Applied Surface Science 510 (2020) 145413

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Applied Surface Science

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Full Length Article

One-step synthesis of iodine-doped g-C3N4 with enhanced photocatalytic T

nitrogen fixation performance
⁎
Xiuli Hu, Wenjun Zhang, Yuwen Yong, Ya Xu, Xuhong Wang, Xiaxi Yao
School of Chemistry and Materials Engineering, Suzhou Key Laboratory of Functional Ceramic Materials, Changshu Institute of Technology, Changshu 215500, PR China

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

Keywords: Photocatalytic nitrogen fixation has attracted great attention recently due to the mild condition with solar en-
One-step pyrolysis ergy as the only energy input. In this work, the iodine-doped g-C3N4 with carbon vacancies has been successfully
Iodine-doped g-C3N4 synthesized via a one-step thermal-decomposition method. The results showed that the band gap of g-C3N4
Carbon vacancy decreased and the average PL lifetime of g-C3N4 increased after iodine doping. This demonstrated the expansion
Photocatalytic nitrogen fixation
of light responsive range and the high separation efficiency of the photo-generated charge carriers in iodine-
doped g-C3N4. The g-C3N4 with 10 wt% iodine doping exhibited excellent performance and well stability for the
photocatalytic nitrogen fixation under simulated sunlight irradiation within 3 h (200.8 mg/L/gcat), which is 2.8
times as high as that of bulk g-C3N4, owing to the reduced band gap, existence of carbon vacancies and enhanced
separation efficiency of the photo-generated charge carriers. A feasible mechanism was proposed for photo-
induced charge separation and nitrogen photofixation over iodine-doped g-C3N4.

1. Introduction
Nitrogen is an indispensable element of life [1]. Therefore, nitrogen
fixation is one of the most important reactions in nature. As everyone
knows, nitrogen is the most abundant component in air with extremely
strong triple bond (N^N). Nowadays, Haber-Bosch process [2] plays an
important role in nitrogen fixation. The reaction condition of Haber-
Bosch is so harsh (pressure of 15–25 MPa and temperature of
300–500 °C) [3] that a large amount of energy was consumed during
the process. This has spurred the development of an environment-
friendly and inexpensive method for nitrogen fixation with solar light as
the only driven energy [4–7].
Due to the high chemical stability, specific electronic structure and
visible light responsive band gap, g-C3N4 has been widely utilized for
hydrogen evolution [8,9], organic pollutants degradation [10,11], and
nitrogen fixation [12,13]. However, the weak electrical conductivity of
graphical carbon nitride greatly limited their practical applications.
Various modifications have been utilized to improve the photoelec-
trochemical properties of g-C3N4, including elements doping [14–17],
composite [8,18], vacancies or defects [19,20], and morphology con-
trol [21,22]. Among them, iodine is always used to increase the elec-
trical conductivity of conjugated polymers, such as polyaniline [23],
and iodine-doped semiconductors have been reported for photo-
catalytic degradation of organic pollutants or photocatalytic water
splitting due to the large charge carrier mobility, strong light absorp-
tion and modified energy band [24–27]. In addition, carbon vacancies
created in g-C3N4 can act as the active sites for the trapping of photo-
generated charge carriers and facilitate the adsorption and activation of
nitrogen molecules, which can decrease the surface recombination of
photoexcited electron-hole pairs and improve the photocatalytic per-
formance [28]. Therefore, it is of great importance to develop an io-
dine-doped g-C3N4 with carbon vacancies for photocatalytic nitrogen
fixation with the advantages of high charge carrier mobility, low re-
combination rate and numerous active sites that are associated with
iodine doping and carbon vacancies.
Herein, we reported a facile large-scale synthesis of iodine-doped g-
C3N4 with carbon vacancies by direct decomposition-thermal poly-
merization with dicyandiamide and KIO3 as precursors. After iodine
doping, the band gap of g-C3N4 reduced from 2.76 to 2.68 eV and the
average PL lifetime of g-C3N4 extended from 2.36 to 2.41 ns, demon-
strating the higher separation efficiency of the photo-generated charge
carriers in iodine-doped g-C3N4. The g-C3N4 with 10 wt% iodine doping
exhibited the highest activity for photocatalytic nitrogen fixation under
simulated sunlight irradiation within 3 h (200.8 mg/L/gcat) due to the
reduced band gap, existence of carbon vacancies and enhanced se-
paration efficiency of the photo-generated charge carriers.

