Bifunctional Material With Organic Pollutant Removing and

Subscriber access provided by UNIV OF NEW ENGLAND ARMIDALE
Article
Bifunctional Material with Organic Pollutant Removing and
Antimicrobial Properties: Graphene Aerogel Decorated
with Highly Dispersed Ag and CeO2 Nanoparticles
Xiafang Tao, Yazhou Zhou, Kai Xu, Yunyan Wu, Jianli Mi, Yi Li,
Qinqin Liu, Xiaonong Cheng, Nan Zhao, Haifeng Shi, and Juan Yang
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.8b04251 • Publication Date (Web): 27 Oct 2018
Downloaded from http://pubs.acs.org on October 31, 2018
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 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 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.
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 40 ACS Sustainable Chemistry & Engineering
1
2
3
4
5
6
7
8
Bifunctional Material with Organic Pollutant
9
10
11
12
Removing and Antimicrobial Properties: Graphene
13
14
15
16
Aerogel Decorated with Highly Dispersed Ag and
17
18
19
20 CeO2 Nanoparticles
21
22
23
24
25 Xiafang Tao,† Yazhou Zhou,*,† Kai Xu,† Yunyan Wu,† Jianli Mi,† Yi Li,† Qinqin Liu,† Xiaonong
26
27 Cheng,† Nan Zhao,† Haifeng Shi,‡ and Juan Yang *,†
28
29
30 †School of Materials Science and Engineering, and ‡Institute of life sciences, Jiangsu University,
31
32
33 Xuefu Road 301, 212013, Zhenjiang, People’s Republic of China
34
35
36 *Email address of corresponding author
37
38
39
40
41 Yazhou Zhou: yazhou@ujs.edu.cn
42
43
44
45 Juan Yang: yangjuan6347@mail.ujs.edu.cn
46
47
48
49 KEYWORDS: Graphene aerogel; Cerium dioxide (CeO2); Silver nanoparticles (Ag NPs);
50
51 Photocatalyst; Antimicrobial material
52
53
54
55
56
57
58
59
60 ACS Paragon Plus Environment
1
ACS Sustainable Chemistry & Engineering Page 2 of 40
1
2
3 Abstract: The graphene aerogels supporting Ag and CeO2 nanoparticles (NPs) (Ag/CeO2/GA) with
4
5
6 bifunctional performances have been fabricated by a modified gelatinization reaction method.
7
8 Through the control of GO concentration and ultrasonic-assisted pre-reduction process, the small
9
10 NPs can be dispersed highly into porous structure of GA. The integration of hierarchical porous
11
12
13
structure and a synergistic effect between CeO2 and Ag NPs grant them bifunctional properties of
14
15 organic pollutant removing (100% of methylene blue and 81.8% of bisphenol A were degraded
16
17 within 12 min and 4 h, respectively), and antimicrobial activity against Escherichia coli
18
19
(MIC100%Ag: 7.5 ppm, MBC100%Ag: 11.3 ppm). The possible mechanism is the improved
20
21
22 photocatalytic performance of CeO2/GA by unique surface plasmonic effect of Ag NPs due to
23
24 increasing light absorption and photoconductivity for photoexcited holes and electrons. Therefore,
25
26 the holes and radicals (especially •OH) can be produced continuously and efficiently from
27
28
29 Ag/CeO2/GA, which can remove organic pollution from water efficiently while protecting the
30
31 water from bacterial pollution. Moreover, a good recycling stability and biocompatibility suggest
32
33 that such bifunctional material has a great promise in water purification applications.
34
35
36
37 Introduction
38
39
40 Graphene has attracted a great attention as nanoscale building blocks to construct the three-
41
42
43
dimensional (3D) macroscopic graphene aerogels (GAs).1-3 Previous work reported that GAs not
44
45 only inherit many properties from two-dimensional (2D) graphene such as large specific surface
46
47 area, high physical and chemical stability as well as excellent electrical, mechanical, and thermal
48
49 properties, but also present high porosity, extremely low density, and extraordinary elasticity
50
51
52 properties.4-6 The constructing macroscopic graphene structure is crucial for promoting the
53
54 graphene in many potential applications.7 In particular, GA has been demonstrated as a promising
55
56
57
58
59
2
1
2
3 candidate for oil spill clean-up,8-11 and water purification applications12-14 on based of several
4
5
6 advantages over the traditional sorbents: (1) be able to efficiently adsorb the organic pollutants
7
8 from water at high speed due to its superhydrophobic and superoleophilic properties; (2) super
9
10 high adsorption capacity because of its high porosity and large surface area; (3) ease separation of
11
12
13
GA from water; (4) be compatible with large-scale applications and easily assembled owing to its
14
15 macroscopic bulk structure, and (5) facile and large-scale synthesis from graphene oxide (GO)
16
17 using many methods such as self-assemble, hydrothermal, hard template and freeze-casting
18
19
methods. Unfortunately, there are still concerning issues for GA in practical water purification
20
21
22 applications. For example, the recycling capacity should be further improved because it is not easy
23
24 to remove the adsorbed organic pollutants from GA. Although, the thermal treatment is a useful
25
26 way, it may cause collapse of the porous structure. It is difficult to clean out the microorganism
27
28
29 such as bacteria out of the polluted water. The adsorbed bacteria on the GA would probably
30
31 proliferate in high speed, which bring the serious microbial contamination to the water. Therefore,
32
33 synthesis of bifunctional GA with high visible-light photocatalytic degradation and excellent
34
35
36
antimicrobial properties is a great strategy to overcome as-described issues.
37
38 A number of photocatalyst nanoparticles (NPs) such as TiO2, ZnO, Ag3PO4, Ag/AgX, CeO2,
39
40 etc. have been supported by 2D graphene sheets to form new types of photocatalysts.15-19
41
42
Graphene, a good photogenerated electrons acceptor and transporter, plays an important role in
43
44
45 improving the photodegradation performance due to its high specific surface area and excellent
46
47 electrical conductivity. Thus, integration of high adsorption ability of GA and good photocatalytic
48
49 activity of NPs may be an ideal for fabrication of the new-type of water purification materials.
50
51
52 CeO2, an abundant and inexpensive rare earth material, has attracted tremendous attention from
53
54 excellent photocatalytic activity under visible-light irradation.20 For instance, Reddy21 and Jha22
55
56
57
58
59
3
1
2
3 have reported the deposition of CeO2 in GA. Nevertheless, there is still a great challenge for the
4
5
6 controllable synthesis of NPs/GAs. One of the most popular approaches for the synthesis of
7
8 NPs/GAs is the integration of metal precursors or NPs with GO into macroscopic bulk structure.23-
9
10 25 The high concentration of GO is necessary for formation of stable macroscopic graphene.26,27
11
12
13
However, due to the high concentration of GO, it’s difficult for the metal precursors or NPs to
14
15 uniformly disperse on the GO sheets, which results in the big size and serious aggregation of NPs
16
17 in GAs.28,29 Some researchers deposited NPs into as-prepared GA by self-assembly method, but it
18
19
also caused serious NP aggregations.30 Thus, creating new strategies for controllable integration
20
21
22 of photocatalytic NPs such as CeO2 NPs with GA is highly desirable for the development of
23
24 excellent water purification materials.
25
26 Microbial contamination of water (such as Escherichia coli, E. coli) is still a very severe
27
28
29 problem that causes gastrointestinal diseases to human, particularly to children in developing
30
31 countries.31 Although the gastrointestinal diseases can be easily controlled by chlorination of
32
33 water, the recontamination is a huge problem in purified water. Moreover, the surviving microbes
34
35
36
adsorbed on the purified materials such as activated carbon would rapidly proliferate, which is
37
38 detrimental to the water quality.32 Ag NPs show a great promise in water treatment application
39
40 owing to the excellent antibacterial activity, controllable biocompatibility as well as the high
41
42
capacity of removing certain ions.33 It has been reported that incorporating Ag NPs can improve
43
44
45 the photocatalytic activity of CeO2 NPs.34 Thus, integration of Ag NPs with photocatalytic
46
47 CeO2/GA (Ag/CeO2/GA) may be an ideal candidate in development of water treatment materials
48
49 that are able to purify the organic pollutants and microbes.
50
51
52 Herein, bifunctional Ag/CeO2/GA materials have been successfully synthesized using a
53
54 modified gelatinization reaction method. As far as we know, this might be the first report
55
56
57
58
59
4
1
2
3 constructing Ag/CeO2/GA with several achieved benefits. (a) The new and versatile strategy has
4
5
6 been demonstrated to fabricate NPs/GA with highly-dispersive of NPs; (b) The ultrasonic-assisted
7
8 process was introduced to form well-dispersed Ag NPs with small size and narrow size distribution
9
10 in the Ag/CeO2/GA materials; (c) The Ag/CeO2/GA displayed bifunctional performances of
11
12
13
removing the organic pollutants such as colorful dye of methylene blue (MB) and colorless
14
15 bisphenol A (BPA), and excellent antibacterial activity. (d) The cost is acceptable due to the low
16
17 Ag NP loading (~7.5 wt%). Such attractive materials hold a great potential in water purification
18
19
applications, and this method is quite superior for creating the new GA-based materials with
20
21
22 attractive properties.
23
24 Experimental Section
25
26
27 Synthesis of CeO2/GA Photocatalyst. The CeO2/GA material was synthesized by a modified
28
29
30
gelatinization reaction method. The positively charged CeO2 NP colloid (3.9 mg mL-1, particle
31
32 size: 11.6 nm) (Figure S1) was firstly prepared according to the reported method (see Supporting
33
34 Information).35 And then, 5 mL of CeO2 colloid was added in 60 mL of GO aqueous solution (0.33
35
36 mg mL-1) to form CeO2 NPs/GO, after 1 h vigorous stirring. Then, CeO2 NPs/GO solution was
37
38
39 concentrated by centrifuging, followed by removing a certain volume of supernatant to obtain 10
40
41 mL of CeO2 NPs/GO solution. The above solution with 20 mg L-ascorbic acid was placed in oven
42
43 at 90 oC for 4 h to form hydrogel. After extracting, freeze-drying, the CeO2/GA material can be
44
45
46 obtained.
47
48 Synthesis of Ag/CeO2/GA Photocatalysts. The Ag/CeO2/GA material was synthesized by as-
49
50 described method, but the ultrasonic-assisted pre-reduction was processed before the gelatinization
51
52
53
reaction. 5 mL (or 6 mL) CeO2 colloid and 0.35 mL of silver nitrate (AgNO3) solution (0.1 M)
54
55 were added into 60 mL of GO aqueous solution (0.33 mg mL-1) to form the Ag+/CeO2/GO
56
57
58
59
5
1
2
3 precursors after vigorous stirring. The same concentrated process was carried out to obtain 10 mL
4
5
6 of Ag+/CeO2/GO solution. Then Ag+/CeO2/GO precursors were pre-reduced by adding 10 mg
7
8 sodium borohydride (NaBH4) using 10 min ultrasonic-assisted process to obtain Ag/CeO2/rGO
9
10 solution. Above solution was then treated as same process as CeO2/GA to form the Ag/CeO2/GA.
11
12
13
The Ag/CeO2/GA photocatalysts prepared by adding 5 mL or 6 mL of CeO2 colloid were labeled
14
15 as Ag/CeO2/GA-5 and Ag/CeO2/GA-6, respectively.
16
17 Characterization. The morphologies of samples were characterized by scanning electron
18
19
microscope (SEM) on a JSM-7001F and transmission electron microscope (TEM) on a JEOL
20
21
22 2011, Japan. The scanning TEM (STEM) and energy dispersive X-ray (EDX) analyses were
23
24 obtained using Titan 80-300 S/TEM equipped with a probe spherical aberration corrector (FEI
25
26 Company) operated at 300 kV. The X-ray photoelectron spectroscopy (XPS) data was performed
27
28
29 using a Kratos AXIS-165 with a monochromatized AlKα X-ray anode (1486.6 eV). The X-ray
30
31 diffraction (XRD) analyses were performed on a Siemens D5000 powder X-ray diffractometer
32
33 with Cu Kα radiation at 40 kV and 30 mA. The optical properties were characterized by ultraviolet-
34
35
36
visible (UV-vis) spectra performed on a Shimadzu UV2450 spectrometer (Japan). The actual metal
37
38 loading was analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES)
39
40 (Thermo-Fisher iCAP 6300, Thermo Fisher Scientiﬁc Inc.).
41
42
Photoelectrochemical Experiments. The typical three-electrode system was employed to
43
44
45 measure the electrochemical impedance spectroscopy (EIS) and transient photocurrent of samples
46
47 (CHI 660E, Chenhua Instrument, Shanghai, China). The platinum foil and Ag/AgCl (3M) were
48
49 used as a counter and reference electrodes, respectively. 0.2 M Na2SO4 aqueous solution was
50
51
52 employed as electrolyte. A Xe lamp (300 W, a 420 nm cut-off filter) was used as visible light
53
54 source. The procedures for preparation of working electrodes are as follow: 5 mg photocatalyst
55
56
57
58
59
6
1
2
3 was dispersed into mixed solution containing 250 μL ethanol, 250 μL ethylene glycol and 40 μL
4
5
6 Nafion; 80 μL above catalytic ink was then dropped onto the fluorine tin oxide (FTO) glass with
7
8 an exposed area of 1 cm2. EIS spectra were recorded in the range from 0.01 Hz to105 Hz at an ac
9
10 voltage of 10 mV. The photocurrent responses were obtained with 1.2 V bias voltage under light
11
12
13
switching on and off.
14
15 Purification Performance of Organic Pollutant Removal from Water. The dye of MB and
16
17 colorless BPA were employed to demonstrate the purification property of samples. A solar
18
19
simulator with Xe lamp (CHF-XM-500W, λ>420 nm, Changtuo, China) was used as the visible
20
21
22 light source. In a typical process of degradation of MB, 30 mg Ag/CeO2/GA-5 (CeO2/GA) were
23
24 dropped in 50 mL of a dye solution (30 mg mL-1) with magnetic stirring without light irradiation.
25
26 After 30 min, the light was turned on. During the experiment, 2 mL of dye solution was taken out
27
28
29 every few minutes. MB concentration was monitored using a UV-vis spectra. For degradation of
30
31 BPA, the process was similar with MB. But, 50 mL BPA (150 mg L-1) and 30 mg materials were
32
33 used. A high-performance liquid chromatography (HPLC, Perkin Elmer) was carried out to
34
35
36
analyze BPA concentration according to the previous work.36 The details can be seen in Supporting
37
38 Information.
39
40 Recycling Stability Test. The recycling and stability properties of the Ag/CeO2/GA catalyst
41
42
were investigated by recycling the catalyst towards degradation of MB for 5 times. In detail, the
43
44
45 aerogel was taken out from the MB solution, and was washed with DI water for 3 times, followed
46
47 by freeze-drying. The degradation of MB was repeated. This process was repeated for 5 times, and
48
49 the change of photocatalyst of sample was recorded. After five-recycle experiment, the stability of
50
51
52 photocatalyst was measured by XRD, and compared with that of initial catalyst.
53
54
55
56
57
58
59
7
1
2
3 Antimicrobial Property Evaluation. The in vitro evaluation was used to characterize the
4
5
6 antimicrobial property of Ag/CeO2/GA against the Gram-negative bacterium E. coli (ATCC 117).
7
8 The antimicrobial measurements include inhibition zone testing, bacterial growth inhibition, and
9
10 bacterial time-kill assay. And then, the minimum inhibitory concentration (MIC100%) and minimum
11
12
13
bactericidal concentration (MBC100%) can be obtained according to the data. The biocompatibility
14
15 and cytotoxicity of Ag/CeO2/GA were characterized using a 3-(4,5-dimethylthiazol-2-yl)-2,5-
16
17 diphenyltetrazolium bromide (MTT) method on the human hepatic carcinoma (HepG2) cell lines.
18
19
The detailed experimental procedures were shown in the Supporting Information and our previous
20
21
22 work.16
23
24
25 Results and Discussion
26
27
28 Synthesis and Characterizations of CeO2/GA and Ag/CeO2/GA Catalysts. The synthesis of
29
30 CeO2/GA includes three main procedures, and its schematic illustration is shown in Figure S1: (1)
31
32
Preparation of NPs/GO by electrostatic self-assembly (Figure S1a); (2) gelatinization reaction of
33
34
35 NPs/GO to form hybrid hydrogel (Figure S1b), and (3) freeze-drying to obtain aerogel with
36
37 macroscopic porous structure (Figure S1c). It is noted that GO concentration is crucial for the
38
39 synthesis of graphene-based aerogels with high quality (> 2mg mL-1, usually). In order to highly
40
41
42 disperse the NPs onto the surface of GO sheets, a low concentration of GO solution (0.33 mg mL-1)
43
44 is initially required in this work because of the fully stripped GO sheets (Figure S1a). After that,
45
46 the GO solution was then concentrated to 2 mg mL-1 by centrifugation (Figure S1b). In doing so,
47
48
49
both highly dispersive of NPs and stable macroscopic bulk structure can be achieved (Figure S1c).
50
51
52
53
54
55
56
57
58
59
8
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
Figure 1. Characterization of CeO2/GA, (a) SEM image, (b, c) TEM images, and (d) HRTEM
37
38 image.
39
40
41 The porous structure of CeO2/GA catalysts was investigated by SEM (Figure 1a). The well-
42
43 defined 3D graphene frameworks can be clearly seen in the cross-section of CeO2/GA catalyst.
44
45
46
The detailed morphologies of CeO2/GA catalysts were further analyzed by TEM (Figure 1b, c). A
47
48 few of graphene layers are folded to form the typical wrinkled and fibrous structures, wherein the
49
50 cubic CeO2 NPs disperse on the graphene sheets. There is no any NP aggregation found in GA,
51
52
indicating that the high dispersion of NPs in GA was achieved. Figure 1d shows the HRTEM
53
54
55 image of CeO2 NPs. The NPs with annotations of planes can be clearly seen, which is consistent
56
57
58
59
9
1
2
3 with fluorite CeO2 crystal structure. For comparisons, two additional CeO2/GA materials were
4
5
6 prepared under different experimental conditions. One is the use of high concentration of initial
7
8 GO solution (2 mg mL-1). However, obvious NP aggregations in GA can be found (Figure S3).
9
10 The other is the use of low concentration of GO solution (0.33 mg mL-1) without centrifuging
11
12
13
process, and the macroscopic hydrogel cannot be formed due to the low GO concentration (Figure
14
15 S4). The results strongly proved that the high-dispersive of NPs and macroscopic structure can be
16
17 both achieved through the control of the GO concentration.
18
19
On the basis of the synthesis of CeO2/GA materials, Ag/CeO2/GA material was further
20
21
22 fabricated, and the synthesis procedures is schematically illustrated in Figure 2. The Ag+ and CeO2
23
24 were attached on the GO surfaces using self-assembly method. After concentrated process, the
25
26 Ag+/CeO2/GA precursors were obtained (Figure 2a). The precursors were then treated by
27
28
29 ultrasonic-assisted pre-reduction process. During this process, the Ag NPs can be attached on the
30
31 rGO surfaces through an in-situ reduction reaction to obtain the Ag/CeO2/rGO (Figure 2b). Finally,
32
33 the Ag/CeO2/GA material was obtained by gelatinization reaction process (Figure 2c), followed
34
35
36
by freeze-drying (Figure 2d). The interaction between NPs and rGO can be strengthened during
37
38 gelatinization reaction process. Importantly, the ultrasonic-assisted pre-reduction process is crucial
39
40 for introducing of small Ag NPs with highly-dispersive in GA, which will be discussed in detail
41
42
later.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
10
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
Figure 2. Schematic illustration of synthesis procedures of Ag/CeO2/GA, (a) preparation of
28
29
30 Ag+/CeO2/GO by (1) self-assembly method and (2) concentrated process; (b) Ag/CeO2/rGO
31
32 prepared by ultrasonic-assisted process; (c) Ag/CeO2/graphene hydrogel prepared by
33
34 gelatinization process; (c) Ag/CeO2/GA prepared by freeze-drying of Ag/CeO2/graphene
35
36
37 hydrogel.
38
39
40 The SEM image of cross-sectional Ag/CeO2/GA material is shown in Figure 3a. The
41
42 Ag/CeO2/GA material shows a similar well-defined 3D porous framework structure with
43
44 CeO2/GA, indicating that the pre-reduction process does not affect the formation of porous
45
46
47 structure. Figure 3b shows the TEM image of Ag/CeO2/GA material. The NPs with an average
48
49 size of 12. 2 nm are uniformly scattered on the graphene sheets, and no obvious NP aggregation is
50
51 detected in large-scale graphene sheets, indicating that NPs with highly-dispersive in GA were
52
53
54
achieved (Figure 3b). In order to further identify the CeO2 and Ag NPs and their distributions, the
55
56 HRTEM and elemental mapping were employed. As shown in the HRTEM image (Figure 3c), the
57
58
59
11
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 Figure 3. (a) SEM, (b) TEM, (c) HRTEM, (d) HAADF-STEM and (e,f) STEM mapping images
50
51
of Ag/CeO2/GA-5, (g) SEM and (h) TEM images of Ag/CeO2/GA-6.
52
53
54
55
56
57
58
59
12
1
2
3 well-resolved lattice fringes with d-spacing of ~ 0.312 nm are observed for the cube-shaped NPs,
4
5
6 corresponding to the {111} interplanar distance of fluorite CeO2 structure. The lattice fringes with
7
8 d-spacing of ~ 0.232 nm can be clearly seen for some particles, which are in high agreement with
9
10 the fcc Ag {111} planes. The high-angle annular dark field scanning TEM (HAADF-STEM)
11
12
13
image (Figure 3d), corresponding elemental mappings for Ce (Figure 3e) and Ag (Figure 3f) also
14
15 demonstrate both Ag and Ce element existing in GA, and they have a homogeneous dispersion in
16
17 GA.
18
19
The crystal structures of CeO2/GA and Ag/CeO2/GA photocatalysts were further characterized
20
21
22 by XRD (Figure 4a). For CeO2/GA photocatalyst, an obvious peak can be found at 2 of 22.5°,
23
24 which is assigned to the C (002) for GA. The other nine peaks appeared at 2 of 28. 6°, 33.1°,
25
26
27 47.5°, 56.3°, 59.1°, 69.4°, 76.7°, 79.1°, and 88.4° are correspondingly assigned to the (111), (200),
28
29 (220), (311), (222), (400), (331), (420), and (422) crystal planes of CeO2, which are highly
30
31 consistent with the fluorite CeO2 structure (JCPDS card no. 34-0394). In contrast, Ag/CeO2/GA
32
33
34 photocatalyst presents four additional peaks at 2 of 38.1°, 44.3°, 64.4°, and 77.5°, corresponding
35
36 to the (111), (200), (220), and (311) crystal planes of fcc Ag structure (JCPDS card no. 04-0783).
37
38 In addition, the CeO2 diffraction peaks in Ag/CeO2/GA photocatalyst are highly consistent with
39
40
41 those of in CeO2/GA, indicating that the pre-reduction process does not affect the crystal structure
42
43 of CeO2. According to the XRD data, the sizes of crystal Ag and CeO2 NPs were calculated using
44
45 the Scherrer equation:37
46
47
0.9𝐾1
48 𝐿=
49 𝐵2 𝐶𝑜𝑠(𝑚𝑎𝑥)
50
51
52
where L is the mean NP size, 𝐾1 is the X-ray wavelength (=0.15418 nm), B2 is the line
53
54 broadening at half the maximum intensity, and max is the Bragg angle of the peak. The average
55
56
57
58
59
13
1
2
3 sizes of Ag NPs and CeO2 NPs calculated from that equation are 14.5 nm and 12.4 nm, which is
4
5
6 in good agreement with that determined from TEM data.
7
8 The elemental analysis of photocatalysts were characterized using XPS. From the C 1s XPS
9
10 spectrum of Ag/CeO2/GA material (Figure 4b), only few oxygen-functional groups remained in
11
12
13
GA compared with GO, indicating the high reducing degree of GA is achieved using as-described
14
15 method. The high-resolution Ce 3d XPS spectrum is shown in Figure 4c. The spin-orbit coupling
16
17 3d5/2 and 3d3/2 XPS peaks are labeled as V and U, respectively. Eight fitted peaks can be clearly
18
19
seen, which are in high agreement with reported spectra of CeO2.38 Specifically, the six peaks
20
21
22 labeled as V, V2, V3, U, U2 and U3 are attributed to Ce4+ state. We also found the Ce3+ state with
23
24 peaks labeled as V1 and U1 in XPS spectrum. The result indicated the cerium in the material is
25
26 present in both Ce4+ and Ce3+ oxidation. Figure 4d shows the Ag 3d XPS spectrum for
27
28
29 Ag/CeO2/GA material. Two individual peaks appear at 368.6 eV and 374.6 eV, corresponding to
30
31 Ag 3d3/2 and Ag 3d5/2, respectively.39,40 The Ag loading in Ag/CeO2/GA material is calculated by
32
33 ICP, and Ag loading in photocatalyst is only 7.5 wt%. The XRD, XPS, and TEM results have
34
35
36
proven that the highly crystalline Ag NPs and CeO2 NPs have been successfully integrated with
37
38 GA.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
14
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
Figure 4. (a) XRD patterns of Ag/CeO2/GA, CeO2/GA and GO, (b) high-resolution C 1s, (c) Ce
49
50
51 3d, (D) Ag 3d XPS spectra of Ag/CeO2/GA, porous structure characterization (e) N2
52
53 adsorption/desorption isotherms and (b) pore size distributions.
54
55
56
57
58
59
15
1
2
3 It’s well known that the antimicrobial activity of Ag NPs strongly depends on their particle
4
5
6 sizes,41 and smaller Ag NPs has better antimicrobial activity than those of bigger Ag NPs.42 In this
7
8 work, the Ag NPs in Ag/CeO2/GA photocatalyst have a small size (~14.5 nm), which are attributed
9
10 to the ultrasonic-assisted pre-reduction process. For comparison, another Ag/CeO2/GA material
11
12
13
was also synthesized without the pre-reduction process. Due to the existing Cl- in CeO2 colloid,
14
15 the AgCl aggregations can be formed by reaction with Ag+ and Cl-, resulting in the serious NP
16
17 aggregations, big size and the large size distribution of Ag NPs on graphene sheets during the
18
19
gelatinization reaction by L-ascorbic acid (Figure S5). The ultrasonic-assisted pre-reduction is
20
21
22 useful to address this issue with the following two benefits: (1) Ag+ can be reduced by the strong
23
24 reductant NaBH4 quickly, which tend to form the small Ag NPs; (2) ultrasonic-assisted condition
25
26 is beneficial for further reducing the Ag NP size and improving the NP dispersion.37 However, we
27
28
29 should be cautious about NaBH4 dosage because it heavily impacts the construction of
30
31 macroscopic structure. The optimal NaBH4 dosage is ~10 mg in this experiment. This amount of
32
33 NaBH4 is enough for reducing the Ag+, but is insufficient for reducing GO. Thus, the
34
35
36
Ag/CeO2/rGO mixed solution still presents the high mono-dispersion after the pre-reduction
37
38 process owing to the sufficient remaining oxygen-functional groups on rGO sheets (Figure 2c),
39
40 which can be further assembled into hydrogel by gelatinization reaction. When higher amount of
41
42
NaBH4 (>15 mg) was used, the powder separated from the solution because a lot of oxygen-
43
44
45 functional groups were removed from rGO sheets by NaBH4, and the above hydrogel cannot be
46
47 formed (Figure S6).
48
49 Using this method, the high NP loading in GA, while maintaining their highly dispersive and
50
51
52 macroscopic structure can be easily achieved. Figure 3g shows the SEM image of CeO2/GA-6
53
54 catalyst with the higher NP loading. The SEM image shows the similar porous structure with
55
56
57
58
59
16
1
2
3 CeO2/GA-5 catalyst, indicating that the change of NP loading does not significantly affect the
4
5
6 porous structure. The NPs are also highly dispersive in GA, and no NP aggregation can be found
7
8 (Figure 3h). Therefore, the method described in this paper is superior for integration of NPs with
9
10 controllable composition and loading and highly dispersive in GA.
11
12
13
The porous structures of photocatalysts were further analyzed by N2 adsorption/desorption
14
15 measurements. The typical N2 adsorption/desorption isotherms of CeO2/GA and Ag/CeO2/GA
16
17 materials are shown in Figure 4e. Clearly, both photocatalysts show the type IV
18
19
adsorption/desorption isotherm with a clear H1 hysteresis loop. Figure 4f shows the pore size
20
21
22 distributions of two photocatalysts obtained using BJH model. Both two photocatalysts have
23
24 hierarchical structures, including the mesopores and macropores. The specific surface area and
25
26 pore volume of Ag/CeO2/GA material are 123 m2 g-1 and 0.32 cm3 g-1, respectively, which are
27
28
29 similar to CeO2/GA material (112 m2 g-1 and 0.23 cm3 g-1). The high specific surface area and
30
31 large pore volume make such photocatalysts suitable for water purification.
32
33 Purification Performance of Organic Pollutant from Water. The purification performance
34
35
36
of Ag/CeO2/GA material is investigated by its ability in removing the dye molecule of MB and
37
38 colorless BPA from water. CeO2/GA and GA are investigated as comparisons. Figure 5a showed
39
40 the MB (30 mg mL-1, 30 mL) removing performance of Ag/CeO2/GA (30 mg). First of all, the
41
42
adsorption behaviors of GA, CeO2/GA and Ag/CeO2/GA toward MB were investigated in the
43
44
45 darkness. The adsorption equilibriums for all the samples are achieved within 15 min. The
46
47 CeO2/GA and Ag/CeO2/GA have similar adsorption efficiencies of 48%, which are higher than
48
49 those of GA (38%). In previous works, graphene derivatives such as GO and rGO were used as
50
51
52 adsorbents for removal the contaminations from water, particularly in organic pollutants.43 They
53
54 have the much higher adsorption capacities than those of graphite, activated carbon, layered double
55
56
57
58
59
17
1
2
3 hydroxide, boron nitride, metal-organic frameworks, and polymer adsorbents due to their strong
4
5
6 - stacking, anion-cation interactions and oxygen-functional groups.44-48 In this work, the 3D
7
8 hierarchical porous structure and high pore volume also promote Ag/CeO2/GA material highly
9
10
efficient for organic pollutant adsorption. Under the visible-light irradiation, the MB purification
11
12
13 efficiency of Ag/CeO2/GA showed in the Figure 5a, which is obtained according to the real-time
14
15 absorption spectra of MB over the material (Figure 5b). Almost 100% of MB molecules were
16
17 degraded within 12 min under visible light irradiation using Ag/CeO2/GA as a photocatalyst, while
18
19
20 87.7% of MB molecules were degraded using CeO2/GA as a photocatalyst. In contrast, negligible
21
22 MB removing was further found when the pure GA was used as photocatalyst, which proves that
23
24 MB removing under light is attributed to the photocatalytic effect. Thus, Ag/CeO2/GA material
25
26
27
exhibits improved MB removing efficiency compared with CeO2/GA material because of
28
29 enhanced photocatalytic activity of CeO2 with Ag NPs. The recycling capacity is also
30
31 demonstrated, which is essential for water purification materials in practical applications. It can be
32
33
clearly seen that the Ag/CeO2/GA photocatalyst still remains a high efficiency of MB purification
34
35
36 after 5 recycles, indicating the excellent recycling capacity (Figure 5c). In addition, the XRD of
37
38 Ag/CeO2/GA after stability measurement is also obtained and compared with initial Ag/CeO2/GA.
39
40 Obviously, the crystal structure of Ag/CeO2/GA has no obvious change after stability
41
42
43 measurement, further proves its high stability (Figure 5d).
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
18
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 Figure 5. (a) Adsorption and photodegradation properties of GA, CeO2/GA and Ag/CeO2/GA
46
47 toward (a) MB, and (e) BPA. (b) Absorption spectra of MB during the purification process. Inset
48
49 of (b) is digital photograph that shows color change during the purification process. Purification
50
51
52
stabilities of photocatalyst toward (c) MB, (f) BPA by five-recycle experiments. (d) The XRD
53
54 patterns of Ag/CeO2/GA before and after five-recycle measurements.
55
56
57
58
59
19
1
2
3 BPA is an important synthetic compound for synthesis of plastic products such as epoxy resins,
4
5
6 polycarbonate, unsaturated polyester-styrene resins, and so on.36 It is also a typical toxic
7
8 endocrine-disrupting chemical. Owing to its wide applications in manufacturing industries, the
9
10 exposure of BPA in water environments has raised great concerns about its harmful impact on the
11
12
13
ecosystem. However, it is still a challenge to remove BPA effectively and completely from water.
14
15 Recently work showed that the visible light-driven photocatalyst can be used for degradation of
16
17 BPA because of their many advantages including environmentally friendly, economic friendly,
18
19
and efficiency.36,49 Here, the BPA is used as the second model to investigate the purification ability
20
21
22 of Ag/CeO2/GA towards organic pollutants. Figure 5e shows the evolution of the BPA degradation
23
24 in the presence of CeO2/GA and Ag/CeO2/GA photocatalysts. Clearly, all the materials display the
25
26 strong absorption of BPA without light irradiation. Under visible light irradiation, 81.8% of BPA
27
28
29 molecules were degraded within 4 h when Ag/CeO2/GA was used as a photocatalyst, while 54.2%
30
31 of BPA molecules were degraded by CeO2/GA photocatalyst. The BPA could be completely
32
33 degraded by Ag/CeO2/GA within 8 h. Therefore, Ag/CeO2/GA shows significantly improved
34
35
36
photocatalytic activity compared with that of CeO2/GA. We also investigate the stability of
37
38 Ag/CeO2/GA photocatalyst towards BPA by five-recycle experiments and compared with that of
39
40 CeO2/GA photocatalyst. As shown in Figure 5f, Ag/CeO2/GA exhibits 85.1% degradation
41
42
efficiency of BPA after stability measurement; while 58.5% efficiency is retained for CeO2/GA.
43
44
45 Therefore, Ag/CeO2/GA photocatalyst shows the good purification property and stability towards
46
47 BPA.
48
49 The photodegradation of organic dyes by CeO2-based materials such as pure CeO2 NPs,20
50
51
52 Ag/CeO2,34 and CeO2/RGO composites19,21 has been reported, which has an obviously low
53
54 efficiency compared to our CeO2/GA and Ag/CeO2/GA materials as tabulated in Table 1. Our
55
56
57
58
59
20
1
2
3 materials also have higher or comparable efficiencies compared with the state-of-the-art 3D porous
4
5
6 photocatalysts such as CeO2/RGA,50 ZnO/rGO foam,51 and RGO/TiO2 aerogel,52 Bi12O15Cl6
7
8 photocatalyst,36 Ag-SCN photocatalyst.49 The good integration of macroscopic graphene with
9
10 photocatalytic NPs has been proven as a great strategy for fabrication of advanced water treatment
11
12
13
materials.
14
15
16
Table 1. Comparison of purification efficiencies of photocatalysts toward organic pollutantsa
17 Dye
Photocatalyst Dye Degradation Degradation Light
18 Conc Ref.
(weight) degraded (%) time (min) source (power)
19 (volume)
20
hollow 20 mg L-1 Visible
21 RhB 93 180 20
CeO2 (10 mg) (50 mL) (300 W Xe)
22
23 Ag/CeO2
RhB
5 mg L-1
99
Visible
24 MB 97 70, 60, 60 34
(50 mg) (100 mL) (500 W)
25 CV 99
26 CeO2/RGO 1 mM 426 nm
27 MO 88.3 60 19
(15 mg) (30 mL) (14.5W/m2)
28
29 rGO-CeO2 10-5 M
MB 72 50 Sunlight 21
30 (50 mg) (50 mL)
31 10 mg L-1 Solar light
32 CeO2/RGA RhB 85 120 50
(100 mL) (150 W Xe)
33
34 ZnO/rGO 5 mg L-1 Solar light
RhB >95 150 51
35 foam (5 mg) (25 mL) (0.1W/cm2)
36 RGO/TiO2 10 mg L-1 UV
37 CBZ 100 90 52
aerogel (200 mL) (~13.5W m-2)
38
39 Bi12O15Cl6 10 mg L-1 Visible
BPA Nearly 100 360 34
40 (30 mg) (40 mL) (350 W Xe)
41 Ag-SCN 10 mg L-1 Visible
42 49
(30 mg) (50 mL) (155 W Xe)
43
44 30 g L-1,
CeO2/GA MB Nearly 100, Solar light This
45 150 mg L-1 18, 240
(30 mg) BPA 54.2 (500 W Xe) work
(50 mL)
46
47 30 g L-1,
Ag/CeO2/GA MB Nearly 100, Solar light This
48 150 mg L-1 12, 240
(30 mg) BPA 81.8 (500 W Xe) work
49 (50 mL)
50 aRhB:rhodamine B; MO: methyl orange; RGA: reduced graphene oxide aerogels; CBZ: carbamazepine; Ag-
51 SCN: Ag-decorated S-doped g-C3N4.
52
53
54
55
56
57
58
59
21
1
2
3 Antibacterial Property. E. coli is one of the most common fecal-derived pathogenic
4
5
6 microorganisms in water. The virulent strains can cause gastroenteritis, urinary tract infections,
7
8 neonatal meningitis, hemorrhagic colitis, and Crohn's disease.53 Thus, E. coli was used as a model
9
10 to demonstrate the antimicrobial activity of Ag/CeO2/GA photocatalyst. Figure S7 shows the
11
12
13
inhibition zones of CeO2/GA and Ag/CeO2/GA photocatalysts toward E. coli. The obvious zone
14
15 with a diameter of 11.6 mm can be seen for 500 ppm Ag/CeO2/GA photocatalyst, while only 3.4
16
17 mm zone can be found for 500 ppm CeO2/GA photocatalyst. Even though the concentration was
18
19
lowered to 200 ppm, the Ag/CeO2/GA photocatalyst still shows the larger zone of 8.4 mm than
20
21
22 that of 500 ppm CeO2/GA material, indicating significant enhancement in antibacterial activity of
23
24 Ag/CeO2/GA photocatalyst. The antibacterial activity was further evaluated by online-monitoring
25
26 of bacterial growth in Luria-Bertani (LB) medium within 20 h. The CeO2/GA and Ag/GA were
27
28
29 used as comparisons. As shown in Figure 6a, CeO2/GA with the high concentration of 120 ppm is
30
31 still inactive for E. coli. In contrast, the E. coli growth exhibited obvious inhibition phenomenon
32
33 with low concentration of Ag/CeO2/GA photocatalyst (80 ppm). Furthermore, the Ag/CeO2/GA is
34
35
36
also more active than that of Ag/GA with the similar Ag loading (50 ppm). The E. coli growth can
37
38 be completely inhibited by 100 ppm Ag/CeO2/GA photocatalyst (Figure 6b). Thus, the MIC100%
39
40 for Ag/CeO2/GA photocatalyst against E. coli can be determined as around 100 ppm. The results
41
42
prove that the Ag/CeO2/GA photocatalyst has significantly improved antibacterial activity by
43
44
45 decoration of Ag NPs in CeO2/GA photocatalyst.
46
47
48
49
50
51
52
53
54
55
56
57
58
59
22
1
2
3
4 (a) (b)
5
6
7
8
9
10
11
12
13
14 (c) 1h 2h 3h 4h
15
16
Water
17
18
19
20
21
22
120 ppm
23
24
25
26
27
28
150 ppm
29
30
31
32
33
34
35 (d) (e)
36
37
38
39
40
41
42
43
44
45
46
47 Figure 6. Antimicrobial characterization of photocatalysts against E. coli. (a, b) The growth curves
48
49 of E. coli treated with different materials, (c) inhibition of bacterial colonies and (d) bacteria time-
50
51 kill curves of E. coli treated with Ag/CeO2/GA. (e) Biocompatibility measurements of
52
53
54 Ag/CeO2/GA against the HepG2 cell lines. The water, Ag/GA, AgNO3 were used as the control
55
56 experiments.
57
58
59
23
1
2
3
4
5
6 The time-killing studies were used to further demonstrate the antimicrobial activity of
7
8 photocatalysts. The E. coli colonies were obtained after treatment with Ag/CeO2/GA photocatalyst
9
10 within 4 h (Figure 6c). The kinetics of killing can be calculated according to the colonies, which
11
12
13
are shown in Figure 6d. The results show that Ag/CeO2/GA photocatalyst has the dose/time-
14
15 response for killing efficacy against E. coli. The E. coli can be completely killed by 150 ppm
16
17 Ag/CeO2/GA material within 4 h. Thus, its MBC100% should be less than 150 ppm. In addition, the
18
19
MIC100%Ag and MBC100%Ag can be normalized in Ag dosage to 7.5 ppm and 11.3 ppm, respectively,
20
21
22 according to the Ag content. The low MIC and MBC indicated that the Ag/CeO2/GA material has
23
24 a higher or comparable antimicrobial activity compared to many of the reported Ag-based
25
26 materials.54 Interestingly, we found that the only 41.2% of E. coli were killed by 150 ppm
27
28
29 Ag/CeO2/GA within 4 h in the completely dark environment. Therefore, the antibacterial activity
30
31 of Ag/CeO2/GA is affected by light irradiation significantly.
32
33 Besides the high antimicrobial activity, the biocompatibility of Ag/CeO2/GA photocatalyst was
34
35
36
also demonstrated using MTT method. As shown in Figure 6e, the Ag/CeO2/GA photocatalyst
37
38 shows the dose-response cytotoxicity on HepG2 cells within 24 h incubation. It exhibits an
39
40 excellent biocompatibility when its concentration lowers to 100 ppm, wherein the high
41
42
antibacterial against E. coli. In addition, the antibacterial activity of Ag/CeO2/GA photocatalyst is
43
44
45 much higher than CeO2-based materials,38,55 and is also higher or comparable with that of some
46
47 state-of-the-art photocatalysts such as C3N4-supported Ag NPs.20,56,57. Therefore, the high
48
49 antimicrobial activity and good biocompatibility make Ag/CeO2/GA potential in elimination of
50
51
52 bacterial contamination during the practical water purification.
53
54
55
56
57
58
59
24
1
2
3 Proposed Mechanisms of Bifunctional Properties. On the basis of the above results,
4
5
6 Ag/CeO2/GA photocatalyst has the excellent organic pollutant purification performance and
7
8 antimicrobial activity. The high efficiency of Ag/CeO2/GA photocatalyst towards organic
9
10 pollutant purification is attributed to its excellent adsorption and photocatalytic activity.
11
12
13 Specifically, the residual oxygen-functional groups, the strong - stacking, anion-cation
14
15 interactions, together with the hierarchical porous structure and high pore volume make
16
17 Ag/CeO2/GA material highly efficient for organic pollutant adsorption.43,44 At the same time, the
18
19
20 organic pollutants can be degraded under the visible light irradiation. Therefore, the organic
21
22 pollutants can be removed from water completely and efficiently. It is well known that the Ag NPs
23
24 are the highly efficient antibacterial materials. However, in this Ag/CeO2/GA material, the main
25
26
27
supplier of antibacterial activity is not Ag NPs due to its ultra-low Ag content in Ag/CeO2/GA
28
29 (~7.5 wt%). Therefore, we consider that the improved photocatalytic activity by a synergistic effect
30
31 between Ag and CeO2 NPs contributes the most on bifunctional properties of Ag/CeO2/GA
32
33
materials.
34
35
36 It is well known that the photoexcited radicals such as •OH, •O2- etc. are main active species
37
38 for photodegradation property of photocatalyst.57 These radicals are also very toxic to bacteria
39
40 based on the reactive oxygen species (ROS) theory.58 Thus, the investigation of photoexcited
41
42
43 radical efficiency by photocatalysis is useful to understand the possible mechanism. Here, the ESR
44
45 spin-trap technique (with DMPO) was used to detect the photoexcited radicals. The typical
46
47 DMPO-•OH and •O2- peaks can be detected in both the mixed aqueous solution (Figure 7a) and
48
49
50
methanol solution (Figure 7b) of CeO2/GA and Ag/CeO2/GA under visible light irradiation; and
51
52 no such signals were detected in the dark. The ESR signals were also strengthened with increasing
53
54 irradiation time, indicating the increase of generated radicals. Furthermore, the efficiency of
55
56
57
58
59
25
1
2
3 photoexcited radicals by Ag/CeO2/GA is much higher than that of CeO2/GA, implying that
4
5
6 improved photocatalytic activity was achieved by a synergistic effect of Ag and CeO2 NPs. The
7
8 ESR results proved that both •OH and •O2- radicals can be generated from Ag/CeO2/GA, with •OH
9
10 radicals as the predominant species.
11
12
13 (a) (b)
14
15
16
17
18
19
20
21
22
23
24 (c) (d)
25
26
27
28
29
30
31
32
33
34
35
36 (e) (f)
37
38
39
40
41
42 Rs Rt
43
44
45 CPE
46
47
48
49 Figure 7. DMPO spin-trapping ESR spectra recorded in 2 g L-1 CeO2/GA and Ag/CeO2/GA (a)
50
51 aqueous dispersions and (b) methanol dispersions at different irradiation times, the effects of
52
53
54
reactive species scavengers on (c) MB purification efficiency and (d) antibacterial activity of
55
56
57
58
59
26
1
2
3 Ag/CeO2/GA. (e) transient photocurrent response and (f) EIS spectra of CeO2/GA and
4
5
6 Ag/CeO2/GA.
7
8
9 In order to further understand the possible mechanism, the effects of radicals on above
10
11 bifunctional properties of Ag/CeO2/GA photocatalyst were investigated using the radical trapping
12
13 experiments. The efficiency of MB photodegradation by Ag/CeO2/GA photocatalyst with/without
14
15
16 scavengers can be seen in Figure 7c. The hole scavenger of disodium ethylenediaminetetraacetate
17
18 (Na2-EDTA), the •OH scavenger of tert-butanol (TBA) and the O2•- scavenger of p-benzoquinone
19
20 (BZQ) were used in the experiments. The inhibition efficiencies of MB photodegradation are
21
22
23 estimated to be 78.5% for Na2-EDTA, 64.8% for TBA, and 35.5% for BZQ, respectively.
24
25 Obviously, the holes and •OH radicals are dominant active species for photodegradation
26
27 performance because of their strong oxidized activity. Furthermore, the holes are crucial for
28
29
30
formation of •OH radicals. Thus, above results are high consistence with ESR analysis. The radical
31
32 effect on antimicrobial activity was also investigated using the growth curve measurement of E.
33
34 coli treated by Ag/CeO2/GA material with/without radical scavenger of N-acetyl-L-cysteine
35
36 (NAC). As shown in Figure 7d, the antibacterial activity of Ag/CeO2/GA was obviously weakened
37
38
39 by adding the NAC or without light irradiation, indicates that photoexcited holes and radicals are
40
41 also crucial for the antibacterial activity. Therefore, Ag/CeO2/GA with improved photocatalytic
42
43 activity has the both organic pollutant purification and antibacterial properties through
44
45
46 photoexcited holes and •OH radicals efficiently.
47
48 The synergistic effect of Ag and CeO2 NPs can improve the activity of photocatalyst through
49
50 modifying electronic structure of photocatalyst. As well as we know, the Ag NPs can be used as
51
52
53
electron accepters and transporters because of their excellent electronic conductivity.57 Therefore,
54
55 the photoexcited electrons can be transported rapidly from CeO2 NPs to Ag NPs, which is useful
56
57
58
59
27
1
2
3 for suppressing the charge recombination and generating more holes and electrons. In order to
4
5
6 prove this synergistic effect, the electronic interaction between Ag NPs and CeO2/GA is studied
7
8 by transient photocurrent measurements, which is shown in Figure 7e. Both CeO2/GA and
9
10 Ag/CeO2/GA photocatalysis showed a sensitive photocurrent response during the on/off visible
11
12
13
light irradiation. The Ag/CeO2/GA photocatalyst has a 4.7 times higher photocurrent value than
14
15 that of CeO2/GA, indicates its better visible light response and more efficient photo-existed
16
17 separation of hole and electron pairs. The electronic structure of Ag/CeO2/GA is further
18
19
investigated by EIS. The EIS Nyquist plots of Ag/CeO2/GA and CeO2/GA electrodes under
20
21
22 visible-light irradiation are shown in Figure 7f. The arc radius for Ag/CeO2/GA photocatalyst is
23
24 much smaller than that of CeO2/GA photocatalyst, indicating that Ag/CeO2/GA has more effective
25
26 separation of photoexcited holes and electrons and faster interfacial charge transfer. Figure S8
27
28
29 shows the UV-vis diffuse reflectance spectra of CeO2/GA and Ag/CeO2/GA photocatalysts.
30
31 Compared with CeO2/GA, the absorption edges of the Ag/CeO2/GA photocatalyst has remarkable
32
33 red shift and significantly enhanced absorption intensities of light.34 That means the Ag/CeO2/GA
34
35
36
photocatalyst has more visible light harvesting, and improved photocatalytic activity compared
37
38 with that of CeO2/GA because of unique optical property of Ag NPs.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
28
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 Figure 8. The mechanism of organic pollutant purification and antibacterial properties for
33
34
Ag/CeO2/GA photocatalyst.
35
36
37
38
Thus, the mechanism of Ag/CeO2/GA in bifunctional properties can be confirmed according to
39
40 above data and analysis, which can be seen in Figure 8. When the Ag/CeO2/GA material is
41
42 irradiated with visible light, the separated hole/electron pairs of CeO2 conductor in Ag/CeO2/GA
43
44
can be generated. These photoexcited electrons can react directly with adsorbed O2 on surface of
45
46
47 catalyst to form the •O2-. The •O2- or h+ anions can combine with H2O or H+ to produce the •OH.
48
49 The h+, •OH, and •O2- can degrade the organic pollutants and kill the bacteria in water.18
50
51 Importantly, the excellent conductivity makes GA and Ag NPs efficient as acceptors and
52
53
54 transporters of photoexcited electrons.18 Thus, the rapid electron transportation from CeO2 NPs to
55
56 GA and Ag NPs is beneficial for keeping the electrons away from CeO2, effective suppressing the
57
58
59
29
1
2
3 charge recombination and generating more holes and electrons. In doing so, the radicals can be
4
5
6 produced continuously and efficiently under the visible-light irradiation, and make Ag/CeO2/GA
7
8 efficient removing organic pollution from water while protecting water from bacterial pollution.
9
10 Furthermore, its good stability and excellent biocompatibility also demonstrate that such
11
12
13
Ag/CeO2/GA material holds a great potential in water purification applications.
14
15 Conclusions
16
17 In summary, we have developed a facile and efficient approach of modified gelatinization reaction
18
19
method for the synthesis of Ag/CeO2/GA. The two processes, adjustment of GO concentration and
20
21
22 ultrasonic-assisted pre-reduction, play the important roles in the formation of macroscopic porous
23
24 graphene-supported small and highly dispersive NPs (Size: 14.5 nm for Ag NPs, 11.6 nm for CeO2
25
26 NPs). This Ag/CeO2/GA material shows the high efficiency for organic pollutant purification
27
28
29 including MB dye and colorless BPA due to its strong absorption ability and highly photocatalytic
30
31 activity. This material also exhibits excellent antimicrobial property with low MIC100%Ag of 7.5
32
33 ppm and MBC100%Ag of 11.3 ppm against E. coli. The unique surface plasmonic effect of Ag NPs
34
35
36
not only can harvest more visible light, but also can decrease the recombination of photoexcited
37
38 holes and electrons thought their photoconductivity for charge transportation. Therefore, the
39
40 radicals can be produced continuously and efficiently under the visible-light irradiation, enabling
41
42
Ag/CeO2/GA to efficiently remove organic pollution from water and protect water from bacterial
43
44
45 pollution. In addition, the good recycling stability and biocompatibility suggest that such
46
47 bifunctional material has a great promise in water purification applications.
48
49 ASSOCIATED CONTENT
50
51
52
53 Supporting Information.
54
55
56 The Supporting Information is available free of charge. ACS Publications website DOI:
57
58
59
30
1
2
3 The chemicals, the synthesis of CeO2 NPs and GO, the detailed procedures for antimicrobial
4
5
6 properties, the procedures of BPA concentration measurement during the photodegradation
7
8 process. The TEM images of CeO2 NPs, CeO2/GA and Ag/CeO2/GA prepared with other
9
10 conditions.
11
12
13
14
Author Information
15
16 Corresponding Author
17
18
19 *E-mail: yazhou@ujs.edu.cn (Y Zhou); yangjuan6347@mail.ujs.edu.cn (J Yang)
20
21
22 Author Contributions
23
24
The manuscript was written through contributions of all authors. All authors have given approval to the final version of the
25
26 manuscript.
27
28
29 The authors declare no competing financial interest.
30
31
32
33
ACKNOWLEDGMENT
34
35 We gratefully acknowledge the financial support from the National Natural Science Foundation of
36
37 China (Grant 51572114, 51672112 and 51702129). Y. Z wants to thank supporting from
38
39
Postdoctoral Science Foundation (2018M630527) and China Scholarship Council
40
41
42 (201708320150). Z. N thanks to the Key University Science Research Project of Jiangsu province
43
44 (16KJB430009).
45
46
47 References
48
49
50 (1) Fu, G.; Yan, X.; Chen, Y.; Xu, L.; Sun, D.; Lee, J. M.; Tang, Y. Boosting Bifunctional
51
52 Oxygen Electrocatalysis with 3D Graphene Aerogel‐Supported Ni/MnO Particles. Adv. Mater.
53
54 2018, 30, 1704609.
55
56
57
58
59
31
1
2
3 (2) Jiang, Y.; Xu, Z.; Huang, T.; Liu, Y.; Guo, F.; Xi, J.; Gao, W.; Gao, C. Direct 3D Printing
4
5
6 of Ultralight Graphene Oxide Aerogel Microlattices. Adv. Funct. Mater. 2018, 28, 1707024.
7
8 (3) Kumar, R.; Singh, R. K.; Singh, D. P.; Joanni, E.; Yadav, R. M.; Moshkalev, S. A. Laser-
9
10 Assisted Synthesis, Reduction and Micro-Patterning of Graphene: Recent Progress and
11
12
13
Applications. Coord. Chem. Rev. 2017, 342, 34-79. DOI: org/10.1016/j.ccr.2017.03.021
14
15 (4) Zhou, Y.; Yen, C. H.; Fu, S.; Yang, G.; Zhu, C.; Du, D.; Wo, P.C.; Cheng, X.; Yang, J.;
16
17 Wai, C. M.; Lin, Y. One-Pot Synthesis of B-Doped Three-Dimensional Reduced Graphene
18
19
Oxide via Supercritical Fluid for Oxygen Reduction Reaction. Green Chem. 2015, 17, 3552-
20
21
22 3560.
23
24 (5) Lv, L.; Zhang, P.; Cheng, H.; Zhao, Y.; Zhang, Z.; Shi, G.; Qu, L. Solution‐Processed
25
26 Ultraelastic and Strong Air‐Bubbled Graphene Foams, Small 2016, 12, 3229-3234.
27
28
29 (6) Zhou, Y.; Yang, J.; Zhu, C.; Du, D.; Cheng, X.; Yen, C. H.; Wai, C. M.; Lin, Y. Newly
30
31 Designed Graphene Cellular Monolith Functionalized with Hollow Pt-M (M=Ni, Co)
32
33 Nanoparticles as the Electrocatalyst for Oxygen Reduction Reaction, ACS Appl. Mater.
34
35
36
Interfaces 2016, 8, 25863-25874.
37
38 (7) Kumara, R.; Joanni, E.; Singh, R. K.; Singh, D. P.; Moshkalev, S. A. Recent Advances in
39
40 the Synthesis and Modification of Carbon-Based 2D Materials for Application in Energy
41
42
Conversion and Storage. Prog. Energy Combust. Sci. 2018, 67, 115-157. DOI:
43
44
45 dx.doi.org/10.1016/j.pecs.2018.03.001
46
47 (8) Ge, J.; Shi, L. A.; Wang, Y. C.; Zhao, H. Y.; Yao, H. B.; Zhu, Y. B.; Zhang, Y.; Zhu, H.W.;
48
49 Wu, H. A.; Yu, S. H. Joule-Heated Graphene-Wrapped Sponge Enables Fast Clean-up of
50
51
52 Viscous Crude-Oil Spill. Nat. Nanotechnol. 2017, 12, 434-442.
53
54
55
56
57
58
59
32
1
2
3 (9) Subrati, A.; Mondal, S.; Ali, M.; Alhindi, A.; Ghazi, R.; Abdala, A.; Reinalda, D.;
4
5
6 Alhassan, S. Developing Hydrophobic Graphene Foam for Oil Spill Cleanup. Ind. Eng. Chem.
7
8 Res. 2017, 56, 6945-6951.
9
10 (10) Huang, J.; Yan, Z. Adsorption Mechanism of Oil by Resilient Graphene Aerogels from
11
12
13
Oil-Water Emulsion. Langmuir, 2018, 34, 1890-1898.
14
15 (11) Luo, Y.; Jiang, S.; Xiao, Q.; Chen, C.; Li, B. Highly Reusable and Superhydrophobic
16
17 Spongy Graphene Aerogels for Efficient Oil/Water Separation. Sci. Rep. 2017, 7, 7162.
18
19
(12) Zhang, P.; Liao, Q.; Zhang, T.; Cheng, H.; Huang, Y.; Yang, C.; Li, C.; Jiang, L.; Qu, L.
20
21
22 High Throughput of Clean Water Excluding Ions, Organic Media, and Bacteria from Defect-
23
24 Abundant Graphene Aerogel under Sunlight, Nano Energy 2018, 46, 415-422.
25
26 (13) Chen, Y.; Song, X.; Zhao, T.; Xiao, Y.; Wang, Y.; Chen, X. A Phosphorylethanolamine-
27
28
29 Functionalized Super-hydrophilic 3D Graphene-Based Foam Filter for Water Purification, J.
30
31 Hazard. Mater. 2018, 343, 298-303
32
33 (14) Cheng, C.; Deng, J.; Lei, B.; He, A.; Zhang, X.; Ma, L.; Li, S.; Zhao, C. Toward 3D
34
35
36
Graphene Oxide Gels Based Adsorbents for High-Efficient Water Treatment via the Promotion
37
38 of Biopolymers. J. Hazard. Mater. 2013, 263, 467-478.
39
40 (15) Zhang, X. Y.; Li, H. P.; Cui, X. L.; Lin, Y. Graphene/TiO2 Nanocomposites: Synthesis,
41
42
Characterization and Application in Hydrogen Evolution from Water Photocatalytic Splitting.
43
44
45 J. Mater. Chem. 2010, 20, 2801-2806.
46
47 (16) Sun, H.; Liu, S.; Liu, S.; Wang, S. A Comparative Study of Reduced Graphene Oxide
48
49 Modified TiO2, ZnO and Ta2O5 in Visible Light Photocatalytic/Photochemical Oxidation of
50
51
52 Methylene Blue. Appl. Catal. B-Environ. 2014, 146, 162-168.
53
54
55
56
57
58
59
33
1
2
3 (17) Xiang, Q.; Lang, D.; Shen, T.; Liu, F. Graphene-modified Nanosized Ag3PO4
4
5
6 Photocatalysts for Enhanced Visible-Light Photocatalytic Activity and Stability. Appl. Catal.
7
8 B-Environ. 2015, 162, 196-203.
9
10 (18) Zhou, Y.; Chen, R.; He, T.; Xu, K.; Du, D.; Zhao, N.; Cheng, X.; Yang, J.; Shi, H.; Lin, Y.
11
12
13
Biomedical Potential of Ultrafine Ag/AgCl Nanoparticles Coated on Graphene with Special
14
15 Reference to Antimicrobial Performances and Burn Wound Healing. ACS Appl. Mater.
16
17 Interfaces 2016, 8, 15067-15075.
18
19
(19) Verma, R.; Samdarshi, S. K. In Situ Decorated Optimized CeO2 on Reduced Graphene
20
21
22 Oxide with Enhanced Adsorptivity and Visible Light Photocatalytic Stability and Reusability.
23
24 J. Phys. Chem. C 2016, 120, 22281-22290.
25
26 (20) Deng, W.; Chena, D.; Hub, J.; Chen, L. A General and Green Approach to Synthesize
27
28
29 Monodisperse Ceria Hollow Spheres with Enhanced Photocatalytic Activity. RSC Adv. 2015,
30
31 5, 80158-80169.
32
33 (21) Choi, J.; Reddy, D. A.; Islam, M. J.; Ma, R.; Kim, T. K. Self-Assembly of CeO2
34
35
36
Nanostructures/Reduced Graphene Oxide Composite Aerogels for Efficient Photocatalytic
37
38 Degradation of Organic Pollutants in Water. J. Alloy Compd. 2016, 688, 527-536.
39
40 (22) Jha, S. K.; Kumar, C. N.; Raj, R. P.; Jha, N. S.; Mohan, S. Synthesis of 3D Porous
41
42
CeO2/Reduced Graphene Oxide Xerogel Composite and Low Level Detection of H2O2.
43
44
45 Electrochim Acta 2014, 120, 308-313.
46
47 (23) Nawaz, M.; Miran, W.; Jang, J.; Lee, D. S. One-step Hydrothermal Synthesis of Porous
48
49 3D Reduced Graphene Oxide/TiO2 Aerogel for Carbamazepine Photodegradation in Aqueous
50
51
52 Solution. Appl. Catal. B-Environ. 2017, 203, 85-95.
53
54
55
56
57
58
59
34
1
2
3 (24) Cui, C.; Li, S.; Qiu, Y.; Hu, H.; Li, X.; Li, C.; Gao, J.; Tang, W. Fast Assembly of Ag3PO4
4
5
6 Nanoparticles within Three-Dimensional Graphene Aerogels for Efficient Photocatalytic
7
8 Oxygen Evolution from Water Splitting under Visible Light. Appl. Catal. B-Environ. 2017,
9
10 200, 666-672.
11
12
13
(25) Fan, Y.; Ma, W.; Han, D.; Gan, S.; Dong, X.; Niu, L. Convenient Recycling of 3D
14
15 AgX/graphene Aerogels (X= Br, Cl) for Efficient Photocatalytic Degradation of Water
16
17 Pollutants. Adv. Mater. 2015, 27, 3767-3773.
18
19
(26) Adhikari, B.; Biswas, A.; Banerjee, A. Graphene Oxide-Based Hydrogels to Make Metal
20
21
22 Nanoparticle-Containing Reduced Graphene Oxide-Based Functional Hybrid Hydrogels. ACS
23
24 Appl. Mater. Interfaces 2012, 4, 5472-5482.
25
26 (27) Kumar, R.; Singh, R. K.; Alaferdov, A. V.; Moshkalev, S. A. Rapid and Controllable
27
28
29 Synthesis of Fe3O4 Octahedral Nanocrystals Embedded-Reduced Graphene Oxide using
30
31 Microwave Irradiation for High Performance Lithium-Ion Batteries. Electrochim. Acta 2018,
32
33 281, 78-87. DOI: org/10.1016/j.electacta.2018.05.157
34
35
36
(28) Kumar, R.; Singh, R. K.; Dubey, P. K.; Singh, D. P.; Yadav, R. M. Self-Assembled
37
38 Hierarchical Formation of Conjugated 3D Cobalt Oxide Nanobead-CNT-Graphene
39
40 Nanostructure Using Microwaves for High-Performance Supercapacitor Electrode. ACS Appl.
41
42
Mater. Interfaces 2015, 7, 15042−15051. DOI: 10.1021/acsami.5b04336.
43
44
45 (29) Kumar, R. Singh, R. K.; Vaz, A. R.; Savu, R.; Moshkalev, S. A. Self-Assembled and One-
46
47 Step Synthesis of Interconnected 3D Network of Fe3O4/Reduced Graphene Oxide Nanosheets
48
49 Hybrid for High-Performance Supercapacitor Electrode. ACS Appl. Mater. Interfaces 2017, 9,
50
51
52 8880-8890. DOI: 10.1021/acsami.6b14704.
53
54
55
56
57
58
59
35
1
2
3 (30) Zhou, Y.; Yen, C. H.; Hu, Y. H.; Wang, C.; Cheng, X.; Wai, C. M.; Yang, J.; Lin, Y.
4
5
6 Making Ultrafine and Highly-Dispersive Multimetallic Nanoparticles in Three-Dimensional
7
8 Graphene with Supercritical Fluid as Excellent Electrocatalyst for Oxygen Reduction Reaction.
9
10 J. Mater. Chem. A 2016, 4, 18628-18638.
11
12
13
(31) Ottoson, J.; Stenström, T. A. Faecal Contamination of Greywater and Associated Microbial
14
15 Risks. Water Res. 2003, 37, 645-55.
16
17 (32) Wu, S. E.; Hwang, K. J.; Cheng, T. W.; Lin, Y. C.; Tung, K. L. Dynamic Membranes of
18
19
Powder-Activated Carbon for Removing Microbes and Organic Matter from Seawater. J.
20
21
22 Membrane Sci. 2017, 541, 189-197.
23
24 (33) Zhou, Y.; Yang, J.; He, T.; Shi, H.; Cheng, X.; Lu, Y. Highly Stable and Dispersive Silver
25
26 Nanoparticle–Graphene Composites by a Simple and Low‐Energy‐Consuming Approach and
27
28
29 Their Antimicrobial Activity. Small 2013, 9, 3445-3454.
30
31 (34) Saravanakumar, K.; Ramjan, M. M.; Suresh, P. ; Muthuraj, V. Fabrication of Highly
32
33 Efficient Visible Light Driven Ag/CeO2 Photocatalyst for Degradation of Organic Pollutants.
34
35
36
J. Alloy Compd. 2016, 664, 149-160.
37
38 (35) Yu, T.; Zeng, J.; Lim, B.; Xia, Y. Aqueous-Phase Synthesis of Pt/CeO2 Hybrid
39
40 Nanostructures and Their Catalytic Properties. Adv. Mater. 2010, 22, 5188-5192.
41
42
(36) Wang, C. Y.; Zhang, X.; Song, X. N.; Wang, W. K.; Yu, H. Q. Novel Bi12O15Cl6
43
44
45 Photocatalyst for the Degradation of Bisphenol A under Visible-Light Irradiation, ACS Appl.
46
47 Mater. Interfaces 2016, 8, 5320-5326.
48
49 (37) Zhou, Y.; Yang, G.; Pan, H. B.; Zhu, C.; Fu, S.; Shi, Q.; Du, D.; Cheng, X.; Yang, J.; Wai,
50
51
52 C. M.; Lin, Y. Ultrasonic-Assisted Synthesis of Carbon Nanotube Supported Bimetallic Pt-Ru
53
54 Nanoparticles for Effective Methanol Oxidation. J. Mater. Chem. A 2015, 3, 8459-8465.
55
56
57
58
59
36
1
2
3 (38) Wang, L.; He, H.; Yu, Y.; Sun, L.; Liu, S.; Zhang, C.; He, L. Morphology-Dependent
4
5
6 Bactericidal Activities of Ag/CeO2 Catalysts Against Escherichia coli. J. Inorg. Biochem. 2014,
7
8 135, 45-53.
9
10 (39) Zhou, Y.; Yang, J.; Cheng, X.; Zhao, N.; Sun, H.; Li, D. Transparent and Conductive
11
12
13
Reduced Graphene Oxide/Silver Nanoparticles Multilayer Film Obtained by Electrical Self-
14
15 Assembly Process with Graphene Oxide Sheets and Silver Colloid. RSC Adv. 2013, 3, 3391-
16
17 3398.
18
19
(40) Zhou, Y.; Cheng, X.; Du, D.; Yang, J.; Zhao, N.; Ma, S.; Zhong, T.; Lin, Y. Graphene-
20
21
22 Silver Nanohybrids for Ultrasensitive Surface Enhanced Raman Spectroscopy: Size
23
24 Dependence of Silver Nanoparticles. J. Mater. Chem. C 2014, 2, 6850-6858.
25
26 (41) Levard, C.; Hotze, E. M.; Lowry, G. V.; Brown, G. E. Environmental Transformations of
27
28
29 Silver Nanoparticles: Impact on Stability and Toxicity. Environ. Sci. Technol. 2012, 46, 6900-
30
31 6914.
32
33 (42) Xiu, Z.; Zhang, Q.; Puppala, H. L.; Colvin, V. L.; Alvarez, P. J. J. Negligible Particle-
34
35
36
Specific Antibacterial Activity of Silver Nanoparticles. Nano Lett. 2012, 12, 4271-4275.
37
38 (43) Kumar, R.; Singh, R. K.; Kumar, V.; Moshkalev, S. A. (2019) Functionalized Nanosize
39
40 Graphene and Its Derivatives for Removal of Contaminations and Water Treatment. In:
41
42
Naushad M. (eds) A New Generation Material Graphene: Applications in Water Technology.
43
44
45 Springer, Cham.
46
47 (44) Kumar, R.; Singh, R. K.; Kumar, V.; Moshkalev, S. A. (2019) Graphene/Graphene Oxide
48
49 and Carbon Nanotube Based Sensors for the Determination and Removal of Bisphenols. In:
50
51
52 Naushad M. (eds) A New Generation Material Graphene: Applications in Water Technology.
53
54 Springer, Cham.
55
56
57
58
59
37
1
2
3 (45) Gu, P.; Zhang, S.; Li, X.; Wang, X.; Wen, T.; Jehan, R.; Alsaedi, A.; Hayat, T.; Wang, X.
4
5
6 Recent Advances in Layered Double Hydroxide-Based Nanomaterials for the Removal of
7
8 Radionuclides from Aqueous Solution. Environ. Pollut. 2018, 240, 493-505. DOI:
9
10 org/10.1016/j.envpol.2018.04.136.
11
12
13
(46) Yu, S.; Wang, X.; Pang, H.; Zhang, R.; Song, W.; Fu, D.; Hayat, T.; Wang, X. Boron
14
15 Nitride-Based Materials for the Removal of Pollutants from Aqueous Solutions: A Review.
16
17 Chem. Eng. J. 2018, 333, 343-360. DOI: dx.doi.org/10.1016/j.cej.2017.09.163.
18
19
(47) Li, J.; Wang, X.; Zhao, G.; Chen, C.; Chai, Z.; Alsaedi, A.; Hayat, T.; Wang, X. Metal-
20
21
22 Organic Framework-Based Materials: Superior Adsorbents for the Capture of Toxic and
23
24 Radioactive Metal Ions. Chem. Soc. Rev. 2018, 47, 2322-2356. DOI: 10.1039/c7cs00543a.
25
26 (48) Zhao, G.; Huang, X.; Tang, Z.; Huang, Q.; Niu, F.; Wang, X. Polymer-Based
27
28
29 Nanocomposites for Heavy Metal Ions Removal from Aqueous Solution: A Review. Polym.
30
31 Chem. 2018, 9, 3562-3582. DOI: 10.1039/c8py00484f.
32
33 (49) Oh, W. D.; Lok, L. W.; Veksha, A.; Giannis, A.; Lim, T. T. Enhanced Photocatalytic
34
35
36
Degradation of Bisphenol A with Ag-Decorated S-doped g-C3N4 under Solar Irradiation:
37
38 Performance and Mechanistic Studies, Chem. Eng. J. 2018, 333, 739-749.
39
40 (50) Kumar, S.; Kumar, A. Enhanced Photocatalytic Activity of rGO-CeO2 Nanocomposites
41
42
Driven by Sunlight. Mater. Sci. Eng. B 2017, 223, 98-108
43
44
45 (51) Men, X.; Chen, H.; Chang, K.; Fang, X.; Wu, C.; Qin, W.; Yin, S. Three-Dimensional
46
47 Free-Standing ZnO/Graphene Composite Foam for Photocurrent Generation and Photocatalytic
48
49 Activity. Appl. Catal. B-Environ. 2016, 187, 367-374.
50
51
52
53
54
55
56
57
58
59
38
1
2
3 (52) Nawaz, M.; Miran, W.; Jang, J.; Lee, D. S. One-Step Hydrothermal Synthesis of Porous
4
5
6 3D Reduced Graphene Oxide/TiO2 Aerogel for Carbamazepine Photodegradation in Aqueous
7
8 Solution. Appl. Catal. B-Environ. 2017, 203, 85-95.
9
10 (53) Tenaillon, O.; Skurnik, D.; Picard, B.; Denamur, E. The Population Genetics of
11
12
13
Commensal Escherichia coli. Nat. Rev. Microbiol. 2010, 8, 207-217.
14
15 (54) Chernousova, S.; Epple, M. Silver as Antibacterial Agent: Ion, Nanoparticle, and Metal.
16
17 Angew. Chem. Int. Ed. 2013, 52, 1636-1653.
18
19
(55) Moongraksathum, B.; Chen, Y. W. Anatase TiO2 Co-Doped with Silver and Ceria for
20
21
22 Antibacterial Application. Catal. Today 2018, 310, 68-74. DOI:
23
24 x.doi.org/10.1016/j.cattod.2017.05.087.
25
26 (56) Khan, M. E.; Han, T. H.; Khan, M. M.; Karim, M. R.; Cho, M. H. Environmentally
27
28
29 Sustainable Fabrication of Ag@g-C3N4 Nanostructures and Their Multifunctional Efficacy as
30
31 Antibacterial Agents and Photocatalysts. ACS Appl. Nano Mater. 2018, 1, 2912-2922. DOI:
32
33 10.1021/acsanm.8b00548.
34
35
36
(57) Wu, Y.; Zhou, Y.; Xu, H.; Liu, Q.; Li, Y.; Zhang, L.; Liu, H.; Tu, Z.; Cheng, X.; Yang. J.
37
38 Highly Active, Superstable, and Biocompatible Ag/Polydopamine/g-C3N4 Bactericidal
39
40 Photocatalyst: Synthesis, Characterization, and Mechanism, ACS Sustainable Chem. Eng. 2018.
41
42
DOI: 10.1021/acssuschemeng.8b02620.
43
44
45 (58) Hou, Y.; Li, X.; Zhao, Q.; