Molecular Catalysis 432 (2017) 64–75

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Molecular Catalysis
journal homepage: www.elsevier.com/locate/mcat

Editor’s choice paper

Creating distortion in g-C3 N4 framework by incorporation of

ethylenediaminetetramethylene for enhancing photocatalytic
generation of hydrogen
Feng-Yun Su, Wei-De Zhang ∗
School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Guangzhou, 510640, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: Relatively narrow visible light responsive region and high recombination probability of photogener-
Received 8 December 2016 ated charge carriers are the main barriers that limit the photocatalytic activity of graphitic carbon
Received in revised form 6 February 2017 nitride (g-C3 N4 ). In this study, modified g-C3 N4 was synthesized by adding minor amount of ethylene-
Accepted 8 February 2017
diaminetetraacetic acid (EDTA) into urea as precursors for subsequent thermal polymerization. The
thermal intermediate product ethylenediaminetetramethylene (EDTM) during decarboxylation of EDTA
Keywords:
was grafted to the framework of g-C3 N4 by connecting adjacent 3,s-triazine units. The special chelate
g-C3 N4
structure of EDTA leads to the distortion of g-C3 N4 to a nonplanar structure, which is responsible for
EDTA
Grafting
extending the light harvesting around 500 nm, and consequently promoting the generation, separation
Photocatalysis and transfer of charge carriers. The H2 evolution rate on an optimized EDTM-grafted g-C3 N4 photocat-
Hydrogen evolution alyst (UCN-10) reaches 116.4 ␮mol h−1 , which is about 3.5 times of that on the pristine g-C3 N4 (UCN).
The formation process of the grafted structure and the mechanism for the enhanced photocatalytic H2
evolution over UCN-10 were proposed based on experimental results.
© 2017 Elsevier B.V. All rights reserved.

Introduction Significant strategies have been developed to improve its photo-

catalytic activity, such as morphological control [28–30], doping
Photocatalytic hydrogen evolution from water splitting under [18,31–33], semiconductor coupling [34], modification with car-
sunlight is attractive and challenging for scientists [1]. Photocatal- bon materials [35–39] and dye sensitization [40], which are usually
ysis and photoelectrocatalysis based on semiconductors provide used for modifying inorganic semiconductor photocatalysts.
promising approaches for solar energy harvesting and conversion Recently, a novel strategy to incorporate small organic
[2–5]. Therefore, developing low-cost, efficient and eco-friendly molecules to the frameworks of g-C3 N4 was designed to tune its
photocatalysts has become research hotspot in the photocatalytic band gap, and further enhance the visible light utilization and pro-
fields. In these years, a metal-free photocatalyst graphitic carbon mote the photo-induced electron-holes separation. Barbituric acid
nitride (g-C3 N4 ) only consisting of carbon and nitrogen elements molecule was firstly incorporated into g-C3 N4 frameworks through
has aroused tremendous interest due to its easy preparation, high copolymerization [41], followed by various organic molecules
physical and chemical stability, well-suited band positions, and containing amino or cyano groups [42,43]. Doing so, various aro-
versatile modification approaches for tuning its physical properties matic rings were incorporated into the carbon nitride networks,
[6]. As a novel and promising photocatalyst, g-C3 N4 has stimu- resulting in improved visible light response and more efficient
lated significant excitement in the applications such as fuel cells photo-induced charge carrier separation. As Schiff base is usually
[7,8], supercapacitors [9,10], electrocatalytic [11–13] or photocat- used to extend the conjugated systems of polymers, a series of aro-
alytic [14–20] water splitting and photodegradation of pollutants matic aldehydes have been incorporate into the g-C3 N4 network
[21–25]. However, the known poor light absorption in the visi- for enhanced visible light utilization [44]. Inspired by the above
ble region, small specific surface area and fast recombination of reports, this study reports grafting of the intermediate species from
photo-induced charge carriers are the serious limitations [26,27]. decarboxylation of EDTA to the framework of g-C3 N4 by connect-
ing to adjacent 3,s-triazine units. For g-C3 N4 polymers, the HOMO
mainly consists of the 2p orbit of N atoms, while hybridized C
∗ Corresponding author. 2p and N 2p orbits contribute to LUMO, forming ␲* interactions
E-mail addresses: [email protected], [email protected] (W.-D. Zhang). [45]. As it is known, g-C3 N4 exhibits strong ␲-␲* transitions near

