Applied Surface Science 489 (2019) 427–434

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Applied Surface Science

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Combination of experimental and theoretical investigation on Ti-doped g- T

C3N4 with improved photo-catalytic activity
⁎ ⁎
Ruoyu Zhanga,b, Siying Niua, Xingchao Zhanga, Zhenyi Jiangb, Jiming Zhenga, , Chongfeng Guoa,
a
National Key Laboratory of Photoelectric Technology and Functional Materials (Culture Base) in Shaanxi Province, National Photoelectric Technology and Functional
Materials & Application of Science and Technology International Cooperation Base, Institute of Photonics & Photon-Technology, Northwest University, Xi'an 710069, China
b
Institute of Modern Physics, Northwest University, No. 229 Taibai North Road, Xi'an, Shaanxi 710069, China

A R T I C LE I N FO A B S T R A C T

Keywords: Ti-doped graphitic carbon nitrides (g-C3N4) were obtained through calcining the mixture of melamine and
Photocatalyst tetrabutyl titanate. The structure and Ti atom position of Ti-doped g-C3N4 were identified through X-ray dif-
Ti doped fraction (XRD) patterns, X-ray photoelectron spectra (XPS) and first principle calculations. After doping, the
g-C3N4 degradation rate of Rhodamine B (RhB) was improved almost 4 times under visible light irradiation, which was
DFT calculation
further confirmed through theoretical and experimental analysis. According to photoluminescence (PL) spectra,
photocurrent and ultraviolet-visible (UV–vis) absorption spectrum, enhanced separation rate of photogenerated
carriers and modified electronic structure were estimated. These results supplement the current understanding
on photocatalytic processes of doping system and the mechanism of layered photocatalysts.

1. Introduction and enhance photocatalytic property.

The shortage of fresh water limits the sustainable development, thus
the purification or degradation of pollutants in wastewater by sunlight-
driven semiconductor photocatalysts has been paid considerable at-
tentions. An ideal sunlight-driven photocatalyst should possess the
advantages of wide absorption spectral range, suitable redox potential,
non-toxic, low-cost, stable and high separation rate of photo-generated
carriers. Graphitic carbon nitride (g-C3N4) is an environment friendly
polymer semiconductor with about 2.7 eV narrow band-gap [1], which
has been extensively investigated because its unique ability to absorb
blue light with λ < 460 nm wavelength [2–5]. However, pure g-C3N4
has a poor charge carrier separation rate and low marginal visible-light
absorption, therefore g-C3N4 is not an ideal candidate to exhibit high
photocatalytic performance [6–9]. Among the various described
methods, doping is one of the most effective and popular way to im-
prove photocatalytic performance by reducing band-gap and photo-
generated charge carrier recombination of pristine g-C3N4 [10–26].
Incorporation of nonmetallic elements (C, F, S, etc.) and metallic ele-
ments (Na, K, Mn, Eu, etc.) into g-C3N4 is a proven way to modify
visible light response and produced more surface-active sites in order to
enhance performance in water splitting or pollutant photo-degradation
[27–35]. In doping system, 3d transition metals have been widely ex-
plored as pπ orbitals of g-C3N4 and 3d orbitals of transition metal atoms
could strongly hybridize [36], which could expand the absorption range
As a typical 3d-transition metal, titanium (Ti) has been employed to
dope in 2D materials to improve their optical and hydrogen storage
abilities, and expected to enhance photocatalytic properties in Ti-doped
g-C3N4 [37,38]. However, position of the doped Ti atoms in g-C3N4 is
not clear and compelling reason or evidence for the enhanced photo-
catalysis is not put forward entirely. Here, Ti-doped g-C3N4 compounds
were prepared through calcinating the homogenous precursor of tet-
rabutyl titanate and melamine. Before experiments, the binding energy
of Ti-doped g-C3N4 was first calculated by first principle to estimate its
stability, electronic property and spectral absorption range, in which
negative binding energy implies doping system is stable and calculation
result is used to measure the variation of band-gap for evaluating its
photocatalytic activity. In the current study Ti-doped g-C3N4 com-
pounds were prepared through calcinating the homogenous precursor
of tetrabutyl titanate and melamine. Initially the binding energy of Ti-
doped g-C3N4 was calculated by first principle to estimate its stability,
electronic properties and spectral absorption range, in which negative
binding energy implied that the doping system was stable. As a com-
parison, the microstructure and the optical properties of the obtained
Ti-doped compounds were also evaluated. Our experiment results in-
dicate that Ti atoms tend to embed into lattice interlayer and reduce
electron-hole recombination of original g-C3N4. Besides, doping of Ti
element leads to a great improvement of its photocatalytic efficiency.