⁎
Corresponding author.
E-mail address: xiaxiyao@cslg.edu.cn (X. Yao).

https://doi.org/10.1016/j.apsusc.2020.145413
Received 8 October 2019; Received in revised form 3 January 2020; Accepted 14 January 2020
Available online 19 January 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
X. Hu, et al.
2. Experimental
2.1. Preparation of bulk g-C3N4 and iodine-doped g-C3N4
All chemicals were analytical-grade reagents purchased from Sigma-
Aldrich, Inc. and used without further purification. Iodine-doped g-
C3N4 was synthesized by an in-situ decomposition-thermal poly-
merization method with dicyandiamide and KIO3 as the precursors. In a
typical procedure, 2 g of dicyandiamide with a certain amount of KIO3
was grounded carefully in an agate mortar and calcined at 823 K for 4 h
with a heating rate of 5 K/min under nitrogen atmosphere in a tube
furnace. The weight percent of KIO3 to dicyandiamide was controlled as
2, 4, 6, 8, 10, and 15%. The corresponding samples were marked as
CNIX, and X represents the weight percent of KIO3 to dicyandiamide.
Pure g-C3N4 was prepared under the same condition but in the absence
of KIO3, and the sample was marked as CN.
2.2. Characterization
The obtained CN and CNIX were characterized by powder X-ray
diffraction (XRD, Rigaku D/max-2200/PC), transmission electron mi-
croscopy (TEM, FEI Tecnai G2 F30), UV/vis spectrophotometer (UV/
vis, Shimadzu UV-2500), X-ray photoelectron spectrometer (XPS,
Thermo Fisher, Al Kα, λ = 0.84 nm), Fourier transform-infrared spectra
(FT-IR, Bruker VECTOR 22), N2 adsorption-desorption isotherms
(Micromeritics ASAP 2020 apparatus), Fluorescence spectrophotometer
(PL, Hitachi F-7000) with an excitation wavelength of 365 nm, Time-
resolved PL spectra (Horiba Scientific), and Elemental analysis (EA,
Elementar Vario MACRO cube) to determine the phase structure,
morphology, UV/vis diffuse reflectance spectra, elemental composi-
tions and chemical states, specific surface area, photoluminescence
spectra and lifetime, and atomic ratio of carbon to nitrogen. The
thermal property of KIO3 was tested by TGA-DSC (Netzsch STA 449 F3).
2.3. Photocatalytic nitrogen fixation
The photocatalytic N2 fixation was conducted in a 50 mL jacketed
beaker with an external cooling water system. Typically, 20 mg of CN/
CNIX powder was dispersed in 30 mL of aqueous solution containing
5 vol% methanol (scavenger) by ultrasound. To remove the gas im-
purity, N2 was bubbled to the suspension with a flow rate of 50 mL
min−1. Before irradiation, the mixture was stirred 30 min in dark with
bubbled N2 to establish equilibrium. The reactor was irradiated using a
300 W Xe lamp (PLS-SXE300D, Beijing Perfectlight Technology Co. Ltd)
with a power density of 191.2 mW/cm2 measured by an optical power
meter (model: CEL-NP2000, Beijing China Education Au-light Co., Ltd),
while the power density of natural sunlight outside was 76.8 mW/cm2.
At a certain time-interval, 2 mL of suspension was taken out for the
following NH3/NH4+ concentration analysis.
Nessler’s reagent method was conducted to analyze the concentra-
tion of NH3/NH4+. First, 1 mL of the suspension was centrifuged and
diluted by 4 mL of DI water in a 10 mL sample tube. Second, potassium
sodium tartrate solution (l mL) was added to the sample tube. Third,
Nessler’s reagent (1 mL) was injected and the system was stood for
10 min for full color processing. Finally, UV–vis spectrophotometer was