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2468-8231/© 2017 Elsevier B.V. All rights reserved.
 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75 65

400 nm extending into the visible range. While the EDTA-modified The electron paramagnetic resonance (EPR) spectra were taken
g-C3 N4 samples show an accessional absorption region around using a Bruker model ER200-SRC spectrometer.
500 nm assigned to n-␲* electronic transitions of N lone pairs,
which are prohibitive for planar s-triazine or heptazine structures Electrochemical Measurements
but become possible for distorted structure [46,47]. The special
chelate structure of EDTA led to the distortion of g-C3 N4 , which A working electrode for electrochemical measurement was pre-
activated the n-␲* transition. The as-prepared samples showed pared by a typical method: 40 mg of the prepared sample was
remarkably enhanced photocatalytic activity for H2 evolution from dispersed into 2 mL of 2 mg/L ethyl cellulose ethanol solution under
water splitting under visible light. In the work, we demonstrated an ultrasonication. The electrode was obtained by coating the disper-
efficient approach to improve the photocatalytic activity of g-C3 N4 sion onto a FTO glass plate by doctor blade method, followed by
by creating distortion in its framework. drying at 120 ◦ C for 1 h. Photoelectrochemical experiments were
performed on an electrochemical work station (CHI-660C, China)
with a standard three-electrode system using a Pt plate as the
Experimental Section
counter electrode, and an Ag/AgCl (saturated KCl) as the reference
electrode in 0.5 M Na2 SO4 electrolyte. The visible light irradia-
Chemicals
tion was obtained from a 300 W xenon lamp (PLS-300/300UV)
EDTA and urea were obtained from Kemiou Chemical Reagent with a 420 nm cut-off filter. The integrated visible light intensity
Co. Ltd. (Tianjin, China) and Fuchen chemical reagents factory was 150 mW/cm2 . The photocurrent response of the electrodes
(Tianjin, China), respectively. Triethanolamine (TEOA, 85%) was was measured at +0.5 V vs. an Ag/AgCl electrode. Electrochemical
purchased from Tianjin Fuyu Fine Chemical Co. Ltd., China. impedance spectroscopy (EIS) plots were measured at the corre-
Chloroplatinic acid (H2 PtCl6 ·6H2 O, Pt ≥ 37.55%) was obtained from sponding open circuit potential over the frequency ranging from
Aladdin Chemistry Co. Ltd., China. Deionized water was produced 100 kHz to10 mHz in the dark in 0.010 M K3 Fe(CN)6 /K4 Fe(CN)6
from a GWA-UN pure water system (Beijing, China). All the chem- aqueous solution.
icals were used without any further purification in this study.
Photocatalytic Production of H2

Preparation Procedure Photocatalytic hydrogen evolution was tested in a closed glass

