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Mixed metal nanoparticle assembly Lin et al.
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COMMUNICATION
Porous Graphitic Carbon Nitride Synthesized via Directly
Polymerization of Urea for Efficient Sunlight-driven Photocatalytic
Hydrogen Production
Yuewei Zhang,a,b,c Jinghai Liu,a,b,c Guan Wua,b and Wei Chen* a
Published on 25 June 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30948C

5 Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x

Energy captured directly from sunlight provides an attractive among mixed-oxide semiconductor electrodes.7 Other reports

Nanoscale Accepted Manuscript

approach toward fulfilling the need for green energy resource demonstrate preference of porous electrodes in the water splitting
on the terawatt scale with minimal environment effect. 55 system as well.8, 9 Recently, catalytic efficiency was found to be
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10 Collecting and storing solar energy into fuel through strongly dependent on the porosity and surface area of g-C3N4.
photocatalysized water splitting to generate hydrogen in a Considering the advantages of porous structure, some synthetic
cost-effective way is desirable. To achieve this goal, low cost strategies have been used to introduce it into g-C3N4. For
and environmentally benign urea was used to synthesize example, when sulfur was doped into g-C3N4 by aftertreatment in
metal-free photocatalyst graphitic carbon nitride (g-C3N4). 60 H2S atmosphere at 450 ℃ , the increased surface area and H2
15 Porous structure is achieved via one-step polymerization of production were obtained.10 Mesoporous structure was introduced
the single precursor. The porous structure with increased with TiO2 spheres, silica particle, anodic aluminium oxides as
BET surface area and pore volume shows much higher hard templates to improve the surface area of as-prepared g-C3N4
hydrogen production rate under simulated sunlight as well.11, 12, 13 However, most of these systems required
irradiation than thiourea-derived and dicyanamide-derived 65 additional hard templates and/or complicated post-treatments.
20 g-C3N4. The presence of oxygen atom is presumed to play a Thus it is highly desirable to develop a simple, template-free and
key role in adjusting the textural properties. Further direct strategy to improve the reactivity of primitive g-C3N4.
improvement of photocatalytic function can be expected with Urea molecule contains C, N, O and H elements only, which
after-treatment due to its rich chemistry. exactly formed original chemical ingredients in a prebiotic soup.
70 Urea is a common, low-cost material suitable for large scale
production. Moreover, it is an active molecular precursor under
25 Mimicking natural photosynthesis to split water into hydrogen is thermal treatment. We reported a convenient approach to obtain
an attractive way to directly store solar-converted energy in the g-C3N4 from urea with self-supported gas.14 Gas bubbles
form of chemical bonds.1, 2 In the photochemical water splitting produced during reaction have been frequently used as soft-
system, a solid surface is required to catalyze the chemical 75 template to help inorganic nanocrystals form porous micro-
reactions. Thus earth abundant, inexpensive and robust structures.15 Compared to other template-synthetic methods, this
30 photocatalysts with highly catalytic activity under visible light are soft-template method is very simple, convenient and avoids the
urgently pursued to meet the needs of terawatt solar energy introduction of impurities, and is therefore suitable for synthesis
transfer.3 Recently, an organic, metal-free photocatalyst graphitic of porous microstructure. Also, generated gas plays an important
carbon nitride (g-C3N4), composed of C and N elements only, has 80 role in the processing of carbon nitride condensation.16 Different
demonstrated great potential in sustainable solar energy polymerized product can in principle adjust the electronic and
35 utilization.4 Condensed g-C3N4 is calculated and proved to feature optical properties. From these two aspects, we can expect the
an electronic band structure with band edges straddling H2O photochemical properties of urea-derived product differ from
redox potentials, and thus it can thermodynamically photosplit those synthesized with cyanamide (monomer),4 dicyandiamide
water in aqueous solution. However, when as-synthesized 85 (dimer),10 melamine (trimer)17 and melamine derivatives.18
materials are applied to produce hydrogen, the efficiency for the Herein, we study the contribution of urea-polymerized powder
40 first generation of g-C3N4 is rather low, with total evolution of (denoted as UCN) with obvious porous structure to the
770 µmol H2 after 72 h, not only because of high recombination photocatalytic activity. Facile one-step synthesis process is
rate of photo-generated electron-hole pairs but also its low conducted in the air without introducing extra hard template. In
surface area.4 90 comparison, thiourea (urea derivative) and dicyandiamide
Porous structure materials are especially attractive as (DCDA, commonly used precursor) are also used as single source
45 heterogeneous catalysts which allow for enhancing the efficiency under the same pyrolysis reaction conditions (denoted as TCN
of energy conversion by increasing semiconductor surface area and DCN). These g-C3N4 powders all showed the characteristic
and creating multiple scattering effects.5 E. A. Speers et al. graphitic-like layer structures and repeating units. However, UCN
reported an method of forming monolithic porous titania glass, 95 possesses high Brunauer–Emmett–Teller (BET) surface area and
which is uniquely suited to photo-formation of H2 from water.6 obviously porous structure, which is a key step towards the
50 Porous BiVO4 was used to fabricate thin-film electrodes on photocatalytic H2 production from water on polymeric g-C3N4.
conducting glass for H2 production from water under visible light, This work clearly presents a promising raw material and shows a
showing the highest photon-to-current conversion efficiency

This journal is © The Royal Society of Chemistry [year] [journal], [year], [vol], 00–00 | 1
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a b a b

35
Fig. 3 Hydrogen production from water by UCN, TCN and DCN. H2
production from water (a) without (black) and with (red) TEA(~10vol.%)
as electron donor under simulated sunlight by Pt-loaded g-C3N4 for 25
hours and 8 hours respectively. (b) Stable hydrogen production for 8
c d 40 hours with TEA.

The nitrogen adsorption-desorption isotherms and Barret-

Published on 25 June 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30948C

Joyner-Halenda (BJH) pore size distribution curves of the three

powders indicate that UCN, TCN and DCN exhibit type Ⅲ
behavior, which is due to the weak adsorbent-adsorbent
interaction (Figure 2a).20 The BET surface areas of TCN (11.3 m2

Nanoscale Accepted Manuscript

45

g-1) and DCN (12.3 m2 g-1) are about one sixth of UCN (69.6 m2
g-1). The measured pore volume of UCN (0.321 cm3 g-1) presents
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more porousification than TCN (0.085 cm3 g-1) and DCN (0.086
cm3 g-1). An average pore diameter of 18.2 nm for UCN can be
Fig. 1 Typical TEM images of g-C3N4. (a) UCN, (b)TCN, (c)DCN. (d) 50 estimated from the BJH pore size distribution (Fig. 2b). These
Experimental XRD patterns of the polymeric carbon nitride, which reveal data illustrate that employing urea as precursor could
a graphitic structure with an interplanar stacking distance of aromatic significantly introduce porous structure with increased surface
5 units of 0.326nm. area, enlarged pore volume and narrow pore size distribution.
new method in optimizing semiconductor-based water splitting In regard to photocatalytic activity property, we examined the
systems. 55 stability and activity of hydrogen evolution under simulated solar
XRD patterns, TEM images, N2 adsorption-desorption irradiation. The catalyst was loaded with Pt (3 wt%) as co-
measurement were tested to investigate the structure of the three catalyst. A typical time course of H2 production is shown in
10 samples. TEM images in Figure 1a shows a two-dimensional Figure 3. As expected, stable hydrogen evolution can be observed
structure consisting of small flat sheets with wrinkles and with three different photocatalysts from pure water for 25 hours.
irregular shape. A typical porous morphology of UCN powders is 60 Moreover, the system shows remarkably improved photocatalytic
exhibited. However, large sheets were presented without porous function (~200 times) using TEA as electron donor than pure
structures in the TCN and DCN samples (Figure 1b-c). XRD water system with good stability (Figure 3a-b). Most importantly,
15 patterns (Figure 1d) show two distinct diffraction peaks. The UCN presents a remarkable improvement in photocatalytic H2
strongest XRD peak (002) at around 27.4° (d=0.325 nm) is a production than TCN and DCN. The final overall activity of
characteristic inter-planar stacking peak of conjugated aromatic 65 UCN was achieved at a rate of 47.2 μmol h-1, which shows an
