Subscriber access provided by University of Newcastle, Australia
Article
Photo-regenerable, bifunctional granules of carbon doped g-C3N4 as adsorptive photocatalyst for the efficient removal of tetracycline antibiotic Suyana Panneri, Priyanka Ganguly, Midhun Mohan, Balagopal N Nair, Abdul Azeez Peer Mohamed, Krishna Gopa Kumar Warrier, and U. S. Hareesh ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.6b02383 • Publication Date (Web): 20 Dec 2016 Downloaded from http://pubs.acs.org on December 21, 2016
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
ACS Sustainable Chemistry & Engineering is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Photo-regenerable, bifunctional granules of carbon doped g-C3N4 as adsorptive photocatalyst for the efficient removal of tetracycline antibiotic
1 2 3
Suyana Panneriab, Priyanka Gangulya, Midhun Mohana, Balagopal N. Naircd, Abdul Azeez Peer Mohameda, Krishna G. Warriera and U. S. Hareeshab*
4 5 6 7 8 9 10 11 12
a
Materials Science and Technology Division, National Institute for Interdisciplinary Science and Technology (CSIR-NIIST), Thiruvananthapuram - 695019, India. b
Academy of Scientific and Innovative Research (AcSIR), New Delhi, India c R&D Center, Noritake Co. Limited, Aichi 470-0293, Japan d Nanochemistry Research Institute, Department of Chemistry, Curtin University, GPO Box UI987, Perth, WA6845, Australia
13 14 15
Corresponding Author
16
E-mail:
[email protected],
[email protected] 17 18 19 20 21 22 23 24 25 26 27 1 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 2 of 41
28
ABSTRACT
29
Environmental remediation employing semiconducting materials offer a greener solution for
30
pollution control. Herein, we report the development of high surface area porous architecture of
31
C3N4 nanosheets by a simple aqueous spray drying process. g-C3N4 nanosheets obtained by the
32
thermal decomposition of urea-thiourea mixture are spray granulated to microspheres using 2
33
weight % poly vinyl alcohol (PVA) as binder. The post granulation thermal oxidation treatment
34
resulted in in-situ doping of carbon leading to improved photophysical properties compared to
35
pristine g-C3N4. The C3N4 granules with surface area values of 150 m2/g rendered repetitive
36
adsorption of tetracycline antibiotic (~75% in 60 min) and the extended absorption in the visible
37
region facilitated complete photocatalytic degradation upon sunlight irradiation (>95% in 90
38
min). The delocalized π bonds generated after carbon doping and the macro-meso porous
39
architecture created by the granulation process aided high adsorption capacity (70 mg/g). The
40
photo-regenerable, bi-functional materials herein obtained can thus be employed for the
41
adsorption and subsequent degradation of harmful organic pollutants without any secondary
42
remediation processes.
43
Key words: graphitic carbon nitride (g-C3N4), spray granulation, carbon doping, adsorptive
44
photocatalyst, photo-regenerable, tetracycline
45 46
1. Introduction Utilization of photocatalytic semiconductors for the degradation of organic pollutants and
47
harmful microbes has been amply demonstrated through a variety of systems like TiO2,
48
ZnO, ZnS etc.1-4 The widespread use of pharmaceutical compounds like antibiotics has,
49
in recent times, posed a major threat to the environment due to issues associated with its
50
degradation and safe disposal. Consequently, we are faced with the emergence of newer 2 ACS Paragon Plus Environment
Page 3 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
51
hazards, like antibiotic resistant bacteria, that call for immediate remedial measures.5-6
52
The greener approach for the alleviation of such issues is the use of sunlight active
53
photocatalysis with appreciable efficiencies and recyclability.7 A recent entrant to the
54
category of semiconductor photocatalysts is graphitic carbon nitride (g-C3N4) with a band
55
gap value of 2.7 eV.8-9 This organic semiconductor characterized by exceptional chemical
56
and thermal stability found wide applications in water splitting, organic pollutant
57
degradation, organic catalysis and as electrocatalysts under visible light.10-13 However the
58
poor surface area, the faster recombination of excitons and the low visible light
59
absorption render g-C3N4 less effective.14 Multiple strategies are adopted to overcome
60
these
61
heterostructure formation and liquid phase exfoliation are employed to improve the
62
catalytic efficiencies.11,
63
electronic properties favorably for increased absorption over an extended wavelength
64
regime.22-25 The thermal oxidation etching process induces exfoliation of the stacked
65
C3N4 layers resulting in significantly improved surface area values.16
66
Conventional adsorption of pollutants is currently practiced through materials like
67
activated charcoal, silica gel, fly ash, MOF, etc by virtue of their high surface area and
68
adsorption efficiency. However, these adsorbents necessitates stringent conditions for
69
desorption making the regeneration process environmentally unfriendly and expensive.26
70
It is therefore desirable to develop materials that combine adsorption with photocatalytic
71
activity resulting in the formation of bifunctional adsorptive photocatalysts. This
72
approach is particularly advantageous as it doesn’t require secondary remediation
73
measures for the removal of the pollutants. The adsorbed pollutant is phtocatalytcially
short
comings.
Consequently
15-21
approaches
like
doping,
thermal
etching,
Among these approaches, self doping in C3N4 alters
3 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 4 of 41
74
degraded under sunlight irradiation offering fast regeneration of the adsorptive
75
photocatalyst and an environmentally benign solution for the complete removal of the
76
harmful contaminants.