circulation system by top-irradiation (Labsolar III AG, Beijing
20 g urea and different amounts (0, 5, 10, 20, 50 and 100 mg) Perfectlight Technology Co. Ltd.) at room temperature. For the
of EDTA were dissolved in 100 mL deionized water at 100 ◦ C under photocatalytic reaction, 50 mg photocatalyst was dispersed in
magnetic stirring, and then the water was removed by evaporation. 100 mL 10 vol% triethanolamine aqueous solution, and 3.0 wt% Pt
The resulted urea-EDTA cocrystals were obtained and named as co-catalyst was deposited on the photocatalyst by in situ photo-
UEA-x (x = 5, 10, 20, 50 and 100). The obtained UEA-x was then reduction of H2 PtCl6 directly dissolved in the above suspension.
put in a 100 mL crucible with a lid and heated at 550 ◦ C for 4 h The suspension was then degassed for 20 min with a vacuum pump
at a heating rate of 10 ◦ C min−1 in a muffle furnace. The obtained to remove the O2 completely inside the reactor before irradiation. A
samples were denoted as UCN (x = 0) or UCN-x (x = 5, 10, 20, 50 and 300 W Xe arc lamp (PLS-SXE 300/300UV, Beijing Perfectlight Tech-
100, respectively). nology Co. Ltd., China) was used as the visible light source with
a 420 nm cut off filter. The integrated visible light intensity was
Characterization of the Samples 100 mW cm−2 . The released H2 was analyzed on a gas chromatogra-
phy (GC 7806, Beijing Shiweipuxin Analytical Instruments Co. Ltd.,
Thermal analysis was carried out using a Q600 SDT China) equipped with a 5A molecular sieve column and a thermal
thermogravimetric-differential thermal analyzer (America, TA conductivity detector (TCD) using N2 as a carrying gas.
ING.) at a ramping rate of 10 ◦ C min−1 with a flow of mixed gases
of 40 mL min−1 O2 and 100 mL min−1 N2 . The X-ray diffraction Results and discussion
patterns of the prepared samples was obtained by an X-ray
diffractometer (XRD, Bruke-D8) operating at a current of 40 mA Thermal analysis was employed to inspect the thermal poly-
and equipped with a Cu K␣ radiation at a scan rate of 0.1◦ /s merization process. According to the TG and DTG curves in Fig. 1A,
in the range from 5 to 80◦ . The Brunauer-Emmett-Teller (BET) violent decarboxylation of EDTA occurred at about 250 ◦ C, followed
surface areas of the samples were measured using a static volume by slow decomposition of the remaining part, ethylenediaminete-
method with a Quadrasorb SI specific surface analysis instru- tramethylene (EDTM). Fig. 1B is the TG and DTG curves of urea
ment (Quantachrome instruments, America). Fourier transform and UEA-10. Urea was firstly polycondensated to melamine above
infrared (FT-IR) spectra were recorded using an IR Affiniy-1 234 ◦ C, then to melem above 389 ◦ C, and finally to g-C3 N4 in the
FTIR spectrometer in the wavenumber of 400–4000 cm−1 . Field semi-closed environment [6]. It can be observed that UEA-10 shows
emission scanning electron microscopy (SEM-Merlin, Zeiss) and less weight loss before the polymerization of urea to melamine
transmission electron microscopy (TEM, JEM-2100F) were per- (234 ◦ C), implying the reaction between urea and EDTA. As the
formed at an acceleration voltage of 5 and 300 kV, respectively amine groups of urea can react with the carboxyl groups of EDTA,
for morphology and structure observation of the samples. The copolymerization between urea and EDTA will take place during
chemical status and surface chemical composition of the prepared the thermal process. However, the weight loss of UEA-10 was faster
samples were analyzed by X-ray photoelectron spectroscopy (XPS) than that of urea around 250 ◦ C, indicating the escaping of car-
using an X-ray photoelectron spectroscope (Thermo ESCALAB boxyls. Interestingly, the weight loss of urea surpassed that of
250XI, USA). UV–vis diffuse reflectance spectroscopy (UV-vis UEA-10, indicating that the remaining EDTM was grafted to g-
DRS) was conducted on a UV-visible spectrophotometer (Hitachi, C3 N4 network. The grafting structure may not be stable according
U-3010, Japan), using BaSO4 as a reference. Photoluminescence to the faster weight loss of UEA-10 above 400 ◦ C (Fig. 1B). How-
(PL) spectra were measured on a fluorescence spectrophotometer ever, the faster weight loss of UCN-10 above 400 ◦ C as indicated
(F-4500, Hitachi, Japan). The excitation wavelength was 350 nm. in Fig. 1C further demonstrates the incomplete removal of the
66 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75

Fig. 1. TG and DTG curves of (A) EDTA, (B) urea and UEA-10 and (C) UCN and UCN-10.

