspects (excepting mass transfer) in the above mentioned
aspects form connection to defects. Hence, it can be understood that
defect engineering holds an important place in modifying the optoe-
lectronic properties, interfacial contact and dissociative study [3]. By
considering their importance, defect induced surface dipoles and their
consequential effect on surface potentials investigated by systematically
increasing their concentration and validating through various char-
acterization tools and photocatalytic studies.
2. Materials and methods
2.1. Material synthesis
All chemicals used during the preparation were of analytical grade.
Ti(OBu)4 and CdSO4 were used as precursors for TiO2-CdS composites
where ethanol served as a solvent. Appropriate amounts of Ti(OBu)4
and CdSO4 were added dropwise and stirred for 1 h. The reaction
system was transferred to a hydrothermal reactor, which was operated
at 200 °C. The precipitate was rinsed with water and dried in the oven
at 80 °C. The obtained product was heated at 450 0C for 3 h to remove
the organics and improve the crystallization of the material. The com-
posites were synthesized at different Cd/Ti weight ratios by following
identical procedure. Hereafter, the composites with varying Cd/Ti ra-
tios (weight) such as 0.1, 0.3, 0.5 and 0.7 are denoted as R1, R2, R3 and
R4 respectively.
2.2. Photocatalytic experiments
The photocatalytic activity was tested in a 100 ml reaction system
(20 ppm MB + catalyst). To ensure adsorption–desorption equilibrium,
0.05 g catalyst was dispersed into a 20 ppm MB and allowed to stir for
1 h under dark conditions. Followed by this, photocatalytic experiments
were conducted under sunlight. Samples were drawn from the reaction
system at periodic intervals (30 min) for further analysis. The con-
centration of MB was determined using UV–Vis spectrophotometer (UV-
3000, Lab India) at an absorption wavelength of 668 nm.
2.3. Characterization

Morphological studies were carried out by using the field emission

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D. Maarisetty, et al. Applied Surface Science 536 (2021) 147843

scanning electron microscope (FESEM). Bandgap studies were con-

ducted using UV–visible diffuse reflectance spectra (UV-DRS) in a wa-
velength range of 200–800 nm (Shimadzu, Japan). The extent of charge
recombination after photo-excitation (ƛ=325 nm) was investigated
with photoluminescence (PL) spectra, obtained from fluorescence
spectrophotometer (Perkin Elmer-LS-55). Surface properties and work
function of the catalysts were determined by X-ray photoelectron
spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS)
respectively in PHI 5000 Versa Probe-II (K alpha from Thermo Fischer
Scientific instruments, UK). For XPS analysis, samples were initially
dispersed in ethanol and drop casted on a silicon wafer. In the next step,
the sample was loaded in a lock chamber where vacuum was main-
tained until the value reached 10−7 mbar and then shifted to the
analysis chamber. C 1 s peak was taken as a reference point and flood
gun was employed to neutralize the charge effect. Electron spin re-
sonance (ESR) spectra were recorded using ESR-JEOL Japan (X-band).

3. Results and discussion

Fig.2. Recombination study at an excitation wavelength of 532 nm (PL
3.1. Impact of crystallographic modifications on the electronic structure spectra).

The change in optoelectronic properties and charge transfer be-

tween metal oxide and metal sulfide in a composite are dependent on
crystallographic modifications resulting from the dopant atoms. Peaks
at 28.20, 24.80, and 47.9° (Fig. 1a) correspond to (1 0 1), (1 0 0), and
(1 0 3) planes of CdS whereas 25.20, 37.80, 54.10 are associated to the
(1 0 1), (1 0 3), (1 0 5) planes of anatase TiO2 respectively [20]. Fig. 1b
shows the drastic change in crystallite size of composites in comparison
to pristine TiO2. This decrease in intensity and simultaneous peak
broadening suggest that Cd clusters are restricted (Fig. 1c) at grain
boundaries and result in inhibition of crystal growth [2]. Here, it should
be noted that since Cd+2 ionic radius (0.097 nm) is too big to enter into
Ti+4 (0.068 nm) lattice, the possibility of Cd+2 entry is ruled out. This
can be confirmed from SAED (selected area electron diffraction) images
of R4 (highest Cd doped sample) where CdS doping did not account for
any lattice distortions or amorphous nature in TiO2 lattice. However, Ti
(IV) ions penetrated into Cd(II) lattice to account for drastic changes in
the absorption spectra and electronic properties of the. In this case, it
should be noted that Cd being group-II acceptor becomes the host atom.
This ensures a positive charge on Ti and acts as electron traps. These Ti
ions are neutralized by electron entrapment around its vicinity by at-
tractive coulombic potential well.
These vacancies and traps prolongs the lifetime of electrons and
holes [21]. Owing to lower energy requirement for electron excitation
from defect states to conduction band, enhanced light absorption can be
expected in the composites (absorption tail up-shift in visible and NIR).
PL spectra of the samples were recorded for TiO2, CdS and the com-
posites (of different compositions). As observed in Fig. 2, the band-band
recombination in the composites has drastically decreased due to
charge transfer between the catalysts. Since photocatalytic experiments
were conducted under sunlight, the excitation was done in the visible
range (532 nm). R2 exhibits the least recombination due to efficient
charge separation while the increased PL intensity at higher dopant
concentrations is attributed to resistance to charge flow at the junction
that ultimately decrease the lifetime of charge carriers; favoring band-
band recombination [22].
Fig.3. (a) UPS spectra of catalysts, (b) Variation of work function values with
doping concentration.
3.2. Dipole moment and dopant concentration

Furthermore, UPS measurements were conducted to determine the
WF values of as-synthesized catalysts. From the experimental results
obtained in this study, the work function (WF) values of TiO2 and CdS
are 6.1 and 3.43 eV respectively. The composites behaved differently as
compared to their pure compounds and opened an avenue for the dis-
cussion into material aspects. The WF values of R1, R2, R3 and R4 cal-
culated from equation ϕs = hυ–Esc [23] are 4.96, 4.86, 6.42 and
7.88 eV (Fig. 3(a)) respectively and the variation of WF with CdS
doping can be understood from Fig. 3(b). Generally, whenever two
dissimilar semiconductors are brought into contact, an electric built-in
field (due to WF difference) is formed at the junction causing the
electron flow from one to another till their Fermi levels are equilibrated
[24]. Since the Fermi level of CdS is higher (WF = 3.43 eV), the
electron flows from CdS to TiO2 until a new equilibrium value is

3
D. Maarisetty, et al.
established between them. Typically, the new equilibrium value that
was attained from this charge transfer falls between 3.43 and 6.1 eV. As
a result, CdS acquires positive charge while TiO2 forms a negative
charge on its side. The differences in charges at the interface cause a
band bending, which additionally hinders the electron flow from CB of
CdS to TiO2 CB. This coulombic repulsion prolongs the carrier life time
[25]; as reflected from PL spectra (Fig. 2). It is noteworthy to under-
stand that this mode of charge transfer (TiO2 CB to CdS VB) not only
provides the spatial separation of charge carriers but also drives the
photocatalytic reactions due to the enhanced redox potentials. Few
reports claim the initial decrease and sudden increase of WF values in
other composites [1326]. However, there are no explanations why
these materials behave in such a way.
The most striking consideration about WF is the discontinuity of the
surface that causes atomic reconstruction (charge redistribution) to give
rise to two different situations. First, electron spilling normally to the
surface to form a negative dipole layer. Second, the contraction of
electron charge clouds occurs to produce a positive dipole [15]. As
expected, the first case increases the WF while the second case de-
creases. Here, the initial decrease in the work function value of the
composite is due to the charge transfer from Cd atoms to the substrate
Ti. Followed by this, the Cd atoms acquire a positive charge and repel
one another to have a uniform distribution on the Ti surface. In short,
each Cd atom becomes an electric dipole directed outward to bring the
WF down.
3.3. Fermi level pinning
Another interlinking factor to surface dipoles that control the elec-
trical conductivity is the Fermi level pinning effect (FLP). Tak et al.
reported the FLP at higher point defect concentrations to increase the
WF values at extreme conditions i.e., oxygen-deficient and oxygen rich
environment (Ga vacancies) [13]. This FLP was witnessed as increased
work function values in R3 and R4, which could be ascribed to two
factors: excess density of point defects and the loss of dipole moment;
nonetheless, the latter is the result of former. Fig. 4 (a-f) represent the
VBM tails shifts with oxygen vacancies. Since R2 possess the least WF
value, it should be noted that smooth flow of electrons is ensured at
higher optimum defect concentration (Fig. 3b). As the vacancy con-
centration is increased, the WF values is increased beyond TiO2 value,
and confirming the resistance to the electron flow at higher defect
concentration. To further support this statement about FLP, Cd 3d
spectra was plotted. As well known before, the increase in binding
energies corresponds to loss of electrons attributed to the extra elec-
trons (induced by S-vacancies). Fig. 4g depicts the reverse flow of
electrons in R3 and R4 from TiO2 to CdS, where the binding energy
shifts were towards the lower energy; indicating the interaction of di-
poles at higher vacancy concentration. Fig. 4h, i depicts the schematic
diagram of defect in the forbidden gap and subsequent band edge
modulations ascribed to FLP.
This band bending was also confirmed in Fig. 4(a–f) in the form of
VBM tail stretching at the interface. Fig. 5(a) and (b) represent the SEM
images of CdS and TiO2 respectively. In composites (Fig. 5(c–e)), the
CdS atoms are decorated on the TiO2 surface. However, at lower doping
concentrations, the morphological deformation (Fig. 5(c, d)) is subtle.
With the further increase in doping concentration, CdS atoms agglom-
erate on the surface and hinder the growth of crystallites [2]. As a
consequence, the dipoles are more densely packed (Fig. 5(e, f)) to have
more interaction between them and consequently lose their strength
[27]. When this interaction becomes significantly higher, it leads to
depolarization effect causing the negative charge to flow back to CdS.
This increases the WF value of the composites (R3 and R4) higher than
TiO2; as observed from Fig. 3a. Moreover, the depolarization caused the
Fermi level to shift in reverse direction and thus leading to FLP at
higher defect densities. Also, the reduced intermolecular distance be-
tween Cd atoms gives rise to high interaction between dipoles. D. Cornil
4
Applied Surface Science 536 (2021) 147843
et al., reported the reduction in intermolecular distance causes depo-
larization (loss of dipoles)[28]. This indicates that the dipole moment of
CdS is greatly reduced when it aggregates on the surface of TiO2. In
another report, the decrease in WF values with an increase in coverage
layer was linked to electron affinity enhancement [27]. This was rea-
soned by increased dipole-dipole repulsion with aggregation causing a
decrease of its surface energy by electrostatic depolarization. However,
both reports are supporting our results where SEM images clearly depict
the aggregates of CdS at higher concentrations. Although this effect is
negligible (as long as atoms are strongly bound), the reduction in dipole
moment was observed via other mechanisms due to the interaction
between dipoles [29]. Hence, interaction between dipoles at higher
defect densities affects the electrical conductivity of composites and
increase the recombination of electron-hole pair.
The schematic representation of the change in WF values with di-
pole concentration is seen in Fig. 6. In Fig. 6, Rm accounts for R1 and R2
while Rn represents R3 and R4 respectively. The work function values
(WF) of TiO2, R1, R2, R3, R4 and CdS are 6.1, 4.96, 4.86, 6.42, 7.88, and
3.43 eV respectively. The modulation of WF values majorly depends on
the dipoles existing at/around the interface. The dipoles when present
in excess concentrations cause a sudden change in the electrostatic
potential at the interface [28]. This can be observed as up-shift in the
vacuum level in Rn (R3 and R4) (Fig. 6). The dipoles usually possess
direction from negative to positive. When the interaction between di-
poles increases (in case of Rn), its direction is reversed thereby causing a
resistance to the electron flow. Furtherly, the increase in defect con-
centration gives rise to Fermi level pinning (FLP). The synergistic effect
of modulation of vacuum level (due to dipoles) and FLP caused an
abrupt increase in the WF values of R3 and R4. On the contrary, for R1
and R2, the surface dipoles accelerated the electron transfer to the
surface and resulted in lowering of work function values. These de-
creased WF values were instrumental in promoting the Z-scheme mode
of electron transfer in TiO2-CdS composites.
Bandgap studies reveal the role of CdS concentration in enhancing
the absorption spectra of the composites. Usually the bands of different
energies are created by the overlapping of orbitals between neighboring
atoms. In TiO2, the conduction in particular arise from the 3d orbitals,
must transfer electrons to the surrounding atoms. The valence band and
conduction band tends to bend at the heterojunction and behave dif-
ferently. The extent of band bending in composite increased with the
CdS concentration due to higher electron transfer before the loss of
dipole moment. The bandgap values of the composites decreased with
the CdS concentration (see Fig. 7) and are consistent with other reports
[30,31]. Kulbeka-Munk equation was used to estimate the bandgap of
catalysts. The values showed consistent decreasing trend with CdS
concentration such as TiO2 (3 eV), R1 (2.39 eV). R2 (2.34 eV), R3
(2.21 eV), and R4 (2.17 eV) (Fig. 7). Similar results attributed to doping
were reported recently; where Cd doping decreased the bandgap of
TiO2-CdS composites [32,33]. Another interesting observation in the
study is the band edge modulation. Here, the S-vacancies accelerates
the electron transfer, arrests recombination and thereby boosting the
photocatalytic activity [34]. The S-vacancies are deep donors present at
1.72 eV above the VBM of CdS [35]. Here, it should be understood that
both S-vacancies and oxygen vacancies (created due to interaction be-
tween titanate and sulfanate) have donor states below conduction band
and may cause the up-shift of conduction band minima. As the CdS
concentration is increased, the oxygen vacancies also increase and re-
sult in up-shift of VBM tails [36] as observed in the Fig. 4(a–f). The
modification of both VBM and CBM tails owing to oxygen defects was
widely discussed in black TiO2 [37,38]. A similar effect was demon-
strated in Fig. 6 where VB was up-shifted with CdS concentration. In
another study the raise of CBM and VBM was reasoned to surface dipole
moment, stemming from oxygen vacancies [39]. The dipoles at the
surface orient in such a way that their electrostatic potential is raised
(relative to vacuum). This rise in band potentials have particular im-
portance in decreasing the schottky barriers. In conclusion, the band
D. Maarisetty, et al.
Fig. 4. (a–f) VB spectra of TiO2, CdS, R1, R2, R3, R4 respectively. (g) Cd 3d spectra illustrating back flow of electrons with sudden shift in binding energies (h)
Schematic diagram of defect formation and subsequent modulation of Fermi level, CB and carrier concentration (i) Defect induced dipoles.
edges are highly sensitive to the vacancies, and their controls are ne-
cessary to obtain desired energy position to drive the photocatalytic
degradation.
3.4. Mode of electron transfer and mechanism of photocatalytic reactions
Generally, the XPS spectra of Ti 2p, Cd 3d and S 2p display doublet
structure resulting from the spin–orbit splitting (typically observed in p
and higher orbitals). The peaks at ca. 160 and 161 eV correspond to S
2p3/2 and S 2p1/2 respectively implying the successful formation of CdS
[40]. The S 2p spectra in the composites showed a peak at ca. 168.8 eV
that is completely different from the CdS spectra (see Fig. 8(a)). This is
attributed to the bidentate attached SO42− ions with Ti4+ on the sur-
face [41], and the intensity increased with CdS concentration. The
SO42− coordinate with TiO2 in the network to give rise to Lewis acidic
sites that capture photo-induced electrons and reduce the recombina-
tion [42]. However, the higher number of sites could hamper the
quantum yield of the process owing to excess trap states favoring re-
combination. Here, an important aspect to be noted is the oxygen va-
cancy creation (small amount) resulting from interaction between ti-
tanate and sulfanate in the composites (during the calcination process).
The identification of oxygen vacancies in the form of Ti3+ will be ex-
plained later. Notably, the peak shifting towards higher energy in S 2p
spectra is attributed to the substitutional doping of Ti4+ in the CdS
lattice causing the charge compensation and giving rise to S-vacancies
[43]. The S-vacancies (Vs) facilitate new energy levels in the forbidden
whereupon trapping the electron it becomes Vs− and Vs2− in the con-
secutive steps. The transition energies of Vs− and Vs2− are 77 and
5
Applied Surface Science 536 (2021) 147843
45 meV [44] respectively; indicating the closeness to Fermi level po-
sition. When these S-vacancies are present in excess amount, it leads to
lack of availability of charge carriers for driving the photocatalytic
reactions. On the other hand, the higher defect density triggers the
thermodynamically favorable undesired back reactions to decrease the
overall yield of the process (will be explained later).
Ti 2p and Cd 3d spectra confirmed the electron transfer between
CdS and TiO2. Ti 2p3/2 and Ti 2p1/2 corresponds to 458.6 and 464.4 eV
(Fig. 8(b)) respectively [45]. Usually, the binding energies of orbital
decreases by gaining electrons [46]. Similarly, 403.6 and 410.5 eV
corresponds to Cd 3d3/2 and Cd 3d5/2 in Cd 3d spectra (Fig. 8(c)) [47].
The peak shifting towards higher binding energies in the composites
indicate the loss of electrons from CdS to TiO2 to form a Z-scheme;
ascribed to the difference in Fermi levels [48]. As discussed before, the
formation of positive and negative layer at the junction causes the band
bending due to electrostatic attraction between them. This up-ward
band bending forbids the photo-excited electrons to transfer electrons
from CdS conduction band to TiO2. In contrast, TiO2 conduction band
electrons migrate to valence band of CdS to recombine with photo-ex-
cited holes [49]. This may result in lowering the probability of re-
combination in same photocatalysts; causing a drastic increase in redox
potentials. Lastly, the electron transfer from CdS to TiO2 is further
concretized by O 1 s spectra (Fig. 8(d)) where shifting of binding en-
ergies towards lower energy corresponds to electron gain.
This can be correlated to a decrease in WF value at lower CdS
doping to contribute to a better electron transfer. With the further in-
crease in doping concentration (in R3 and R4), peak shifting was ob-
served towards higher binding energies due to increase in WF as
D. Maarisetty, et al. Applied Surface Science 536 (2021) 147843

Fig. 5. SEM images of (a) CdS, (b) TiO2, (C) R1, (d) R2, (e) R3, and (f) R4.

Fig. 6. Relation between surface dipole moment and work function.

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D. Maarisetty, et al. Applied Surface Science 536 (2021) 147843

Fig. 7. Bandgap of catalysts.

Fig. 9. ESR spectra of as-synthesized catalysts: black to navy blue corresponds
(bottom to top) to TiO2, CdS, R1, R2, R3 and R4 respectively.
reflected from UPS measurements (Fig. 3(a, b)). Apart from this, con-
duction and valence band potentials were deduced from equation:
EVBM = ECBM + Eg [50]. The EVBM values for TiO2 (2.85 eV), R1 reduction reactions and support the generation of ROS species. The ROS
(1.99 eV), R2 (1.9 eV), R3 (1.6 eV) and R4 (0.88 eV) were obtained from species (such as superoxide ions and OH radicals) form the basis for the
UPS spectra (Fig. 3a). The conduction band minimum was later calcu- oxidation of organic pollutants. A higher difference between band po-
lated by subtracting VBM values with bandgap. The CBM values for tential and thermodynamic potential drives the photocatalytic reactions
TiO2, R1, R2, R3 and R4 are −0.15, −0.4, −0.44, −0.61, and −1.29 eV at faster rate.
respectively. It can be understood that oxygen reduction reactions are
O2 + e− O2− E = -0.33 V (1)
not possible in TiO2, and R1 owing to thermodynamic constraints (see
Eq. (1)). On the other hand, higher electrical resistance at junction OH− + hVB+ OH* E = 1.99 V (2)
interface blocks the electron movement and thereby leading to charge
H2O + hVB+ OH* + H +
E = 2.34 V (3)
recombination. In R2, the higher reduction potentials drive the Oxygen

Fig. 8. (a) S 2p spectra of CdS, R2, and R4, (b) Ti 2p spectra of TiO2, R2, and R4, (c) Cd 3d spectra of CdS, R3, and R4 and (d) O 1s spectra TiO2, R2, and R4.

7
D. Maarisetty, et al.
ESR measurements were performed for as-synthesized catalysts and
results show that O2− ions formation is more common in the compo-
sites and CdS (due to high reduction potential) as compared to TiO2.
However, OH* (radicals) are more prevalent in TiO2 composites (due to
high oxidation potential EVB = 2.85 eV) as compared to pure CdS.
Fig. 9 shows the ESR spectra of TiO2, CdS, and all the reported com-
posites. The characteristic signals of OH* and O2− ions were recognized
from the standard spectra of OH* (g = 2.0032, B = 3369.1G) [51] and
O2− (g = 2.093 and g = 2.006) [52] respectively. Of all the compo-
sites, R2 has a clear superoxide ion spectra emphasizing the role of
optimal dopant concentration in enhancing the charge transfer and also
due to its higher reduction potential. In pure CdS, it is understandable
that OH radical formation is limited by its lower oxidation potential.
However, in composites, although the lifetime of charge carriers was
improved, the holes were stuck at the interface; hampering its entry
into TiO2 [49]. Moreover, it can be noticed from results that electrons
in R2 effectively participate in ORR activity although reaction (3) is
prohibited. In case of R3 and R4, poor electron transfer at interface
hampered the photocatalytic activity. On the flip side, TiO2 fails to
satisfy the thermodynamic requirement for ORR (Eq. (1)) due to which
the photocatalytic mechanism is completely holes dominated. Never-
theless, in composites, the XPS, ESR and UPS measurements prove that
WF values play a decisive role. This concludes the reaction mechanism
of photocatalytic degradation of MB over composites is different from
TiO2. Apart from this, it is noteworthy to understand the absence of
oxygen defects; as CdS cannot penetrate into Ti lattice to replace
oxygen. This makes the overall efficiency of the process highly depen-
dent on WF and electron band structures; as there were no modifica-
tions in interface properties attributed to doping.
3.5. Vacancies as the probable source of surface dipoles
The S-vacancies create a difference in charge density on the surface
to form dipoles [53]. The formation of dipoles assists in charge transfer
by favoring the chemisorption of oxygen molecules on the surface.
Furtherly, these oxygen containing groups transform to reactive oxygen
species (ROS). The vacancies form corrugations (due to the missing
atom) and tend to spill out electron charges at these sites in order to
smoothen the abrupt variation of the location of positively charged
nuclei [54]. This can be reasoned by the fact that electrons are less
localized as compared to nuclei. Electron transporting abilities are
naturally enhanced at the interface due to this phenomena. The positive
shift in binding energies of S 2p spectra (Fig. 10a) reflects the S-va-
cancies [55] and the concentration of S-vacancies increased with CdS
doping. The oxygen vacancies in the composites were identified in R2
and R4 resulting from sulfate coordination with titanate (as observed
from S 2p spectra). Usually, Ti3+ is an indicator of oxygen vacancies
[56] in TiO2; as the extra pair of electrons induced by defects reduce the
neighboring Ti4+ ions. Fig. 10b, c indicates the presences of oxygen
vacancies in R2 and R4, which could synergistically complement the S-
vacancies in all the modifications pertaining to optoelectronics and
dissociative adsorption [57].
Moreover, this may also indicate the unlikeliness of Cd penetration
into Ti lattice; as the oxygen vacancies are formed due to interaction
between sulfate and titanate in the composite catalysts. Another in-
teresting observation is the decrease in Ti3+ concentration in R4 in
comparison to R2. This decrease could be attributed to formation of CdS
clusters grown big enough on TiO2 (at higher concentration) and
weakened the interaction between them; due to loose contact [58].
Fig. 10d represents the Raman spectra of TiO2, R2 and R4 where the
chemical shift in the composites were ascribed to OV on anatase. The
characteristic peaks of anatase TiO2 can be identified at ca. 145, 395.9,
518.8 and 639.4 cm−1 [59]. It can be understood from Fig. 10d that
with increasing CdS concentration, the peaks at 395.9, 518.8 and
639.4 cm−1 started diminishing while simultaneously showing the
emergence of new peaks at ca. 260, 425, and 603.5 cm−1
8
Applied Surface Science 536 (2021) 147843
(corresponding to CdS nanoparticles). When these vacancies (here at-
tributed to doping foreign atom) exceed an appropriate concentration,
the dipoles at the defect states start to interact with neighboring dipoles
to give rise to depolarization (discussed in the earlier sections). The
electrostatic energy renormalizes activation and formation energies as
consequence of dipole interaction [60]. This smoothening of electron
charge density over the surface was described as the Smoluchowski
effect and has an important role in the field of surface science. Variation
of local work function values, charge density variation, and irregular
distribution of adsorbates are classical examples of this effect [61]. The
decrease in work function values (as observed from the UPS spectra)
could be attributed to the dipole moment; induced by vacancies (op-
timal concentration). Also, the defect sites have connection to surface
adsorption and reactivity due to higher coordination at the corrugated
sites. These local properties may assist in binding the surface adsorbates
and increase the reactivity, which was observed in numerous studies
associated to oxygen defects [62]. Fig. 11 depicts the charge accumu-
lation at lower defect sites and depletion at the upper defect sites with
dipole moment Pz.
3.6. Photocatalytic degradation
To validate the characterization results, the degradation of MB was
carried out under sunlight with as-synthesized catalysts. The photo-
degradation results of all the reported catalysts were plotted in
Fig. 12(a). In the absence of a catalyst (photolysis), there was hardly
any change in the MB concentration. From Fig. 12(a) it can be noticed
that R2 exhibited the highest MB removal (96%). In this discussion, R3
and R4 draw more attention due to sudden underperformance owing to
its higher WF values. Although both TiO2 and CdS are photocatalysts,
the superior performance of former over the latter is attributed to
greater thermodynamic potential differences. In R3 and R4, the en-
hanced WF values hampered the charge transfer thereby increasing the
probability of recombination. The same is reflected in the PL spectra
where R3 and R4 have higher intensities owing to band-band re-
combination. Since CdS is prone to undergo photo corrosion, recycl-
ability tests were conducted to check the photo-stability of catalysts. In
a Z-scheme mode of charge transfer, the electrons in the conduction
band of CdS will be deprived of holes (due to its recombination with
electrons from the TiO2 conduction band) thereby arresting the photo-
corrosion effectively [63]. Fig. 12(b) displays the recyclability de-
gradation tests for R2 under sunlight. From the results, it can be inferred
that there is no substantial change in photocatalytic activity and
therefore the possibility of photo corrosion can be safely ruled out. In
this journey of understanding the photo corrosion, an interesting re-
velation about the flow of electrons in R2 and R4 was also unveiled and
concretized the discussion in earlier sections. As observed in Fig. 8(c),
the Cd 3d spectra shifted towards higher binding energy (in R2 and R4)
due to the loss of electrons from CdS to TiO2. However, it should be
noted the shift was more pronounced in R2 as compared to R4; sug-
gesting the hindrance in electron flow from CdS. The higher con-
centration of dipoles in R4 induced the depolarization effect; causing
the work function value to increase. Moreover, the recyclability results
also show R2 as the best performer among the catalysts under con-
sideration and therefore, the optimum ratios of Cd/Ti also aid in ar-
resting the photo corrosion. Fig. 13 depicts the role played Z-scheme
mode of electron transfer in arresting the recombination.
3.7. Parametric variation
Furthermore, to understand the influence of process parameters on
degradation rate, the concentration of pollutants, catalyst loading and
pH of the solution were systematically varied. Catalyst loading was
varied from 0.3 g/L to 0.9 g/L to determine the optimum loading. From
Fig. 14(a) it can be understood that beyond the optimum loading
(0.5 g/L), the degradation of MB was limited by aggregation of
D. Maarisetty, et al.
Fig. 10. (a) S 2p spectra of CdS, R2 and R4, Ti3+ identification (induced by OV) and comparison between (b) R2 and (c) R4, and (d) Raman spectra (excitation at
532 nm) of CdS, R2 and R4.
Fig. 11. Schematic representation of surface electric dipole arising from spill-
out of electrons.
nanoparticles; thereby decreasing the surface area. Additionally, the
passage of light could be blocked by the shielding effect [64]. The in-
itial concentration of MB was varied to evaluate the uptake capacity of
the catalyst (R2). Fig. 14(b) shows the change in % degradation against
change in the initial concentration of MB. The uptake capacities of R2
calculated from the degradation results (0.5 g/L and pH-6) at 20, 30, 40
and 50 are 37.2, 46.8, 50.4 and 45 mg/g respectively. Fig. 14(c) dis-
plays the pH dependency on overall photocatalytic degradation.
Fig. 14(d) represents the dark experiment that was conducted to ensure
the adsorption-desorption equilibrium.
9
Applied Surface Science 536 (2021) 147843
3.8. Defects optimality: To abort undesired thermodynamically favored
back reactions
The higher defect density in the photocatalysts are usually subjected
to thermo-dynamically favored backward reactions. This may lead to
recombination of charge carriers via trap states [16]. Although defects
aid in enhancing the rate of photocatalytic reactions, a higher number
of vacant sites supports charge recombination through multiple trans-
fers from one energy state to another; as indicated from PL spectra of
R3, R4 [65]. Besides this, there are sufficient enough reports that stu-
died a reduction in photocatalytic activity at excess defect density [66].
However, hardly any of them explained how the higher defect density
triggers the undesired thermodynamically favored backward reactions
are triggered. In this section, we demonstrate the step-by-step proce-
dure by accounting all the modifications ascribed to S-vacancies (in the
composites) with an effective comparison between optimum and higher
defect concentration catalysts.
Fig. 15 represents the mechanism of photocatalytic degradation of
MB in R2 and R4 with both photo-excited electrons and holes following
desired/undesired pathways. Cases (a) and (b) discusses the clear
contrast between catalysts with different defect densities as mentioned.
Step (i) shows the higher probability of charge trapping with plenty of
energy states in the forbidden region and found to be more common in
R4. Though R4 experiences higher trap states, a single catalyst system
such as TiO2, CdS lacks an electron cocatalyst at the interface thereby
promoting band to band recombination. This was clearly seen in case
(b) (step (v)), where the energy offset for charge transport at interface
was meager; attributed to modification by cocatalyst. On the other
hand, thermodynamically undesired backward reactions in case (a)
(step (iii)) may significantly hinder the ORR that produces OH radicals.
But in case (b), due to lower defect density, a higher probability for step
D. Maarisetty, et al. Applied Surface Science 536 (2021) 147843

4. Conclusion

In this work, a series of composite catalysts at different CdS doping

percentages were synthesized. Samples were tested through various
characterizations such as XRD, SEM, XPS, UV-DRS, PL and UPS. Results
showed that an appropriate dopant concentration could dramatically
decrease the work function of the composites. XPS studies reveal the
mode of electron transfer between TiO2 and CdS; confirming the Z-
scheme. Excess concentration of dopant causes a complete over layer on
the surface thereby leading to depolarization. This loss of dipole mo-
ment may cause the electron flow in reverse direction as understood
from UPS results where work function values have drastically in-
creased. Besides, the excess surface defects also have a similar effect to
resist the electron flow at junction interface. Consequentially, band-
band recombination has drastically enhanced at higher Cd doping
concentrations. The composites showed good absorption in the visible
as revealed by bandgap studies. As the mobility of holes was obstructed
by the TiO2 shell, the photocatalytic mechanism was completely
dominated by the oxygen reduction reaction (ORR) in the composites.
Recyclability tests confirms that Z-scheme mode of electron transfer
forms a key in addressing the photo-corrosion in composites. Finally, it
was concluded that excess defect density in the catalysts may have a
detrimental effect on photocatalytic efficiencies.

Declaration of Competing Interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.

Fig. 12. Photocatalytic degradation of MB: (a) comparison of catalysts for

overall yield, (b) Recyclability tests. Acknowledgment

This work was supported financially by the Department of Science

(v) can be assumed. In conclusion, the lower defect densities in case (b),
and Technology (DST), Government of India (EMR/2016/003370). We
efficiently addresses the highly probable charge trapping bypassing step
would also like to express our gratitude to Director, BITS-Pilani, K K
(i) and favoring the MB degradation through steps (iv) and (v).
Birla Goa campus for the support to use the institutional infrastructure
for the development of this paper.

Fig. 13. Addressing the photo corrosion by Z-scheme mode of electron transfer.

10
D. Maarisetty, et al.
Fig. 14. Photocatalytic degradation of MB at varying catalyst loading (a), initial concentration of MB (ppm) (b), and pH (c), (d) dark experiments (adsorption).
Fig. 15. Change in photocatalytic mechanism with defect concentration: (a) R2 and (b) R4.
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