77
Use of free flowing microspheres is advantageous in packed bed systems and is thus
78
favored for industrial applications.27 One of the techniques employed for the fabrication
79
of microspheres is the silica template approach that warrants post synthetic etching
80
processes using fluorinated solvents that are time consuming and environmentally
81
hazardous.28-31 The alternate approach of solvothermal synthesis utilizes organic solvents
82
that pose issues related to its safe disposal.32-33 Aqueous spray drying is an
83
environmentally benign solution amenable for industrial scale powder granulation.27,
84
Spray drying consists of atomizing a solution into liquid drops in a hot air flow to get dry
85
solid particles after water evaporation. In this work, spray drying was employed for the
86
first time to develop adsorptive photocatalysts based on granulated g-C3N4 with high
87
surface area. This template free spray drying process followed by thermal oxidation in air
88
atmosphere enabled the formation of microspheres having wider pore size distribution. As
89
an added benefit, the incomplete burn out of the PVA binder induced self doping of
90
carbon in C3N4 sheets leading to improved light absorption and reduced exciton
91
recombinations. The adsorption and subsequent photocatalytic activity of the as prepared
92
sample was evaluated by tetracycline (TC) degradation under sunlight irradiation. The TC
93
adsorption on of spray dried C3N4 has been further analyzed by using the different
94
kinetics and equilibrium adsorption isotherm models. TC molecules adsorbed in the
95
granules were successfully degraded by sunlight induced photocatalysis and the
96
recyclability studies showed no significant loss of activity. The study thus provides
34
4 ACS Paragon Plus Environment
Page 5 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
97
processing pathways for the realization of photocatalysts that are bifunctional and photo-
98
regenerable.
99
Results and Discussion
100
Crystal Structure
101
XRD pattern of spray dried C3N4 (CSDC) showed consistent peaks with that of the bulk C3N4
102
(BC) indicating that the C3N4 phase has been retained after spray drying and thermal oxidation
103
(Figure 1). The main peak at 27.48° corresponded to the (002) plane and signified the
104
interplanar stacking of aromatic units.35 The low angle reflection peak (100) at about 13.1° was
105
attributed to the crystal plane of tri-s-triazine units.16 Compared with bulk C3N4, the peak at
106
27.48° was shifted to 27.73°, indicating a decreased gallery distance between the layers of C3N4
107
sheets. The IR spectra of the CSDC granules and BC are presented in Figure S1 which showed
108
identical peaks as that of bulk C3N4 reported earlier.36
109
110 111 112 113
Figure 1. XRD pattern of bulk C3N4 (BC) and spray dried C3N4 (CSDC) granules (inset shows the shift in main intensity peak).
114
Morphological Features 5 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 6 of 41
115
The morphology of spray dried samples was analyzed by SEM imaging. Figure 2 depicting the
116
SEM images of spray dried granules indicated a gradation in granule sizes up to 20 microns. The
117
magnified image of a typical granule suggested that the C3N4 sheets are spheriodised using the
118
PVA binder (Figure 2 a and b). C3N4 sheets dispersed in the aqueous slurry containing very low
119
amounts of PVA binder yielded near spherical granules on atomization. The larger distribution of
120
granule sizes, from 5-20 micron is a characteristic feature of the spray drying process. The
121
morphological features of the granules are however retained after the calcination and thermal
122
oxidation etching processes (Figure 2 c and d). Figure S2 illustrates the SEM images of CSDC
123
at different magnifications and Figure S3a and b shows the TEM image and EDX analysis of
124
sheet like bulk C3N4 (BC). The TEM images of the spray dried granules (Figure S4) revealed the
125
nature of porosity. The high magnification image of the granule presented in Figure S4
126
confirmed the porous nature of the granules. The granules appeared as an assembly of C3N4
127
sheets with slits and pores in between them. The template free method of granulation from
128
aqueous slurries used in our studies is an environmentally benign process devoid of any chemical
129
etching commonly employed for template based spheriodisation process.
130
6 ACS Paragon Plus Environment
Page 7 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
131
Figure 2. SEM images of spray dried C3N4 granules (a) and (b) before calcination, (c) and (d)
132
after calcination.
133
Optical Properties
134
UV-Visible absorption analysis
135
The electronic band structures of the samples were analyzed by diffused reflectance spectra
136
(Figure 3a). The BC showed shoulder around 440 nm. The absorption spectra of CSDC granules
137
indicated a red shift extending up to 800 nm with increased absorption intensity. This red shift
138
and increased intensity was attributed to the in situ doping carbon present in the spray dried
139
granules, which was also clear from the colour changing from pale yellow to brown. The
140
bandgap value was estimated from Tauc equation1.37
141
ℎ/ = ℎ − )
142
Where α, hν, Eg and A were absorption coefficient, the photon energy, direct bandgap and a
143
constant, respectively. In the equation n, is a number indicating the nature of transition in the
144
material with values of ½ and 2 for direct and indirect transitions respectively. C3N4 is an
145
indirect bandgap material and the procedure to measure bandgap is given in the supporting
146
information. Figure 3b indicated a reduction of bandgap from 2.80 eV for BC to 2.54 eV for the
147
CSDC granules. The reduction in bandgap facilitated by carbon doping induced extension of
148
absorption to longer wavelength region as reported earlier.22, 24
Equation (1)
149
7 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 8 of 41
150 151
Figure 3. (a) UV-Visible absorption spectra and (b) band gap estimation of bulk C3N4 (BC) and
152
spray dried C3N4 (CSDC) granules.
153
The band edge potentials of both spray dried C3N4 and bulk C3N4 was estimated using the
154
equation 2 and 3.38
155
= χ − 0.5
Equation (2)
156
= −
Equation (3)
157
where EVB, ECB and χ represented respectively the valence band edge potential, conduction band
158
edge potential, and the electronegativity of the semiconductor in Mulliken’s scale (which is the
159
geometric mean of constituent atoms). Ee and Eg provided the energy of free electrons on the
160
hydrogen scale (4.5 eV vs. NHE) and the band gap of semiconducting photocatalyst respectively.
161
The χvalue for the C3N4 is 4.64.38-39 The valence band (VB) edge potentials are 1.54 and 1.41 eV
162
and conduction band (CB) edge potentials are -1.26 and -1.13 eV for bulk and spray dried
163
granules respectively. Both the CB and VB edge potentials shifted significantly after carbon
164
doping improving the absorption in the visible region.
8 ACS Paragon Plus Environment
Page 9 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
165
Photoluminescence emission
166
The mass normalized PL emission spectra presented in Figure 4 compare the separation
167
efficiency of photogenerated electron-hole pairs in C3N4 sheets and granules. The broad emission
168
peak at 460 nm is a characteristic of C3N4 due to band-band emission ascribed to the n-π*
169
electronic transitions involving lone pairs of nitrogen atom in C3N4.15 The significant reduction
170
in peak intensity observed for spray dried C3N4 granules revealed lowered exciton
171
recombinations as reported in many other systems.40 This is ascribed to carbon doping arising
172
out of the residual carbon from the incomplete binder (PVA) burn out process. This has been
173
earlier observed in carbon doped C3N4 obtained by glucose incorporation and by pre-treatment
174
with absolute ethanol.22, 24 The large delocalized π bonds originating from carbon doping induces
175
reduced exciton recombinations.41
176 177
Figure 4. PL emission spectra of bulk and spray dried C3N4 at an excitation wavelength of 360
178
nm.
179
Chemical Composition Analysis
180
The C/N ratios of pure C3N4 and spray dried samples were done by elemental analysis and the
181
value of 0.627 calculated for the spray dried sample was slightly higher than that of pure C3N4
9 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 10 of 41
182
(0.564) as has been observed previously.22 The increased C/N ratio in CSDC granules sample
183
indicated the inclusion of residual carbon arising out of the incomplete burn out of PVA during
184
the heat treatment at 550 °C. This in situ doping of carbon was an outcome of the nitrogen rich
185
environment created during the thermal oxidation etching of C3N4 in the temperature range of
186
400-550 0C. The self doping of carbon was further confirmed through XPS analysis.
187
XPS analysis of bulk (BC) and spray dried C3N4 (CSDC) is presented in Figure 5. XPS
188
survey spectrum of both samples revealed that the elemental composition is carbon and
189
nitrogen (Figure S5). Both exhibited similar C 1s and N 1s spectra without any
190
significant peak shift indicating similar chemical states of C 1s and N 1s in both the
191
samples. The deconvoluted C 1s spectra showed four peaks at 283.7, 284.4 286.4 and
192
288.2 eV which corresponds to graphitic C=C or the cyano-group, adventitious carbon,
193
C-NH2 species and N-C-N coordination in the graphitic carbon nitride respectively
194
(Figure 5 a and c).42 The N 1s peak (Figure 5 b) of bulk C3N4 is deconvoluted into two
195
peaks at 397.7 eV and 399.1 eV due to sp2 N in the triazine rings and bridging nitrogen
196
atoms respectively.43 The intensity of C 1s peak at 283.7 eV is increased while the N 1s
197
peak at 397.7 eV is decreased in the CSDC sample (Figure 5 c and d). This is presumed
198
to be due to the deficiency of N in CSDC prompted by the thermal oxidation etching
199
process and subsequent in situ doping of carbon from the residue of PVA burn out. The
200
C/N ratio estimated from the XPS analysis indicated an increase from 0.86 for bulk C3N4
201
to 1.08 for spray dried calcined granules. This further substantiated the postulation of in
202
situ carbon doping in spray dried samples. It is already reported that the replacement of
203
bridging nitrogen by carbon due to doping, could create large delocalized π bonds that
204
enhances the electrical conductivity and impedes the electron hole recombinations. The
10 ACS Paragon Plus Environment
Page 11 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
205
presence of large delocalized π bonds is also reported to favor increased adsorption of
206
organic moieties due to strong π−π interactions.24, 41
207
208 209
Figure 5. High resolution of XPS patterns (a) C 1s and (b) N 1s of bulk C3N4 (BC) and (c) C 1s
210
and (d) N 1s of carbon doped spray dried C3N4 granules (CSDC).
211
Granulation process
212
The synthesis procedure involving urea and thiourea as a precursor mix produced C3N4 sheets in
213
good yield and enhanced surface area compared to single precursors. Nevertheless, the obtained
214
particles are still aggregated due to which a mechanical exfoliation process like ball milling was
215
essential to arrive at aqueous slurry of good dispersibilty. Atomization of the slurry with PVA as
216
binder yielded aggregation and spheriodisation of C3N4 sheets resulting in micron sized granules.
217
Subsequent calcination of the spray dried granules in air at 550 °C produced porous granules due
218
to thermal oxidation etching as reported before. The formation steps are shown in Figure 6.
219
After the calcination process the colour of the material is changed from yellow to brown
11 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 12 of 41
220
indicating the in-situ doping of carbon, as confirmed from the optical as well as chemical
221
composition analysis.
222 223 224
Figure 6. Schematic representation of the formation of spray dried porous C3N4 granules with carbon doping (CSDC).
225
Surface area and pore Characteristics
226
The spherical arrangement of sheets during the atomization process lead to micron sized granules
227
and the subsequent post granulation thermal oxidation etching process yielded high surface area
228
granules with increased porosity. The bulk C3N4 obtained from the urea-thiourea mixture yielded
229
surface area values of 67 m2/g. On spray granulation and thermal oxidation, the surface area
230
values increased many fold to 151 m2/g. The adsorption isotherms provided in Figure 7 a
231
indicated type II b adsorption behavior, characteristic of adsorption on surface and in cavities
232
formed by the agglomeration of sheet like structures. The pore size distribution by BJH method
233
(Figure 7 b) provided pore sizes in the range of 2-150 nm. It is likely that the agglomerates
234
initially consisted of meso and macropore architecture. The spray dried granules had a wider
235
pore distribution and their total pore volume and surface area (0.46 cc/g and 151 m2/g) were
236
significantly better than the bulk sample (0.33 cc/g and 67 m2/g). The textural properties of the 12 ACS Paragon Plus Environment
Page 13 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
237
bulk and spray dried C3N4 is summarized in Table S1. The presence of large number of surface
238
active sites is presumed to facilitate the adsorption and transfer of pollutant molecules through
239
the interconnected porous network structure favoring superior photocatalytic activity.
240
241 242
Figure 7. (a) Nitrogen adsorption-desorption isotherms and (b) BJH pore size distribution
243
curves of bulk C3N4 (BC) and spray dried C3N4 (CSDC) granules.
244 245
Bifunctional application: Adsorption and Photocatalytic degradation of tetracycline (TC)
246
antibiotic
247
To demonstrate the bi-functional nature of granules, adsorption and photocatalytic experiments
248
were carried out under dark and sunlight irradiation respectively using tetracycline (TC) as a
249
model pollutant. Figure 8 presents the change in concentration of TC with time for the CSDC
250
granules in comparison with BC. The TC does not undergo self photolysis as its concentration
251
remains unchanged with time. The spray dried C3N4 granules showed higher percentage
252
adsorption (79.4%) compared to bulk C3N4 (8%). Adsorption of TC is monitored for 180 minutes
253
and it is observed that adsorption equilibrium is reached within 60 minutes (Figure S6).The 13 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 14 of 41
254
porous morphology and enhanced surface area of the granules induced high rates of adsorption
255
and the adsorbed TC was degraded to greater than 90% within 30-90 minutes of sunlight
256
exposure. The spray dried granules containing the in situ doped carbon created large number of
257
delocalized π bonds which effectively contributed to the enhanced adsorption and photocatalytic
258
degradation, whereas bulk g- C3N4 degraded 54 % only. The extended visible light activity due
259
to small amount of doped carbon and enhanced surface area ensured high photocatalytic activity
260
in spray dried C3N4 granules. As the spray dried granules indicated high adsorption, the samples
261
were further analyzed for its adsorption features.
262 263
Figure 8. Adsorption cum photocatalytic degradation of 100 µm TC using spray dried C3N4
264
granules (CSDC) and bulk C3N4 (BC).
265
Adsorption studies
266
Adsorption capacity
267
The adsorption capacity qe (mg g-1) of the sample was estimated by evaluating the samples in
268
various concentrations of TC for a fixed period of time (60 min). Figure 9 illustrates the
269
variation in qe as a function of different TC concentrations. As the TC concentration increases,
270
the qe also increases, reaching a maximum value at 100 µM [qm (mg g-1)]. Further increase in the 14 ACS Paragon Plus Environment
Page 15 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
271
concentration of TC reduces the qe due to adsorption equilibrium. The spray dried C3N4 granules
272
(CSDC) showed the highest adsorption capacity of 70 mg g-1 and was significantly higher than
273
that for the bulk C3N4 (BC) (5 mg g-1). The carbon doping in spray dried granules induced π-π
274
interactions with the aromatic moieties of tetracycline leading to the enhanced adsorption of the
275
latter.23, 41 Through DFT calculations, it is established that the carbon doping in C3N4 leads to
276
substitution of bridging N atoms with C atoms. This induces formation of large delocalized
277
π bonds among the substituted carbons and the hexatomic rings.24 The aromatic π system in
278
tetracycline molecule effectively interact with the delocalized π system of the carbon doped
279
C3N4. This strong π-π interaction leads to enhanced Tetracycline adsorption on the surface of
280
carbon doped spray dried C3N4 granules.
281
realized by the granulation process and the consequent increase in the surface area favoured
282
improved adsorption properties compared to pristine C3N4.
Moreover the macro-meso porous architectures
283 284
Figure 9. Adsorption capacity of different concentrations of TC using spray dried C3N4 (CSDC).
285
Adsorption isotherm
286
The rate of adsorption followed pseudo second order kinetics and the isotherm fitted well with
287
the Freundlich isotherm model. This is attributed to the presence of larger pore volume in the
288
spray dried granules which can host larger sized antibiotic molecules in their pore channels. The
15 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 16 of 41
289
adsorption data of 100 µM TC was evaluated using the isotherm models of Langmuir,
290
Freundlich, and Dubinin–Kaganer–Radushkevich (DKR). The TC adsorption on spray dried g-
291
C3N4 predominantly followed the Freundlich isotherm model where the linear form is
292
represented as44
293
=
294
where Ce (mgL-1) is the equilibrium TC concentration, Kf (mg1-1/n g-1 L1/n) is the Freundlich
295
constant related to the Gibb’s free energy of adsorption and n (g L-1) is another Freundlich
296
constant related to the adsorption intensity. Figure 10 shows the Freundlich isotherm plot for the
297
adsorption of TC on the CSDC granules. Table 1 summarizes the parameters of Freundlich
298
isotherm. The Langmuir and DKR isotherm equations (S8 and S9) and plots of TC adsorption
299
are presented in Figure S7. The slope is a measure of adsorption intensity or surface
300
heterogeneity, a value closer to zero implies more heterogeneity.
!
Equation (4)
301 302
Figure 10. Freundlich adsorption isotherm of 100 µm TC using spray dried C3N4 (CSDC)
303
granules.
304
Table 1. Summary of the parameters related to Freundlich isotherm Concentration
100 µM 16
ACS Paragon Plus Environment
Page 17 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
305
Isotherm
Freundlich isotherm
306
r2
0.99928
1/n
0.51702
Kf
0.710959
307 308 309 310
The rate at which the TC is adsorbed from an aqueous solution of the spray dried granules is
311
analyzed using different kinetic models. The adsorption data of 100 µM TC fits the pseudo-
312
second order kinetics which can be represented as44
313
"
"
= × "
Equation (5)
$ $ ×
314 315
where K2 (g mg-1 min
-1
316
adsorbed on the surface per unit mass of adsorbent (mg g-1) at the contact time of t. Figure 11
317
shows typical pseudo-second order kinetics plot for the adsorption of TC on the surface of the
318
composite prepared at 100 µM. Table 2 summarizes the details of pseudo-second order kinetics.
319
The regression correlation coefficient value is close to 1 and the estimated qe value using
320
this model is comparable with the experimentally determined value of qe. Thus, it verifies that
321
the adsorption of TC on spray dried g-C3N4 (CSDC) follows pseudo-second order kinetics. In
322
short, the adsorption studies indicated that the CSDC (0.5 gL-) possessed higher adsorption
323
capacity (qm) of 70 mg g-1 for 100 µM TC solution compared to a value of 5 mg g-1 for bulk
324
C3N4 (BC) sheets. The higher adsorption capacity observed for the spray dried sample could be
325
due to the larger surface area and pore volume of the spray dried sample compared to the bulk
326
sample. Moreover, as is clear from Figure 7b, the spray dried sample contained significant
) is pseudo-second order rate constants and qt is the amount of TC
17 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 18 of 41
327
amount of larger pores compared to the bulk sample. This adsorption rate followed the pseudo
328
second order kinetics and fitted well with the Freundlich isotherm model.
329 330
Figure 11. Pseudo second order kinetics of adsorption 100 µm TC using spray dried C3N4
331
(CSDC) granules.
332
Table 2. Summary of the parameters related to pseudo-second order kinetics Concentration
100 µM
Kinetics
Pseudo-second order
r2
0.97616
K2
0.002
qe (calculated)
75
qe (experimental)
70
333 334
Different reactive oxygen scavengers (ROS) were employed to detect the reactive species.
335
10mM of Isopropyl Alcohol (IPA) (the quencher of hydroxyl radical)., 6mM AgNO3 (the
336
quencher of electron), 6mM Benzoquinone (BQ) (the quencher of superoxide anion radical),
337
10mM Triethanolamine (TEA) (the quencher of holes) were respectively added in the
338
photocatalytic reaction mixture and irradiated under sunlight.45 Figure 12 compares the
18 ACS Paragon Plus Environment
Page 19 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
339
formation of active species, through trapping experiments, during the photocatalytic reaction. It
340
is found that photocatalytic degradation of TC was not affected by the addition of isopropyl
341
alcohol indicating that the mechanism is not dominated by hydroxyl radicals. On the other hand,
342
a significant reduction in activity was observed by the addition of AgNO3 confirming the
343
mechanistic role of electrons in the photodegradation process. The degradation, however, was
344
drastically quenched by the addition of triethanolamine and benzoquinone indicating that the
345
dominant reactive species controlling the photocatalytic degradation of tetracycline are holes and
346
super oxide anions radicals respectively. Therefore, it can be concluded that the species affecting
347
the degradation is in the order of holes>superoxide anions>electrons.
348 349
Figure 12. Reactive oxygen species trapping of spray dried C3N4 (CSDC) granules using IPA,
350
TEA, BQ, and AgNO3 under sun light irradiation.
351
Based on the ROS experiments, UV-Vis absorption, and PL emission analysis a possible
352
mechanism for the photocatalytic degradation of the TC molecule is illustrated in Figure 13.
353
From the band edge potential calculations, it is noted that both the CB and VB edge potentials
354
altered significantly after carbon doping leading to the improved visible light absorption ability.
355
Also the high surface area enabled more surface active sites for the adsorption of TC molecules 19 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 20 of 41
356
on spray dried granules and exhibited more photocatalytic degradation. Under visible light
357
irradiation C3N4, generates excitons. The reduction potential of O2/O2- is -0.33 eV and hence the
358
photogenerated electrons could easily react with O2 and reduces it into superoxide radical (O2-)
359
anions that degrade the TC molecules. On the other hand, EVB value of g-C3N4, is +1.41 eV and
360
is lower than the standard redox potential of OH*/H2O (+2.68 eV) and OH*/OH- (1.99 eV). Thus,
361
the photogenerated holes present in the valence band cannot react with H2O or OH- to generate
362
active oxidative species OH*. Hence holes (h+) in the valence band of spray dried C3N4, degrades
363
the TC molecules directly.41,
364
monitored by conducting chemical oxygen demand (COD) experiment (Figure S8). The COD
365
value of 100 µm TC soluton is 202 mg/L where as after adsorption and photocatalysis the values
366
are 28 and 60 mg/L respectively. This increse in value after adsorption is attributed to the
367
formation of intermediate carbonaceous species during photocatalysis.
46
The degree of mineralization of TC degradation preocess is
368 369
Figure 13. Photocatalytic mechanism of tetracycline degradation by spray granulated C3N4
370
(CSDC).
20 ACS Paragon Plus Environment
Page 21 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
371
The efficiency of the developed granules for repeated adsorption and photocatalysis are
372
evaluated through cyclic studies. Figure 14 presents the data on adsorption and photocatalytic
373
degradation of tetracycline under sunlight irradiation after five cycles of repetition. There is
374
hardly any loss of activity in the adsorption and photocatalytic performance of the granules after
375
five cycles. The XRD and FTIR patterns of samples recorded after the cyclic studies, presented
376
in Figure S9 and S10 indicated no changes in phase and functional groups respectively. The
377
prepared material is thus photo-regenerable exhibiting good stability even multiple 4 cycles.
378 379
Figure 14. Cyclic tests on the adsorption and photocatalytic degradation of 100 µm TC using
380
spray dried C3N4 (CSDC) granules.
381
The extended π-π interactions resulting from in-situ carbon doping combined with high surface
382
area and favorable pore characteristics lead to high amount of TC adsorption by the spray dried
383
granules. The adsorbed as well as the TC retained in solution was subsequently degraded under
384
sunlight irradiation. The improved visible light absorption, reduced exciton recombinations
385
thorough carbon doping and enhanced surface area by virtue of the porous architecture aided
386
better photocatalytic activity. Thus the template free, aqueous spray drying process leading to
387
the formation of bifunctional and photo-regenerable C3N4 granules offers an environmentally
388
benign solution for the emerging water pollutants without any secondary treatment.
21 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 22 of 41
389
Conclusions
390
Bulk C3N4 sheets derived from the pyrolysis of urea-thiourea mixture was converted to high
391
surface area granules employing a template free spray drying process followed by thermal
392
oxidation at 500 °C. The spray granulation and oxidation process introduced carbon doping in
393
C3N4 resulting in reduced band gap and extended absorption in the visible light region. The C3N4
394
granules thus formed are demonstrated to perform the dual functions of both adsorption and
395
photocatalysis for the efficient degradation of tetracycline. Recyclability studies indicated no loss
396
of activity even after five cycles. The template free spray drying approach offer a greener
397
pathway for the development of photo-regenerable, bifunctional photocatalysts for the effective
398
degradation of organic contaminants in the environment.
399
ASSOCIATED CONTENT
400
Supporting Information: Detailed experimental procedures for the synthesis of spray dried
401
C3N4 granules, tetracycline adsorption measurements, tetracycline adsorption cum photocatalytic
402
degradation, regeneration, characterization techniques employed, Detailed procedure for band
403
gap measurement, FTIR, XPS survey spectrum, SEM, TEM and elemental analysis of bulk and
404
spray dried C3N4, Textural property table, adsorption of tetracycline in the dark, Langmuir and
405
DKR isotherm plots, COD measurements, XRD and IR of spray dried C3N4 granules before and
406
after photocatalysis.
407
Author Information
408
Corresponding Author
409
E-mail:
[email protected],
[email protected] 410
Tel: 04712535504 (Office), 09446337222 (mobile)
411
Acknowledgements 22 ACS Paragon Plus Environment
Page 23 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
412
Mr. Chandran and Mr. Kiran Mohan are thankfully acknowledged for the SEM and HRTEM
413
micrographs respectively. Ms. Athira A. S. is kindly acknowledged for the COD measurements.
414
The authors are grateful to Council of Scientific and Industrial Research (CSIR, Government of
415
India) for the 12th five year plan project on “IntelCoat” (CSC0114). Author S P thanks CSIR for
416
the research fellowship.
417 418
References
419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 448 449 450
1. Leyland, N. S.; Podporska-Carroll, J.; Browne, J.; Hinder, S. J.; Quilty, B.; Pillai, S. C., Highly Efficient F, Cu doped TiO2 anti-bacterial visible light active photocatalytic coatings to combat hospitalacquired infections. Sci. Rep. 2016, 6. 2. Suyana, P.; Nishanth Kumar, S.; Madhavan, N.; Dileep Kumar, B. S.; Nair, B. N.; Mohamed, A. P.; Warrier, K. G. K.; Hareesh, U. S., Reactive oxygen species (ROS) mediated enhanced anti-candidal activity of ZnS-ZnO nanocomposites with low inhibitory concentrations. RSC Adv. 2015, 5 (94), 76718-76728. 3. Schneider, J.; Matsuoka, M.; Takeuchi, M.; Zhang, J.; Horiuchi, Y.; Anpo, M.; Bahnemann, D. W., Understanding TiO2 Photocatalysis: Mechanisms and Materials. Chem. Rev. 2014, 114 (19), 9919-9986. 4. Amna, S.; Shahrom, M.; Azman, S.; Kaus, N. H. M.; Ling Chuo, A.; Siti Khadijah Mohd, B.; Habsah, H.; Dasmawati, M., Review on Zinc Oxide Nanoparticles: Antibacterial Activity and Toxicity Mechanism. Nano-Micro Lett. 2015, 7 (3), 219-242. 5. Levy, S. B.; Marshall, B., Antibacterial resistance worldwide: causes, challenges and responses. Nat. Med. 2004, 10 (12), S122-S129. 6. Vaz-Moreira, I.; Nunes, O. C.; Manaia, C. M., Bacterial diversity and antibiotic resistance in water habitats: searching the links with the human microbiome. FEMS Microbiol. Rev. 2014, 38 (4), 761-778. 7. Schneider, J.; Bahnemann, D. W.; Ye, J.; Puma, G. L.; Dionysiou, D. D., Photocatalysis : Fundamentals and Perspectives. RSC Energy. Environ. Series 2016, 1-436. 8. Cao, S.; Low, J.; Yu, J.; Jaroniec, M., Polymeric Photocatalysts Based on Graphitic Carbon Nitride. Adv. Mate. 2015, 27 (13), 2150-2176. 9. Papailias, I.; Giannakopoulou, T.; Todorova, N.; Demotikali, D.; Vaimakis, T.; Trapalis, C., Effect of processing temperature on structure and photocatalytic properties of g-C3N4. Appl. Surf. Sci. 2015, 358, Part A, 278-286. 10. Wang, X. C.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, J. M.; Domen, K.; Antonietti, M., A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat. Mater. 2009, 8 (1), 76-80. 11. Ong, W.-J.; Tan, L.-L.; Ng, Y. H.; Yong, S.-T.; Chai, S.-P., Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability? Chem. Rev. 2016, 116 (12), 7159-7329. 12. Verma, S.; Nasir Baig, R. B.; Nadagouda, M. N.; Varma, R. S., Photocatalytic C–H Activation of Hydrocarbons over VO@g-C3N4. ACS Sustainable Chem. Eng. 2016, 4 (4), 2333-2336. 13. Ye, S.; Wang, R.; Wu, M.-Z.; Yuan, Y.-P., A review on g-C3N4 for photocatalytic water splitting and CO2 reduction. Appl. Surf. Sci. 2015, 358, Part A, 15-27.