⁎
Corresponding authors.
E-mail addresses: zjm@nwu.edu.cn (J. Zheng), guocf@nwu.edu.cn (C. Guo).

https://doi.org/10.1016/j.apsusc.2019.05.362
Received 12 January 2019; Received in revised form 24 May 2019; Accepted 31 May 2019
Available online 01 June 2019
0169-4332/ © 2019 Published by Elsevier B.V.
R. Zhang, et al.
Fig. 1. (a) XRD patterns of varied Ti concentration doped samples; (b) Calculated crystal structures of pristine and doped g-C3N4, the SEM images of (c) pristine and
(d) Ti 5/g-C3N4 together, with the high resolution XPS spectra of (e) C 1s, (f) N 1s, (g) Ti 2p in pure and Ti 5/g-C3N4. The scale in the figure (c) and (d) represents
500 nm.
2. Experimental
2.1. Sample preparation
The Ti-doped and pure g-C3N4 powders were synthesized by heating
method, in which analytical grade chemicals tetrabutyl titanate
(C16H36O4Ti), melamine (C3H6N6) and ethanol (C2H6O) were used
without further purification. In order to protect Ti source from hydro-
lysis, varied stoichiometric amounts of tetrabutyl titanate (0, 0.5, 1, 3,
5 mmol) were dissolved in into a 20 ml (1,1) ethanol-acetic acid mix-
ture. 5 g melamine was added into the mixture and stirred for several
munities till a homogeneous solution was formed. The solution was
dried at 70 °C for 6 h to form a solid mixture and then calcined at 550 °C
for 4 h. Ti doped g-C3N4 with varied Ti dosage were abbreviated as Ti-
x/C3N4, where x represents the doped Ti amount of raw materials tet-
rabutyl titanate (0, 0.5, 1, 3, 5 mmol).
2.2. Characterization
The phase purities were determined by X-ray diffraction (XRD)
patterns using Rigaku-Dmax 3C powder X-ray diffractometer with Cu
Kα radiation (λ = 1.5406 Å) at a range 10° ≤ 2θ ≤ 70°. X-ray photo-
electron spectra (XPS: AXIS-ULTRA DLD) were corrected using C 1 s
(284.8 eV) as reference energy. The photoluminescence (PL) and
UV–vis spectra were collected on Edinburgh FLS920 fluorescence
spectrophotometer and VARIAN CARY 5000, respectively. The mor-
phology and composition of compounds were characterized by a
Hitachi SU-8010 field emission scanning electron microscope (FE-SEM)
and transmission electron microscopy (TEM) measurements. The sur-
face area measurements were used through a surface area analyzer
(3H2000-PS2).
The photocatalytic ability was estimated by the degradation rate of
Rhodamine B (RhB) aqueous solution under white LED (5 W) irradia-
tion, in which the ratios of RhB dye concentration at varied time to its
original concentration were used to determine the photocatalytic abil-
ities of the compounds. Typically, 10 mg sample was added into 50 ml
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Applied Surface Science 489 (2019) 427–434
RhB solution at a concentration of 2 × 10−2 mmol/l, and then kept in
dark for 0.5 h to establish equilibrium of adsorption-desorption. During
irradiation, 3 ml suspension was collected every 20 min and the con-
centrations of RhB aqueous solutions were analyzed with a spectro-
photometer (TU-1901).
2.3. Computational models and methods
All calculations were performed using Vienna Ab Initio Simulation
Package (VASP 5.4.1) [39], in which the generalized gradient approx-
imation (GGA) and van der Waals (vdW) correction were included by
using DFT-D3(BJ) approach to get optimized structure [40]. As is well
known that the systems containing d-orbital could not be accurately
calculated by only using GGA function, thus GGA + U calculations were
used to more accurately describe the localized d-orbital in Ti-doped g-
C3N4 [41,42]. Transition metal (TM) embedded in g-C3N4 sheets illu-
strated that reasonable value of (U-J) is greater than or equal to 3 eV,
herein the values of U and J were set as 4.5 eV and 0.5 eV, respectively
[43]. Furthermore, the cutoff energy was set as 500 eV, and the criteria
for convergence in energy and force were 10−5 eV and 0.01 eV/Å, re-
spectively. 5 × 5 × 1 k-point sampling grid was applied in structural
optimization and a 7 × 7 × 1 k-point grid in static calculation. We
modeled 1× 1 × 2 supercell of g-C3N4 (001) surface and Ti-doped g-
C3N4 slab with four atomic layers, a vacuum region of 20 Å was used to
avoid interactions in z direction. HSE06 hybrid function (instead of
standard GGA function) was adopted in the calculation of electronic
properties to avoid underestimation of semiconductor band-gap [44].
In order to confirm doping is stable, the binding energy (Eb) of the
system was calculated by following formula:
Eb = E Ti/C3N4 − EC3N4 − E Ti
where EC3N4 and ETi are the energy of pristine g-C3N4 and bare Ti atom,
ETi/C3N4 represents the total energy after doping. The absolute value of
binding energy is −1.72 eV, in which the negative value implies a
stable doping system.
R. Zhang, et al. Applied Surface Science 489 (2019) 427–434

Fig. 2. (a) TEM image of Ti-doped samples, (b, c, d) elemental mapping images of the sample. The scale in the figure represents 500 nm.

Fig. 3. Band structure of (a)pure and (b)Ti-doped g-C3N4 as well as their TDOS and PDOS (c) and (d) together with (e) UV–vis absorption spectra of compounds and
(f) estimated band-gaps of sample.

3. Results and discussion
3.1. Structure and composition
The crystal structure and phase of all materials were affirmed by
XRD as function of doped Ti concentration (Fig. 1a). For these samples,
two main peaks at about 13.5° (001) and 27.3° (002) appeared in
pristine and doped g-C3N4, in which no any new diffraction peaks were
observed after doping Ti. Comparing XRD patterns of the pristine and
Ti-doped g-C3N4, the strongest diffraction peaks (001) and (002) gra-
dually shift from 13.5° to 14.1°or from 27.3° to 27.9° with increasing Ti
contents, which indicates interlayer distance and cell volumes decrease
and further implies that the dopants have entered into the lattice of g-
C3N4 and no impurities formed. Previous publications demonstrated
that transition metal atoms prefer to enter into the hexagonal ring of g-
C3N4 instead of substitution site due to the large radius difference be-
tween Ti (1.45 nm) and C (0.86 nm) or N (0.80 nm) atoms [45]. After
first principle optimization, the space between layers theoretically

429
R. Zhang, et al.
Fig. 4. (a) PL of g-C3N4 with varied concentration of Ti dopants and (b) pure and Ti-doped g-C3N4 partial charge densities (at arbitrary isosurface levels) of VBM and
CBM.
becomes smaller and the average layer distance changes from 3.56 to
3.36 nm as shown in Fig. 1b, which is consistent with XRD results.
Obviously, the optimized Ti-doped g-C3N4 crystal structure is interlayer
bridging pattern, in which Ti atoms connected with adjacent two layers
in Ti-doping framework.
The high resolution XPS were used to further analyze the compo-
sition of Ti-doped compounds and the valence state of Ti atoms. C1s,
N1 s, Ti2p of the pure and Ti-doped g-C3N4 were presented in Fig. 1e-g
with a comparable method, respectively. Three bonding states of
carbon species were fitted in the doped and un-doped compounds (in
Fig. 1e), in which peak of binding energy at 284.8 eV is attributed to
CeC bonds, the peaks at 285.6 and 288.1 eV are assigned to sp2 C]N
bonds and N-C=N for C in N-containing aromatic rings. However, there
are three and two peaks in N 1 s high-resolution spectra of Ti-doped
compounds and pure g-C3N4, in which the predominant peak at
398.4 eV corresponds to sp2 hybridized N in triazine rings (C-N=C) but
centered at 399.6 and 401.1 eV are ascribed to titanium nitride or hy-
droxides of Ti and N atoms in Ti-doped or pure g-C3N4 [46], as dis-
played in Fig. 1f. For the peak at 457.4 and 468.8 eV in Ti-doped sample
(in Fig. 1g), it comes from the binding energy of Ti 2p in Ti4+ doped g-
C3N4, which further confirms that Ti atoms exist in the lattice.
The morphologies of the pristine and Ti 5/C3N4 samples were also
characterized by SEM in Fig. 1c and d, suggesting that g-C3N4 consists
of curved porous sheets and randomly stack together to assemble a
porous structure. The average pore size and the specific surface area of
the doped and un-doped g-C3N4 compounds are 0.047/0.045 cm3/g and
9.5/7.9 m2 g−1, which indicates doping process has minimum influence
on macrostructure and unable to produce a significant role to enhance
photocatalytic efficiency. The microstructure of Ti-doped g-C3N4 and
corresponding composition were characterized via TEM and elemental
mapping. No apparent morphology difference could be observed after
doping Ti, which consists of porous sheets, similar to SEM results
(Fig. 2a). Element mapping analysis (in Fig. 2b-d) clearly shows that the
doped compounds are made of C, N and Ti elements and the Ti element
is uniformly distributed throughout the whole g-C3N4.
3.2. Optical properties
The band-gaps of photocatalysts determine their photo-catalytic
activities, which are calculated by first principle theory and illustrated
in Fig. 3a-d. It is observed that g-C3N4 is a direct band-gap semi-
conductor (shown in Fig. 3a) with 2.80 eV band-gap, which is con-
sistent with previous theoretical or experimental results [17]. However,
Ti-doped g-C3N4 transforms into an indirect band-gap semiconductor
and the band-gap reduces to around 1.8 eV, as shown in Fig. 3b. Gen-
erally, the smaller band-gap is favorable to expand the absorption
spectrum range and an indirect band- gap semiconductor is more
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Applied Surface Science 489 (2019) 427–434
conductive in obtaining better photocatalytic activity compare to direct
band-gap semiconductor. This is due to that photo-excited electrons
back to VB need to travel an extra k-space distance and require addi-
tional kinetic energy [47], which could reduce recombination rate by
prolonging the recombination path of photo-generated carriers. Results
for total and partial density of states (TDOS and PDOS) of pristine g-
C3N4 and Ti-doped g-C3N4 were shown in Fig. 3c and d to further un-
derstand the intrinsic character of semiconductor. It is observed that the
valence band (VB) edge mainly consists of C-2 s and N-2p orbitals and
conduction band (CB) edge is mainly composed of C-2 s and N-2 s or-
bitals in pristine g-C3N4. The similar occupational energy range of C-2p
and N-2p orbitals (−6 to 0 eV) proved their strong coupling, inducing
the formation of π bond [48]. For Ti-doped g-C3N4 plannar framework,
it is clearly observed that Fermi level enters the CB, and both CB and VB
are mainly determined by the hybridization of C, N and Ti 3d orbitals,
in which the empty orbits in 3d orbitals play an important role. Fig. 3d
shows that the impurity level induced by the dopant atoms Ti appears
between the original CB and the VB. In fact, these doping states reduce
electrionic transitions energy and provide a “bridge” for lower energy
photo-generated electrons. In addition to being excited to the CB, the
photon can also be excited onto the impurity levels induced by these
dopings. The impurity levels induced by doping Ti atoms provide more
orbitials and smaller energy for transition of photon from ground state
to excited state, leading to red shift of UV–vis absorpsion spectra.
To experimentally determine the band-gap of the pure and Ti-doped
samples, diffuse reflection spectra (DRS) were monitored. The absorp-
tion edges of pure g-C3N4 locate at around 460 nm, while it gradually
shifts to 528, 531, 527 and 507 nm as the concentration of Ti increases
to 0.5, 1, 3, and 5% (Fig. 3e). Obviously, 1% Ti-doped samples exhibit
the strongest absorption in long wavelength region. The band-gap of
sample can be estimated according to equation [49]: (αhυ)n = A(hν-
Eg)n, where α, hν, Eg, A and n are the absorption coefficient, photo-
energy, band-gap, a constant and n value is 1/2 for direct band-gap
semiconductor or 2 for indirect band-gap semiconductor, respectively.
Fig. 3f displayed the curves plotted the value of (αhυ)n vs. hv, n value is
1/2 for pristine g-C3N4 and 2 for Ti-doped g-C3N4 according to the
results of DFT calculation, and the extrapolation of the curve on the
abscissa allows estimation of the band-gap of pure and Ti-doped com-
pounds to be 2.8 (pure) and 2.55 (0.5% Ti), 2.5(1.0% Ti), 2.63 (3.0%
Ti) and 2.65 eV (5.0% Ti). This result further confirms that the band-
gap could be narrowed by doping, which is consistent with above
theoretical calculation results.
Doping Ti into g-C3N4 leads to narrower band-gap and transition of
band structure from direct to indirect, which is favorable to enhance the
separation rate. PL spectrum is an effective way to understand re-
combination processes. Fig. 4a shows PL spectra of Ti-doped g-C3N4 as
function of Ti dosage under 365 nm excitation, in which PL intensity
R. Zhang, et al.
Fig. 5. (a) Photocatalytic activity of as-synthesized compounds for degradation
of RhB; (b)the plots of ln(C0/C) vs irradiation time and inset for photo-de-
gradation rate constants for varied compounds; (c) Cycling photocatalytic test
of Ti 1/C3N4;
abruptly decline with the introduction of Ti due to lower electron-hole
pair recombination rate. Comparing with pure and other Ti doped
samples, 1% Ti-doped g-C3N4 exhibits the highest separation rate of
photo-induced charge carries for the weakest PL emission intensity,
which could also be confirmed by partial charge densities of VBM and
CBM, the charge distributions on VBM and CBM were shown in Fig. 4b.
In pristine g-C3N4, the N1 atom connects each heptazine unit and al-
most no charge distribution, which means that photo-generated elec-
trons do not transfer at the N1 site. It suggests that the charge transfers
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Applied Surface Science 489 (2019) 427–434
between the heptazine units are greatly suppressed and electrons are
active only in heptazine unit, leading to high recombination rate of
photo-induced carriers and intense PL emission. While in Ti-doped
samples, photo-generated electrons can move freely across N1 atom in
the g-C3N4 plane due to Ti atoms can transport electrons across two
adjacent layers as a bridge (in Fig. 1b) instead of the only channel (N1)
in the plane, which reduce recombination rate of charge carriers and PL
intensity. Further comparing the PL emission spectrum of pristine with
those of Ti-doped compounds, a slightly red shift from 465 to 467 nm
appeared in intrinsic PL emission, which due to the narrowed band-gap
and the introduced extra impurity levels.
3.3. Photocatalytic activity and mechanism
The current study results showed that doping Ti atoms in g-C3N4
leads to a narrower band-gap and lower combination rate of photo-
generated charge carriers, which made an improved photocatalytic
performance. To confirm our speculation, photocatalytic activities of
pure and Ti-doped samples towards the degradation of RhB under the
irradiation of simulated sunlight white LED (5 W) were evaluated ac-
cording to the varied value of C/C0 and displayed in Fig. 5a by mon-
itoring the characteristic emission intensity of RhB, where C and C0 are
concentration at a time and initial concentration of RhB. In order to
avoid the error of physical adsorption during photocatalytic processes,
absorption-desorption equilibrium behavior of the catalyst was estab-
lished in dark for 30 min prior to light irradiation. Obviously, the de-
gradation rate of RhB reaches about 61% over the pristine g-C3N4 while
around 99% RhB was degraded over the Ti-doped g-C3N4 after 100 min
irradiation, proving that photocatalytic ability enhanced after doping Ti
atoms. Among the doped compounds, 1% Ti doped g-C3N4 exhibits the
best performance during the photocatalytic process and 99.4% RhB was
degraded, which could also be explained by redox potentials in Fig. 3d.
Moreover, degradation kinetics behaviors in the process of RhB de-
composition can be ascribed with a simplified Lagmuir-Hinshelwood
model and the degradation kinetics curves (in Fig. 5b) over the varied
compounds were plotted according to formula ln(C/C0) = −kt, where k
is the pseudo-first-order kinetics rate constant and reflects the photo-
catalytic efficiency [51]. The k values are 0.0102, 0.0368, 0.0461,
0.0325 and 0.0299 with increasing the Ti concentration from 0 to 5%,
photocatalytic efficiency of the best one Ti 1/C3N4 is > 4 times higher
than that of pristine g-C3N4 as given in the inset of Fig. 5b. For practical
application, stabilities of photocatalysts were also representatively
evaluated through the degradation of RhB using cycling experiments on
the optimal sample Ti 1/C3N4, and no significant deactivation was
found for its photo-catalytic activity after 3 times cycling reactions (in
Fig. 5c).
Seen from Fig. 6a, all five electrodes have generated photocurrent
with the switching of the light (on/off). The photocurrents of all Ti-
doped compounds are obviously higher than that of pristine g-C3N4,
among which the photocurrent density of all compounds decreased in
the order Ti 1/g-C3N4 > Ti 0.5/g-C3N4 > Ti 3/g-C3N4 ≈ Ti 5/g-
C3N4 > pure g-C3N4 under visible-light irradiation. This result in-
dicates that doping is benefit for enhancing carrier separation rate. For
further exploration in the reactive radical species during photocatalytic
process of doped samples, several scavengers including Na2C2O4 (h+
quencher), BQ (•O2– quencher) and IPA (•OH quencher) were used
during the course of RhB degradation experiment. Compared with the
case without scavengers, photocatalytic reaction was hindered by all
three kinds of trapping agents in varying degrees (in Fig. 6b), but RhB
photodegradation was obviously depressed after addition of BQ in
comparison with addition other scavengers, which indicate that re-
duction reaction O2 (O2 + e− → •O2−) is mainly responsible for the
photodegradation of RhB.
Above results suggested that the RhB degradation ability of Ti-
doped g-C3N4 was greatly improved because of the reduced re-
combination rate of the photo-generated carriers and the reduced band-
R. Zhang, et al.
Fig. 6. (a) Transient photocurrent response of pure and Ti-doped samples with varied concentrates. (b) Charge carrier trapping with varied scavengers on de-
gradation of RhB.
Fig. 7. Work Function of (a) pure and (b) Ti-doped compounds.
Fig. 8. Possible photocatalytic mechanism of pure and Ti-doped samples with
simulated sunlight irradiation.
gap. Actually, it is also attributed to the distance of redox potentials to
its CB and VB, the VB potentials (EVB) and CB potentials (ECB) of
compound are calculated using electronegativity theory equations [50]:
EVB = X –E0 –0.5Eg
ECB = EVB –Eg
where X (defined as the geometric mean of absolute electronegativity of
the constituent atoms), E0 and Eg are the electro-negativity of
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Applied Surface Science 489 (2019) 427–434
semiconductor, normal hydrogen electrode (NHE, about 4.5 eV) and
band-gap of host. Generally, the trace doping is not enough to affect the
value of X, thus X value is 4.73 eV according to previous publication
[51] and Eg is 2.8 eV and 2.5 eV for pristine g-C3N4 and Ti 1/C3N4 ac-
cording above experimental results. So, EVB /ECB of g-C3N4 and Ti 1/
C3N4 are 1.58/−1.12 and 1.48/−1.02 eV vs. NHE, respectively. The
valance band edges upper shift while the CB down shift for Ti-doped
samples, which is consistent with result of above DFT calculation. This
leads to the positions of VB and CB are much closer to redox potentials
of oxygen and hydrogen, respectively, which is beneficial to excellent
photocatalytic efficiency [51]. Therefore, the reduced band-gap en-
hances photon absorption capacity of Ti-doped g-C3N4, while the ele-
vation of EVB and decline of ECB make the photo-generated holes and
electrons generate more easily and efficiently.
Experimental results illustrated that the optimal concentration for
Ti-doped g-C3N4 is determined as Ti 1/C3N4 but the photocatalytic ef-
ficiency will decrease with further increase the concentration of Ti,
which could be explained though work functions and Fermi level.
Fig. 7a and b displayed the work functions of pure and Ti-doped
compounds, respectively, in which the work function(Ф) is defined as
Ф = Evac-EF. Here, Evac is the vacuum potential energy at infinite dis-
tance and EF is the Fermi level in the system, thus the work function of
pure and Ti-doped compounds was calculated to be 4.22 and 3.23 eV,
respectively. It is obviously deduced that the doped atoms transfer
electrons to the host, leading to the variation of Ti-doped C3N4 work
function. Ti dopant will donate more electrons with increasing con-
centration, and the photocatalytic efficiency will decrease due to EVB
exceed the O2 redox potential, which is in agreement with previous
predication [48].
The possible mechanism was proposed according to the position of
R. Zhang, et al.
VB and CB from experimental results, as shown in Fig. 8. During irra-
diation by simulated sunlight, excited photo-generated electrons are
able to transfer to CB and leave holes in VB (g-C3N4 + hν → e− + h+),
since EVB of pure and Ti-doped compounds are more negative than that
of E0(O2/•O2−), superoxide radical anion (•O2−) could be generated by
reducing O2 (O2 + e− → •O2−) on g-C3N4 surface and h+ in valance
band could generate hydroxyl radicals simultaneously (h++H2O →
•
OH + H+) due to high oxidizing potential. The existence of •O2– may
form hydrogen peroxide (H2O2) and then form •OH eventually
(2•O2– + 2H+ → H2O2 + O2, H2O2 + e− → OH– + •OH). Finally, gen-
erated •OH which is strong oxidizing agents could degrade RhB.
4. Conclusions
In summary, Ti doped g-C3N4 has been successfully synthesized and
the photo-catalytic ability was greatly enhanced after doping Ti, which
has been proved by combining experiments with theoretical calcula-
tions. No significant structural changes were found with the introduc-
tion of Ti in pure samples, while XPS and the calculations illustrated
that Ti entered into g-C3N4 units and Ti atoms linked two adjacent
layers and improved carrier separation capability. The experimental
and theoretical calculation of Ti-doped g-C3N4 further indicated that
the reduced band-gap led to the broadened spectral absorption. The
optimal concentration of Ti in present work was determined as Ti 1/
C3N4 according to the photocatalytic results, and its photo-degradation
RhB activity was significantly improved by four times in comparison
with that of pristine g-C3N4. The reason could be assigned to the nar-
rowed band-gap and reduced charge carrier combination rate of photo
induced charge carriers due to introduced extra impurity levels and
transition from direct band structure to indirect with doping Ti in g-
C3N4 host. The present result may provide a new avenue for designing
other photocatalysts through doping.
Acknowledgments
This work was supported by National Natural Science Foundation of
China (No. 51672215, 11274251, 51572219, 51872227) and The
Youth Innovation Team of Shaanxi Universities.
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