systems. Another distinct peak (100) at 13.1° (d=0.675 nm) can increase by a factor of 3.1 than 15.1 μmol h-1 for TCN and a
be attributed to in-planar structural packing motif. They confirm a factor of 2.26 than 20.9 μmol h-1 for DCN. The enhanced activity
20 graphitic-like layer structure for UCN, TCN and DCN.4 Except corresponds to the enlarged surface area and porousification of
for the same peak value, the (200) peak of UCN displays a the UCN sample.
broadening peak and decreased peak intensity than those of TCN 70 It is interesting to analyze the measured electronic properties
and DCN, indicating that the crystal growth of graphitic carbon of resulted UCN, TCN and DCN. Herein, UV-Vis DRS results in
nitride is inhibited by the utilization of urea according to Figure 4a show typical semiconductor optical characteristics. The
25 Scherrer’s formula. 19 These results along with FTIR spectra absorption edge was at about 455, 476 and 466 nm for UCN,
(Figure S1) and XPS spectra (Figure S2-5) state clearly that g- TCN, DCN separately, corresponding to optical band-gap energy
C3N4 can be synthesized either using two novel urea-series raw 75 of each polymer ca. 2.73, 2.60 and 2.66 eV. Our photo-
materials or traditional DCDA, while UCN powders from urea luminescence measurements (Figure 4b) show fluorescence
favors porous structure. emission peaks of 452, 463, 460 nm for UCN, TCN, DCN
samples. Moreover, apparently enhanced strong PL signals of
a b a b

30

Fig. 2 (a) N2 adsorption-desorption isothermal curves and (b) Fig. 4 (a) The UV-Vis diffuse reflectance absorption spectra of graphitic
Corresponding BJH pore-size distribution curves of as-prepared UCN, 80 carbon nitride, where the F(R) represents the optical absorption of UCN,
TCN and DCN. The pore diameter distribution was determined from the TCN and DCN based on Kubelka–Munk equation. (b) Photoluminescence
desorption branch of the isothermal. (PL) spectra for UCN, TCN and DCN samples under 370 nm excitation.
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Table 1 Microstructure and photocatalytic properties of photocatalysts

synthesized from different precursors.

SA PV PD C/N H2 evolution H2 evolution Band

[m2 g-1] a[cm3g-1]b [nm]c molar rate rate Gap
rationd [μmol h-1]e [μmol h-1]f [eV]
UCN 69.6 0.321 18.2 0.72 0.25 47.2 2.73
TCN 11.3 0.085 26.2 0.78 0.066 15.1 2.60
DCN 12.3 0.086 24.4 0.79 0.083 20.9 2.66
a
BET surface area. b Pore Volume: BJH desorption cumulative volume of
pores. c Pore Diameter: Average pore diameter determined by BJH
5 method. d Element analysis from XPS survey. e Hydrogen production
from pure water. f Hydrogen production from solution with TEA as
sacrificial donor.

TCN and DCN are observed, indicating the more intensive

Published on 25 June 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30948C

10 recombination efficiency of photogenerated charge in TCN and

DCN. The reduced bandgap and stronger PL signals can both be Scheme 1 Microscopic mechanism of polymeric carbon nitride.
contributed to the higher order and better condensation of TCN
and DCN, which leads to a stronger conjugative effect.10 For this

Nanoscale Accepted Manuscript

60 different porous properties, effect of chemical structure must be
reason, the minimum energy for electron transition decreases, so taken into consideration. On one hand, due to the much stronger
that intrinsic absorption edge for highly condensed g-C3N4 red- electronegativity of O atom in urea molecule than S in thiourea,
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15

shifted. Moreover, better condensed structure can be exsited hydrogen bonds during the synthesis process from urea
advantageous to the emergence and the move of delocalized will lower the heat of polymerization, which is unfavorable to
electron. XPS revealed a larger C/N molar ratio of TCN (0.78) 65 high polymerization of UCN. On the other hand, the stronger C-O
and DCN (0.79) than UCN (0.72) (Table 1), along with the (358 kJ/mol) than C-S bond energy (272 kJ/mol) decelerates the
20 smaller ratio of N2 (either tertiary nitrogen N-(C)3 groups linking rate of releasing H2X (X=O, S) after reacted with self-supported
structural motif (C6N7) or amino functions carrying hydrogen NH3, which leads to low polymerization as well. As a whole,
((C)2-N-H) in connection with structural defects and incomplete although self-generated NH3 exsits in both systems, pyrolysis
condensation) to N1 (occurrence of C-N=C groups) in the N 70 with urea obviously prefers a less condensed and more porous
element fitting curve (Figure S3b, 4b, 5b), also indicating that the product, in accord with our experiment results.
25 condensation was promoted by using thiourea and DCDA,16 as
less pendant amino groups existed in the polymerized TCN and Conclusions
DCN.
Generally, TCN and DCN with reduced bandgap than UCN are In summary, we have explored porous g-C3N4 simply
assumed to be favorable for photocatalytic system by absorbing polymerized from urea in air with semiconductor characteristics
30 more light and providing more available electrons. In the matter 75 without extra templates. The efficiency of hydrogen production
of fact, the ratio of normalized activity to specific surface area from the photocatalytic reduction of water can be enhanced
was 0.4: 0.8:1 for UCN, TCN and DCN, indicating that the largely by a fact of 3.1 than g-C3N4 prepared by sulfur-involved
alternated electronic structure can make a contribution to the urea derivative and 2.26 than commonly used DCDA. Thus, it is
improved photocatalytic activity. However, according to the worthy to exploit further development of graphitic carbon nitride
35 overall measured activity of photocatalyst water splitting, in our 80 polymerized with inexpensive, active, oxygen-involved urea.
case, surface area plays a more prenominant role in influencing We would like to thank National Natural Science Foundation
hyrdrogen production than electronic properties. of China (21143004), Science and Technology Support Key
Finally, to understand the advantages of urea as precursor, the Project from Jiangsu Province (BE2009643), Natural Science
microscopic mechanism of the reaction paths of g-C3N4 may be Foundation of Jiangsu province (BK2011365) and Special
40 sketched as Scheme 1 on the basis of the above discussion, along
85 Foundation of President of The Chinese Academy of Sciences.
with former experimental studies21-24 and ab initio calculation.16,
25

As usual, DCDA is recommended to be used as a precursor and Notes and references

promotes a rather rapid passage of the melamine phase to a
i-Lab, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese
45 increase the mass efficiency in the polymerization process. Academy of Sciences, 398 Ruoshui Road, Suzhou, 215123, P. R. China.
DCDA goes through a more direct polyaddition process than E-mail: [email protected]; Fax: +86 (0)512-62603079; Tel: +86
urea-series precursors to form melamine. Since only minute 90 (0)512-62872528
b
quantity of NH3 was released during the reaction, well-structured Graduate University of Chinese Academy of Sciences, 19A Yuquan Road,
and ordered polymer can be obtained without the presence of Beijing, 100049, P. R. China
c
50 much gas bubbles, which is proved by less exsited dangling Institute of Chemistry, Chinese Academy of Sciences, No. 21st North
Street Zhongguancun, Beijng, 100190, P. R. China
amino groups as well. From this point, less condensed and
95 † Electronic Supplementary Information (ESI) available: Methods for
ordered, polymeric UCN than DCN can be expected, which leads preparing and characterizing UCN, TCN and DCN sample. Methods for
to porousification of UCN. examining the photocatalytic hydrogen production. FTIR, XPS, digital
Two urea-series precursors undergo similar thermal photos of three products are shown in Fig. S1-6. See
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