23 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 487 488 489 490 491 492 493 494 495 496
Page 24 of 41
14. Yu, W.; Xu, D.; Peng, T., Enhanced photocatalytic activity of g-C3N4 for selective CO2 reduction to CH3OH via facile coupling of ZnO: a direct Z-scheme mechanism. J. Mater. Chem. A 2015, 3 (39), 19936-19947. 15. Suyana, P.; K. R, S.; Nair, B. N.; Karunakaran, V.; Mohamed, A. P.; Warrier, K. G. K.; Hareesh, U. S., A facile one pot synthetic approach for C3N4-ZnS composite interfaces as heterojunctions for sunlight-induced multifunctional photocatalytic applications. RSC Adv. 2016, 6 (22), 17800-17809. 16. Niu, P.; Zhang, L.; Liu, G.; Cheng, H.-M., Graphene-Like Carbon Nitride Nanosheets for Improved Photocatalytic Activities. Adv. Funct. Mater. 2012, 22 (22), 4763-4770. 17. Bu, Y.; Chen, Z., Effect of oxygen-doped C3N4 on the separation capability of the photoinduced electron-hole pairs generated by O-C3N4@TiO2 with quasi-shell-core nanostructure. Electrochim. Acta 2014, 144, 42-49. 18. Hu, S.; Ma, L.; You, J.; Li, F.; Fan, Z.; Lu, G.; Liu, D.; Gui, J., Enhanced visible light photocatalytic performance of g-C3N4 photocatalysts co-doped with iron and phosphorus. Appl. Surf. Sci. 2014, 311, 164-171. 19. Lu, C.; Chen, R.; Wu, X.; Fan, M.; Liu, Y.; Le, Z.; Jiang, S.; Song, S., Boron doped g-C3N4 with enhanced photocatalytic UO22+ reduction performance. Appl. Surf. Sci. 2016, 360, Part B, 1016-1022. 20. Tian, W.; Li, N.; Zhou, J., A novel P-doped g-C3N4/Zn0.8Cd0.2S composite photocatalyst for degradation of methylene blue under simulated sunlight. Appl. Surf. Sci. 2016, 361, 251-258. 21. Ma, W.; Wang, X.; Zhang, F.; Fei, X.; Zhang, X.; Ma, H.; Dong, X., Synergetic effect of Li doping and Ag deposition for enhanced visible light photocatalytic performance of g-C3N4. Mater. Res. Bull. 2017, 86, 72-79. 22. Zhao, Z.; Sun, Y.; Dong, F.; Zhang, Y.; Zhao, H., Template synthesis of carbon self-doped g-C3N4 with enhanced visible to near-infrared absorption and photocatalytic performance. RSC Adv. 2015, 5 (49), 39549-39556. 23. Li, Y.; Wu, S.; Huang, L.; Wang, J.; Xu, H.; Li, H., Synthesis of carbon-doped g-C3N4 composites with enhanced visible-light photocatalytic activity. Mater. Lett. 2014, 137, 281-284. 24. Dong, G.; Zhao, K.; Zhang, L., Carbon self-doping induced high electronic conductivity and photoreactivity of g-C3N4. Chem. Commun. 2012, 48 (49), 6178-6180. 25. Fang, S.; Lv, K.; Li, Q.; Ye, H.; Du, D.; Li, M., Effect of acid on the photocatalytic degradation of rhodamine B over g-C3N4. Appl. Surf. Sci. 2015, 358, Part A, 336-342. 26. Ali, I., New Generation Adsorbents for Water Treatment. Chem. Rev. 2012, 112 (10), 5073-5091. 27. Kalluri, S.; Seng, K. H.; Guo, Z. P.; Du, A.; Konstantinov, K.; Liu, H. K.; Dou, S. X., Sodium and Lithium Storage Properties of Spray-Dried Molybdenum Disulfide-Graphene Hierarchical Microspheres. Sci. Rep. 2015, 5. 28. Sun, J.; Zhang, J.; Zhang, M.; Antonietti, M.; Fu, X.; Wang, X., Bioinspired hollow semiconductor nanospheres as photosynthetic nanoparticles. Nat. Commun. 2012, 3. 29. Zheng, D.; Pang, C.; Liu, Y.; Wang, X., Shell-engineering of hollow g-C3N4 nanospheres via copolymerization for photocatalytic hydrogen evolution. Chem. Commun. 2015, 51 (47), 9706-9709. 30. Groenewolt, M.; Antonietti, M., Synthesis of g-C3N4 Nanoparticles in Mesoporous Silica Host Matrices. Adv. Mater. 2005, 17 (14), 1789-1792. 31. Shi, L.; Liang, L.; Wang, F.; Liu, M.; Chen, K.; Sun, K.; Zhang, N.; Sun, J., Higher Yield Urea-Derived Polymeric Graphitic Carbon Nitride with Mesoporous Structure and Superior Visible-Light-Responsive Activity. ACS Sustainable Chem. Eng. 2015, 3 (12), 3412-3419. 32. Dai, H.; Gao, X.; Liu, E.; Yang, Y.; Hou, W.; Kang, L.; Fan, J.; Hu, X., Synthesis and characterization of graphitic carbon nitride sub-microspheres using microwave method under mild condition. Diamond Relat. Mater. 2013, 38, 109-117.
24 ACS Paragon Plus Environment
Page 25 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
497 498 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529 530 531 532 533
ACS Sustainable Chemistry & Engineering
33. Gu, Q.; Liao, Y.; Yin, L.; Long, J.; Wang, X.; Xue, C., Template-free synthesis of porous graphitic carbon nitride microspheres for enhanced photocatalytic hydrogen generation with high stability. Appl. Catal.,B 2015, 165, 503-510. 34. Lu, Y.; Zhao, Q.; Zhang, N.; Lei, K.; Li, F.; Chen, J., Facile Spraying Synthesis and High-Performance Sodium Storage of Mesoporous MoS2/C Microspheres. Adv. Funct. Mater. 2016, 26 (6), 911-918. 35. Zhu, B.; Xia, P.; Ho, W.; Yu, J., Isoelectric point and adsorption activity of porous g-C3N4. Appl. Surf. Sci. 2015, 344, 188-195. 36. Pany, S.; Parida, K. M., A facile in situ approach to fabricate N,S-TiO2/g-C3N4 nanocomposite with excellent activity for visible light induced water splitting for hydrogen evolution. Phys. Chem. Chem. Phys. 2015, 17 (12), 8070-8077. 37. Wang, X.-j.; Yang, W.-y.; Li, F.-t.; Xue, Y.-b.; Liu, R.-h.; Hao, Y.-j., In Situ Microwave-Assisted Synthesis of Porous N-TiO2/g-C3N4 Heterojunctions with Enhanced Visible-Light Photocatalytic Properties. Ind. Eng. Chem. Res. 2013, 52 (48), 17140-17150. 38. Chen, Y.; Huang, W.; He, D.; Situ, Y.; Huang, H., Construction of Heterostructured gC3N4/Ag/TiO2 Microspheres with Enhanced Photocatalysis Performance under Visible-Light Irradiation. ACS Appl. Mater. Interfaces 2014, 6 (16), 14405-14414. 39. Yan, T.; Yan, Q.; Wang, X.; Liu, H.; Li, M.; Lu, S.; Xu, W.; Sun, M., Facile fabrication of heterostructured g-C3N4/Bi2MoO6 microspheres with highly efficient activity under visible light irradiation. Dalton Trans. 2015, 44 (4), 1601-1611. 40. Wang, K.; Li, Q.; Liu, B.; Cheng, B.; Ho, W.; Yu, J., Sulfur-doped g-C3N4 with enhanced photocatalytic CO2-reduction performance. Appl. Catal.,B 2015, 176–177, 44-52. 41. Xue, J.; Ma, S.; Zhou, Y.; Zhang, Z.; Jiang, P., Synthesis of Ag/ZnO/C plasmonic photocatalyst with enhanced adsorption capacity and photocatalytic activity to antibiotics. RSC Adv. 2015, 5 (24), 1883218840. 42. Yang, S.; Gong, Y.; Zhang, J.; Zhan, L.; Ma, L.; Fang, Z.; Vajtai, R.; Wang, X.; Ajayan, P. M., Exfoliated Graphitic Carbon Nitride Nanosheets as Efficient Catalysts for Hydrogen Evolution Under Visible Light. Adv. Mater. 2013, 25 (17), 2452-2456. 43. Dai, K.; Lu, L.; Liang, C.; Zhu, G.; Liu, Q.; Geng, L.; He, J., A high efficient graphiticC3N4/BiOI/graphene oxide ternary nanocomposite heterostructured photocatalyst with graphene oxide as electron transport buffer material. Dalton Trans. 2015, 44 (17), 7903-7910. 44. Jiang, J.-Q.; Yang, C.-X.; Yan, X.-P., Zeolitic Imidazolate Framework-8 for Fast Adsorption and Removal of Benzotriazoles from Aqueous Solution. ACS Appl. Mater. Interfaces 2013, 5 (19), 9837-9842. 45. He, Y.; Zhang, L.; Teng, B.; Fan, M., New Application of Z-Scheme Ag3PO4/g-C3N4 Composite in Converting CO2 to Fuel. Environ. Sci. Technol. 2015, 49 (1), 649-656. 46. Xue, J.; Ma, S.; Zhou, Y.; Zhang, Z.; He, M., Facile Photochemical Synthesis of Au/Pt/g-C3N4 with Plasmon-Enhanced Photocatalytic Activity for Antibiotic Degradation. ACS Appl. Mater. Interfaces 2015, 7 (18), 9630-9637.
534 535 536 537 538 539 25 ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 26 of 41
For Table of Contents only
540 541 542 543 544 545
Photo-regenerable, bifunctional granules of carbon doped g-C3N4 as adsorptive photocatalyst for the efficient removal of tetracycline antibiotic
546 547 548
Suyana Panneri, Priyanka Ganguly, Balagopal N. Nair, Abdul Azeez Peer Mohamed, Krishna G. Warrier and U.S. Hareesh*
549 550 551 552
Synopsis: Porous C3N4 granules as high capacity adsorptive photocatalysts for a greener solution of tetracycline removal
553 554
26 ACS Paragon Plus Environment
Page 27 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
TOC 60x48mm (150 x 150 DPI)
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Figure 1. XRD pattern of bulk C3N4 (BC) and spray dried C3N4 (CSDC) granules (inset shows the shift in main intensity peak). 180x156mm (300 x 300 DPI)
ACS Paragon Plus Environment
Page 28 of 41
Page 29 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Figure 2. SEM images of spray dried C3N4 granules (a) and (b) before calcination, (c) and (d) after calcination. 42x32mm (300 x 300 DPI)
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Figure 3. (a) UV-Visible absorption spectra and (b) band gap estimation of bulk C3N4 (BC) and spray dried C3N4 (CSDC) granules. 219x186mm (300 x 300 DPI)
ACS Paragon Plus Environment
Page 30 of 41
Page 31 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Figure 4. PL emission spectra of bulk and spray dried C3N4 at an excitation wavelength of 360 nm. 36x32mm (300 x 300 DPI)
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Figure 5. High resolution of XPS patterns (a) C 1s and (b) N 1s of bulk C3N4 (BC) and (c) C 1s and (d) N 1s of carbon doped spray dried C3N4 granules (CSDC). 43x37mm (300 x 300 DPI)
ACS Paragon Plus Environment
Page 32 of 41
Page 33 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Figure 6. Schematic representation of the formation of spray dried porous C3N4 granules with carbon doping (CSDC). 254x184mm (300 x 300 DPI)
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Figure 7. (a) Nitrogen adsorption-desorption isotherms and (b) BJH pore size distribution curves of bulk C3N4 (BC) and spray dried C3N4 (CSDC) granules. 240x106mm (300 x 300 DPI)
ACS Paragon Plus Environment
Page 34 of 41
Page 35 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Figure 8. Adsorption cum photocatalytic degradation of 100 µm TC using spray dried C3N4 granules (CSDC) and bulk C3N4 (BC). 40x32mm (300 x 300 DPI)
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Figure 9. Adsorption capacity of different concentrations of TC using spray dried C3N4 (CSDC). 39x32mm (300 x 300 DPI)
ACS Paragon Plus Environment
Page 36 of 41
Page 37 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Figure 10. Freundlich adsorption isotherm of 100 µm TC using spray dried C3N4 (CSDC) granules. 40x32mm (300 x 300 DPI)
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Figure 11. Pseudo second order kinetics of adsorption 100 µm TC using spray dried C3N4 (CSDC) granules. 39x32mm (300 x 300 DPI)
ACS Paragon Plus Environment
Page 38 of 41
Page 39 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Figure 12. Reactive oxygen species trapping of spray dried C3N4 (CSDC) granules using IPA, TEA, BQ, and AgNO3 under sun light irradiation. 167x129mm (300 x 300 DPI)
ACS Paragon Plus Environment
ACS Sustainable Chemistry & Engineering
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Figure 13. Photocatalytic mechanism of tetracycline degradation by spray granulated C3N4 (CSDC). 219x123mm (300 x 300 DPI)
ACS Paragon Plus Environment
Page 40 of 41
Page 41 of 41
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
ACS Sustainable Chemistry & Engineering
Figure 14. Cyclic tests on the adsorption and photocatalytic degradation of 100 µm TC using spray dried C3N4 (CSDC) granules. 32x32mm (300 x 300 DPI)
ACS Paragon Plus Environment