Fig. 2. Preparation procedure of UCN-x.

 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75 67

Fig. 3. SEM images of (A) UCN, (B) UCN-5, (C) UCN-10, (D) UCN-20, (E) UCN-50 and (F) UCN-100.

grafted EDTM. According to the above analyses, the polyconden- images of the prepared UCN and UCN-x are shown in Fig. 4. Similar
sation process is supposed and illustrated in Fig. 2. EDTA and urea to the SEM image in Fig. 3A, the TEM image of UCN in Fig. 4A shows
combined together by hydrogen bonding through carboxyl groups ultrathin nanosheet morphology with some wrinkles. Such a folded
of EDTA and amine groups of urea. When the carboxyl groups structure of 2D crystals has been demonstrated to be essential to
were removed, the remaining EDTM was grafted to the generated keep stable, similar to single-layered graphene. As shown in Fig. 4,
melamine and finally became the site of the distorted framework the folded nanosheets were replaced by curved nanosheets to form
of g-C3 N4 . hollow structure, which was enhanced upon increasing the amount
The morphology and microstructure of the samples were of EDTA. This is in consistent with the SEM observation. The bending
observed by SEM and TEM. As shown in Fig. 3A, UCN exhibits typi- of the nanosheets of UCN-x is coincident with the proposed distor-
cal nanosheet structure, while the nanosheets become thicker and tion of g-C3 N4 framework, demonstrating the existence of grafted
frizzled for UCN-x samples upon the increase of EDTA. The TEM EDTM as the distortion center.
68 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75

Fig. 4. TEM images of (A) UCN, (B) UCN-5, (C) UCN-10, (D) UCN-20, (E) UCN-50 and (F) UCN-100.

The XRD patterns of UCN and the UCN-x samples are displayed in According to Bragg’s law, the decreased 2␪ value corresponds to
Fig. 5. Two characteristic diffraction peaks are found for all the sam- increased interlayer distance. This may be due to the incorporated
ples. In detail, the stronger peak at around 27.6◦ can be assigned to EDTM obstructing the staking of g-C3 N4 layers, which enlarges the
the (002) inter-planar graphitic stacking of aromatic segment. The gap between the layers.
peak at 12.8◦ corresponds to the (100) plane presenting in-plane The specific surface area is an important factor to determine the
structural packing motif of tri-s-triazine [48]. The peaks of (100) photocatalytic performance of a catalyst. N2 adsorption/desorption
and (002) planes in the XRD patterns of the samples indicate that isotherms of UCN and UCN-x are recorded and the result is shown
incorporation of EDTM in the framework of g-C3 N4 well remains the in Fig. 5C. All the samples displayed a type IV isotherm and their
initial crystal structure of g-C3 N4 . However, the magnified view of adsorption capacity enhanced significantly with increasing the rel-
(002) diffraction peaks in Fig. 5B show regularly shift toward lower ative pressure. UCN-5 and UCN-10 exhibited remarkably enhanced
angles compared with UCN upon increasing the amount of EDTA. N2 adsorption capacity compared with UCN, while excess EDTM
 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75 69

Fig. 5. (A, B) XRD patterns, (C) N2 adsorption/desorption isotherms and (D) BJH pore size distribution curves of UCN and UCN-x.

Table 1 centered at 1700–1200 cm−1 in Fig. 6B, the peaks located at 1236
BET surface area of UCN and UCN-x samples.
(C N), 1315 (C N) and 1407 (C N) cm−1 of UCN shifted toward
UCN UCN-5 UCN-10 UCN-20 UCN-50 UCN-100 high frequencies with increasing the amount of EDTA for the UCN-
2
BET (m /g) 89.4 90.2 106.5 98.7 80.3 79.4 x samples. It seems possible that the shifts might be caused by C N
bonds in the grafted EDTM adjacent to CN in aromatic CN hetero-
cycles, resulting in the enhanced strength of C N covalent bonds.
Thus, it can be concluded that the generated EDTM has been grafted
(samples of UCN-20, 50 and 100) resulted in lower N2 adsorption into the framework of g-C3 N4 .
capacity. The BET surface areas of the prepared samples were sum- X-ray photoelectron spectra were recorded to disclose more
marized in Table 1. UCN-10 displayed the largest BET surface area of information about the chemical compositions of the UCN and UCN-
106.5 m2 g−1 , resulting from the bending nanosheets. However, the 10 samples. The survey spectra (Fig. 7A) demonstrate that UCN and
BET surface areas became smaller upon increasing amount of EDTA UCN-10 are mainly composed of C and N. UCN and UCN-10 display
added, which is ascribed to thickening of the curved nanosheets, similar C 1 s spectra (Fig. 7B) with two peaks located at about 285.04
in accordance with the TEM observation. Larger specific surface and 288.30 eV, respectively. According to the previous reports, the
area will provide more active sites for improving the photocatalytic peak at 288.30 eV is related to the carbon with C N C bonding,
performance. The BJH pore size distribution curves are illustrated while the peak located at 285.04 eV denotes the adventitious car-
in Fig. 5D. Obviously, all UCN-x samples exhibited more uniform bon. Fig. 7C is the high resolution N 1 s spectra of UCN and UCN-10,
mesopores and less micropores compared with UCN. The larger all displaying four peaks at the binding energy of 398.60, 399.5,
pores were formed due to the distortion of the framework of g- 401.0, and 404.6 eV, which are attributed to the sp2 hybridized aro-
C3 N4 . matic nitrogen in the triazine units (C N C groups), the bridging
FT-IR spectra are utilized to further confirm the incorpora- N atoms in N (C)3 or H N (C)2 groups, quaternary N of amino
tion of EDTM in g-C3 N4 . As shown in Fig. 6A, all the samples groups (N H) and ␲ electron excitations in g-C3 N4 heterocycles,
exhibit several typical absorption bands, revealing the characteris- respectively. The C N and C C bonds in EDTM and the proposed
tic structure of g-C3 N4 . In detail, the broad band between 3500 and C N bonds between EDTM and 3,s-triazine unit were not identi-
3000 cm−1 is assigned to N H stretching vibration mode which fied because of the existence of C N bonds in g-C3 N4 framework
comes from the surface uncondensed amine groups. The peaks and the C C bonds from adventitious carbon, as well as the small
centered at 1700–1200 cm−1 relate to the stretching modes of aro- amount of EDTA addition.
matic C N heterocyclicstretches of the triazine (C6N7) ring and the The optical properties of the UCN and UCN-x samples were
peak located at 807 cm−1 represents the breathing mode of the tri- investigated by UV–vis diffuse reflectance absorption (DRS) and
azine units. However, according to the magnified view of the peaks
70 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75

Fig. 6. FT-IR spectra of UCN and UCN-x.

Fig. 7. XPS spectra of UCN and UCN-10, (A) survey spectrum, high resolution spectra of (B) C 1 s and (C) N 1 s of UCN and UCN-10.

photoluminescence (PL) spectroscopy. As shown in Fig. 8A, UCN-10 was observed for all the UCN-x samples corresponding to the n-␲*
exhibits enhanced absorption in the whole solar spectrum rang- transition of N lone electron pairs [46,47]. According to our pre-
ing from 200 to 800 nm and the absorption edge of UCN-x shifts vious work, the n-␲* transition was induced by the distortion of
a little to longer wavelength in comparison to that of UCN. The g-C3 N4 framework due to the grafting of carbon atoms [18]. In
shift increases upon increasing the amount of EDTA added in the the present work, the grafted EDTM shows similar effect due to
precursors. Significantly, an additional absorption around 500 nm its special chelate structure, as displayed in Fig. 2.
 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75 71

Fig. 8. (A) UV–vis absorption spectra and (B) PL spectra of UCN and UCN-x.

Fig. 9. PL spectra of (A) UCN-10 and (B) UCN dispersed in deionized water under different excitation wavelengths.

Fig. 10. (A) Periodic ON/OFF photocurrent response of UCN and UCN-x in 0.5 M Na2 SO4 electrolyte under visible light irradiation (␭ > 420 nm) at 0.5 V vs. Ag/AgCl electrode,
and (B) electrochemical impedance spectroscopy Nyquist plots of UCN and UCN-10 in 0.010 M K3 Fe(CN)6 /K4 Fe(CN)6 electrolyte in the dark.

Photoluminescence (PL) emission was examined to reveal the cating the prevented recombination of photogenerated electrons
recombination of photo-induced electrons and holes in the sam- and holes in UCN-x photocatalysts. At the same time, the emis-
ples. As shown in Fig. 8B, UCN shows a strong emission peak at ca. sion peaks of UCN-x show apparent red shifts compared to that of
480 nm, while the peaks of UCN-x samples decreased largely, indi- UCN (from 480 to 510 nm). The weaker PL peaks and the red shift of
72 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75

emission peaks of UCN-10 and UCN were excitation-independent.

Compared with the emission peak at 450 nm of UCN in Fig. 9A, the
peak of UCN-10 is shifted to 470 nm corresponding to the ␲-␲*
transitions, which is in accordance with the above result of UV–vis
DRS. Furthermore, UCN-10 shows a new peak at 500 nm, which is
ascribed to n-␲* transition of the N lone pair electrons. In addition,
the peaks at 360 and 404 nm of UCN-10 become stronger under the
excitation wavelength shorter than 280 nm, indicating that more
inner shell electrons are excited [49,50]. The emission peaks at
360 nm and 404 nm can be attributed to the radiative recombi-
nation of ␲-␲* and n-␲* transition, respectively. The enhanced
emission peak at 404 nm of UCN-10 confirms the n-␲* transition
induced by the distorted framework and the enhanced emission
peak at 360 nm of UCN-10 indicates the extended delocalization
of ␲-electrons in UCN-10, which are beneficial for the utilization
of visible light and the migration of photo-induced charge carriers,
Fig. 11. EPR spectra of UCN-10 and UCN in the dark and under visible light irradia- respectively.
tion (␭ > 420 nm) at room temperature with a g-value 1.999. The prepared samples were used to fabricate photoelectrodes
for further investigating the photo-induced charge transfer and
separation behaviors. According to Fig. 10A, UCN-5 and UCN-10
absorption edge of UCN-x comes from the EDTM-grafting structure, showed apparent enhancement of photocurrent compared with
which could promote the ␲*-electron delocalization in the g-C3 N4 UCN, indicating improved charge separation. However, excess
network and activate the n-␲* transition. EDTA led to lower photocurrent, which is in accordance with the
PL spectra of UCN-10 and UCN under different excitation wave- BET result. Larger specific surface area will provide more active sites
lengths were also recorded. As depicted in Fig. 9A and B, the

Fig. 12. (A) The amount of H2 evolution and (B) H2 evolution rate over the prepared samples under visible light irradiation (␭ > 420 nm); (C) Wavelength dependence of H2
evolution rate over UCN-10 and UCN, and (D) stability of UCN-10 during prolonged photocatalytic reaction.
 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75 73

Fig. 13. Schematic illustration for the photocatalytic process over UCN-10 photocatalyst under visible light irradiation (␭ > 420 nm).

for improving the photocatalytic performance. In addition, excess lengths (Fig. 12C). Obviously, the photocatalytic performance of the
grafted EDTM can introduce more defects to the framework of g- prepared samples is closely accordant with their optical absorp-
C3 N4 , which are recombination sites for photogenerated electrons tion property (Fig. 8A), suggesting that the harvested photons is the
and holes, causing low photocatalytic activity. The Electrochem- main impetus of the photocatalytic reaction. In addition, UCN-10
ical impedance spectroscopy (EIS) was measured in the dark to still shows high photocatalytic performance (HER = 20.9 ␮mol h−1 )
gain deeper insights into charge transport behavior in the sam- even when the irradiation wavelength is extended to 500 nm, while
ples (Fig. 10B). UCN-10 displayed obvious decrease in semicircular the photocatalytic H2 evolution rate falls to 4.2 ␮mol h−1 over UCN
Nyquist plot compared with UCN, indicating an improved elec- at 500 nm. This result demonstrates that UCN-10 exhibits advanced
tronic conductivity, which is beneficial for faster charge transfer optical property to drive photochemical reactions. In addition, the
and separation. This result clearly demonstrates that modification apparent quantum yield (AQY) for UCN-10 was determined at
of g-C3 N4 framework with EDTM could effectively promote the ␭ = 450 nm. The average intensity of irradiation was assayed to be
photo-induced charge transfer and separation, which leads to obvi- 2.04 mW cm−2 and the irradiation area was 38.47 cm2 . The num-
ous improvement of photocatalytic performance. ber of the incident photons (N) in 1 h was calculated by following
Room temperature electron paramagnetic resonance (EPR) was equation:
employed to further investigate the electronic property of the
E␭ 2.04 × 10−3 × 38.47 × 3600 × 450 × 10−9
EDTM-modified g-C3 N4 . Fig. 11 shows one single Lorentzian line at N= =
hc 6.626 × 10−34 × 3 × 108
a g-value of 1.999 for UCN and UCN-10, which are attributed to the
unpaired electrons in the aromatic rings of carbon atoms [18,35]. = 6.40 × 1020 (1)
The EPR intensity of UCN-10 is greatly enhanced both in the dark
and under visible light irradiation compared to that of UCN, sug-
The rate of H2 evolution was 43.7 ␮mol h−1 . The AQE was calcu-
gesting a greater delocalization and mobility of the spins leading to
lated by following equation:
higher charge carrier density, which confirms that the optical and
electronic property of UCN-10 was modified. 2 × 6.02 × 1023 × 43.7 × 10−6
The photocatalytic activity of the prepared samples was evalu- AQE = × 100% = 8.2% (2)
ated by H2 release reaction. As shown in Fig. 12A, the production 6.4 × 1020
of H2 increased linearly upon prolonging the irradiation time. This AQE value is much higher than the reported data (5.1% at
UCN-5 and UCN-10 show remarkably enhanced photocatalytic per- 420 nm, the highest of all the metal-free g-C3 N4 nanosheets pho-
formance. However, excess EDTA resulted in smaller BET surface tocatalysts [51]).
area and lower photocurrent, indicating less active sites and less The stability of UCN-10 was evaluated by repeating the photo-
efficient separation of charge carriers for H2 evolution. Thus, UCN- catalytic reaction under the same condition for four cycles (16 h).
20, 50 and 100 exhibited lower photocatalytic activity. According As shown in Fig. 12D, no significant decrease was observed in pho-
to Fig. 12B, the average H2 evolution rate within 4 h over UCN- tocatalytic H2 evolution rate, confirming the high stability of the
10 reaches 116.4 ␮mol h−1 , which is 3.5 times of that over UCN EDTM-grafted g-C3 N4 .
(33.1 ␮mol h−1 ). To investigate the driving force of the photocat- Based on the above analyses, a visible light photocatalytic evo-
alytic reaction, the wavelength-dependence H2 evolution over UCN lution mechanism on UCN-10 is proposed in Fig. 13. Under the
and UCN-10 was examined with band-pass filters of different wave- visible light illumination, both ␲-␲* and n-␲* electron transition
74 F.-Y. Su, W.-D. Zhang / Molecular Catalysis 432 (2017) 64–75

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