applied to measure the NH3/NH4+ concentration at 420 nm.
3. Results and discussion
As displayed in Fig. 1(a, b), the bulk g-C3N4 and iodine-doped g-
C3N4 showed the typical lamellar structure with a sub-micrometer size.
After doping with iodine, the yellow color of CN becomes a little darker
(Fig. 1c, d). The specific surface areas and pore volumes of CN and CNIX
were determined by the nitrogen adsorption-desorption isotherms (Fig.
S1). The CN, CNI2, CNI4, CNI6, CNI8, CNI10 and CNI15 featured the
surface area of 5.3, 5.2, 7.3, 4.9, 4.7, 5.5 and 5.3 m2/g, respectively
2
Applied Surface Science 510 (2020) 145413
Fig. 1. TEM images and digital photographs of CN (a, c) and CNI10 (b, d).
(Table S1), and the pore volume slightly increased after iodine doping.
Therefore, there is no substantial difference in the specific surface area
of CNIX. The mild change may be attributed to the thermal expansion
caused by the decomposition of KIO3 (Equation (1)) during the calci-
nation process.
KIO3 → KI + 3/2O2 (1)
Fig. 2a and Fig. S2 presented the XRD patterns of CN and CNIX. Two
characteristic peaks at about 13.1° and 27.2° were ascribed to (1 0 0)
and (0 0 2) planes of g-C3N4, representing in-plane packing and inter-
facial stacking of g-C3N4 sheets, respectively [29]. After iodine doping,
the relative intensity of (1 0 0) peak became weaker than that of CN,
which was attributed to the decreased order degree of in-plane struc-
tural packing. Furthermore, the peak position of (0 0 2) plane shifted a
little to higher 2θ values, indicating a reduction of the distance between
nanosheets [8,19,29]. The addition of excess KIO3 during the calcina-
tion process may influence the thermal decomposition-polymerization
of dicyandiamide due to the space baffle effect and cause the weak
crystallinity of g-C3N4 because of the formation of a broad peak be-
tween 20° and 25°. No diffraction peaks assigned to KI were detected in
the XRD patterns of CNIX. TGA-DSC was performed to explore the
thermal properties of KIO3 (Fig. 2b). The curve indicated that KIO3
decomposes at 822 K with a 24.0% mass decrease, which can be as-
cribed to the release of oxygen according to Equation (1). Moreover, the
residue of KIO3 calcined at 823 K for 4 h was checked by XRD (Fig. 2a).
The diffraction peaks matched well with KI (PDF No.04-0471). How-
ever, no KI component was found after calcining the mixture of di-
cyandiamide and KIO3, indicating that a reaction possibly happened
between dicyandiamide and KIO3 during the decomposition process.
As shown in Fig. 3, similar features were observed in the FT-IR
spectra of CN and CNI10, suggesting that the main chemical skeleton
was not changed by iodine doping process. The characteristic breathing
mode of triazine units at 812 cm−1 was observed [30]. Interestingly, in
CNI10, two new peaks at 2172 cm−1 and 539.9 cm−1 were detected,
caused by stretching vibration of cyanogen (eC^N) [31–33] and
carbon-iodine bond (CeI) [34], respectively. It should be noted that the
onset decomposition of KIO3 is 822 K (Fig. 2b) and may react with
amine groups in dicyandiamide or restrain the reaction of cyanogen of
dicyandiamide, introducing the cyano group and carbon-iodine bond
during the formation of CNIX [31].
The compositions and states of CN and CNI10 were further
X. Hu, et al. Applied Surface Science 510 (2020) 145413

Fig. 2. (a) XRD patterns of CN, CNI10 and residue of KIO3 calcined at 823 K. (b) TGA-DSC curves of KIO3 under N2 atmosphere.

formation of carbon vacancies due to the decrease of sp2-bonded carbon

(Table S2) [14,46]. Elemental analysis was conducted to further con-
firm the carbon vacancies in iodine-doped g-C3N4. As shown in Table
S2, the N/C atomic ratio increased from 1.30 in CN to 1.67 in CNI10
and then deceased a little to 1.58 in CNI15, which demonstrated the
existence of carbon vacancy as well. The ratio of N/H in CNI10 (11.48)
was higher than that in CN (8.12), showing the formation of cyano
group during the heating process [9,15]. In addition, the peak area ratio
of C = N-C/N-(C)3 increased from 4.36 in CN to 14.94 in CNI10 and
then decreased to 5.52 in CNI15, showing the bond break of Ne(C)3
during the doping process [14].
Fig. 5 and Fig. S3a presented the UV–Vis diffuse reflectance spectra
of CN and CNIX. The CN sample showed the intrinsic absorption edge
around 450 nm due to the band gap of 2.76 eV. After doping with io-
dine, the absorption edge had an obvious red shift. The band gap en-
ergies of g-C3N4 and iodine-doped g-C3N4 were calculated according to
the following equation:

Fig. 3. FT-IR spectra of CN and CNI10. α hν = A(hν − Eg ) n (2)

where α, h, ν, Eg and A represent absorption coefficient, Planck con-

investigated by XPS, indicating that the CN sample was mainly com-
stant, light frequency, band gap energy, and a constant, respectively.
posed of C, N, and O elements, while the CNI10 sample consisted of C,
The band gap decreased from 2.76 eV to 2.68 eV with the increase of
N, O, and I elements (Fig. 4a). The O element could be attributed to the
KIO3 amount from 0 wt% to 10 wt% and then increased to 2.70 eV with
absorbed H2O or ·OH. The four peaks at 398.3, 398.9, 400.5, and
15 wt% KIO3 (Fig. S3b).
404.2 eV fitting from the N 1s spectrum were resulted from the nitrogen
The migration, separation and recombination of the photogenerated
in the C]NeC structure, [Ne(C)3] structure, amino groups, and π
charge carriers were investigated by the PL emission spectra. As in-
excitation, respectively (Fig. 4b). No obvious peak shift of N 1s was
dicated in Fig. 6 and Fig. S4, CN exhibited a main emission peak at
found between CN and CNI10, suggesting that the chemical states of
around 472 nm, which could be related to the recombination rate of the
nitrogen in CNI10 were almost the same as that in CN. In C1s spectra,
photoexcited electron-hole pairs. With the increase of iodine amount
the peaks centered at 284.5 eV, 286.4 eV and 288.1 eV were assigned to
from 2 wt% to 10 wt%, the peak intensity had a remarkable decrease,
CeC, CeN and NeC]N bonds, respectively [31,35,36]. The signal
implying that the charge recombination rate of CNIX was much lower
intensity of 286.4 eV in CNI10 was reinforced compared to that in CN
than that of CN [13,15,35,47]. Then, the emission intensity at 472 nm
(Fig. 4c), showing the existence of cyano groups (as known in FT-IR)
had little change for the further increased iodine amount. Time-re-
since cyanogen possess similar binding energies to that of CeN [31,36].
solved fluorescence decay spectra of CN and CNI10 were presented in
Notably, a new peak appeared at 295.1 eV in CNI10, which may be
Fig. 6b. Two-exponentials fitting was applied to calculate the decay
assigned to the binding energy of the CeI bond [37–41]. In Fig. 4(d),
time constants, as listed in the inset of Fig. 6b. Compared with CN
the binding energies of I 3d in CNI10 shifted to a lower value than that
(average lifetime 2.36 ns), CNI10 (average lifetime 2.41 ns) presented
in residue of calcined KIO3, indicating the change of I chemical sur-
slower decay kinetics, confirming the higher separation efficiency of the
rounding and the doping of g-C3N4 with iodine [11,30,42–45]. The
photogenerated charge carriers [3,45,48].
doping of iodine into g-C3N4 can improve the charge carrier mobility,
Photocatalytic nitrogen fixation was conducted to evaluate the
increase the light absorption, and cause the change of energy band,
photocatalytic performance. Controlled experiment indicated that
which is favorable for the enhancement of photocatalytic performance
NH4+ cannot be detected in the absence of light or photocatalyst. As
[25].
shown in Fig. 7a, CN exhibited a low activity for photocatalytic ni-
Furthermore, the peak area ratio of (N = C-N)/(C-NHx) decreased
trogen fixation (71.9 mg/L/gcat) under simulated sunlight irradiation
after iodine doping according to the XPS spectra, clearly indicating the
within 3 h. After doping with iodine, the photocatalytic performance

3
X. Hu, et al.
Fig. 4. XPS survey spectra (a) and high-resolution spectra of N 1s (b) and C 1s (c) of CN and CNI10. (d) High-resolution spectra of I 3d in CNI10 and calcined residue
of KIO3.
Fig.5. UV–vis diffuse reflectance spectra of CN and CNI10. Inset: Plots of (αhν)2
versus energy (hν) of CN and CNI10.
improved and then decreased with the increase of KIO3 amount, and
CNI10 showed the highest activity with an ammonia evolution rate of
200.8 mg/L/gcat, which was 2.8 times higher than that of CN. In order
to explore the effect of the heating residuals of KIO3 on the photo-
catalytic nitrogen fixation, the mixture of CN and the heating residuals
4
Applied Surface Science 510 (2020) 145413
of KIO3 were used as the photocatalyst for the nitrogen fixation. The
results indicated that the addition of KI almost had no effect on the
photocatalytic performance of pure g-C3N4 (Fig. S5). The stability of
CNIX was evaluated by cycling photocatalytic nitrogen fixation ex-
periments, as shown in Fig. 7b. There is no obvious decrease of the
photocatalytic activity even after five consecutive cycling tests, in-
dicating that the CNI10 is sufficiently stable for photocatalytic reaction.
Actually, the photocatalytic performance was affected by many
factors, including phase structure, morphology, composition, specific
surface area, light absorption, charge separation and so on. In this
work, the samples were well characterized by powder X-ray diffraction,
transmission electron microscopy, UV/vis spectrophotometer, X-ray
photoelectron spectrometer, Fourier transform-infrared spectra, N2
adsorption-desorption isotherms, fluorescence spectrophotometer, and
Elemental analysis to determine the phase structure, morphology, light
response, elemental compositions and chemical states, specific surface
area, charge separation and lifetime, and atomic ratio of carbon to ni-
trogen. The results showed that the 10 wt% iodine-doped g-C3N4
sample (CNI10) had narrower band gap (2.68 eV), lower PL emission
intensity, longer average PL lifetime (2.41 ns), and more carbon va-
cancies in comparison with undoped g-C3N4. All these characteristics
resulted in expanded light responsive range, weak charge recombina-
tion, and increased active sites, which were favorable for the enhanced
photocatalytic performance. In addition, the energy band changed a
X. Hu, et al.
Fig. 6. Photoluminescence (PL) characterizations of CN and CNI10 (a) and nanosecond-level time-resolved PL spectra monitored under a 370 nm laser excitation.
little after iodine doping. Fig. 8a showed the Mott-Schottky (MS) plots
of CN and CNI10 samples, which were measured in an aqueous solution
of Na2SO4 through a typical three-electrode system. The calculated flat-
band potentials for CN and CNI10 were −1.06 and −0.96 V (vs. Ag/
AgCl), respectively. According to the band gaps obtained from the
UV–vis diffuse reflectance spectra, the valence band positions for CN
and CNI10 were 1.7 and 1.72 V (vs. Ag/AgCl), respectively. Therefore,
the improved photocatalytic nitrogen fixation of CNI10 was partially
ascribed to the enhanced oxidation power of holes to TEOA sacrificial
reagent [49]. With further increasing the amount of KIO3 to 15 wt%,
the photocatalytic activity dramatically decreased. Actually, there was
no obvious difference in the optical absorption, PL emission and BET
surface area. However, the addition of excess KIO3 during the calci-
nation process may influence the thermal decomposition-polymeriza-
tion of dicyandiamide due to the space baffle effect and cause the weak
crystallinity of g-C3N4 because of the formation of a broad peak be-
tween 20° and 25° in the XRD pattern. This phenomenon may lead to
the dramatic decrease of the photocatalytic activity of CNI15 sample.
Furthermore, a possible path for the photocatalytic process in CNIX
system was proposed in Fig. 8b. Iodine was doped into g-C3N4 during
the in-situ calcination method. Compared with CN, the improved pho-
tocatalytic performance of CNIX could be divided into the following
steps: (1) nitrogen was easily adsorbed on CNIX to accelerate the rate of
photocatalytic fixation due to the existence of carbon vacancies [14].
(2) The photogenerated electrons and holes could be well separated
Fig. 7. (a) The photocatalytic nitrogen fixation over CN and CNIX under simulated sunlight irradiation; (b) Cycling experiments for photocatalytic nitrogen fixation
over CNI10.
5
Applied Surface Science 510 (2020) 145413
(Eq. (3)) and the electrons were trapped by the carbon vacancies [46].
(3) The trapped electrons transferred from the carbon vacancies to ni-
trogen molecules and reduced nitrogen to form NH4+ with the protons
from H2O (Eq. (4)) [13,14,19,20,45,50].
CNIX + hν → e− + h+ (3)
− −
N2 + 6H +
+ 6e + H2O → NH4 +
+ OH (4)
4. Conclusions
Iodine-doped g-C3N4 (CNIX) was successfully synthesized by an in-
situ decomposition-thermal polymerization method with dicyandiamide
and KIO3 as precursors. After iodine doping, the band gap of g-C3N4
reduced from 2.76 eV of CN to 2.68 eV of CNI10. The average PL
lifetime of CNI10 (2.41 ns) is longer than that of pure CN (2.36 ns),
confirming the higher separation efficiency of the photo-generated
charge carriers in iodine-doped g-C3N4. The CNI10 showed excellent
performance for the photocatalytic nitrogen fixation with a rate of
200.8 mg/L/gcat under simulated sunlight irradiation within 3 h due to
the reduced band gap, carbon vacancies, and efficient charge separa-
tion, which was 2.8 times as high as that of bulk g-C3N4. This work
demonstrates a possible pathway for the large-scale synthesis of g-C3N4
with iodine-doping for improved photocatalytic nitrogen fixation.
X. Hu, et al.
Fig. 8. (a) Mott-Schottky (MS) plots of CN and CNI10 and (b) the possible process of photocatalytic nitrogen fixation over CNI10.
CRediT authorship contribution statement
Xiuli Hu: Conceptualization, Methodology, Investigation, Writing -
original draft. Wenjun Zhang: Investigation, Data curation. Yuwen
Yong: Investigation. Ya Xu: Investigation. Xuhong Wang: Resources.
Xiaxi Yao: Supervision, Writing - review & editing.
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.
Acknowledgments
The financial supports provided by the National Natural Science
Foundation of China (grant numbers 51702022, 51702023) and
Natural Science Research of Jiangsu Higher Education Institutions of
China (grant number 17KJB430001).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2020.145413.
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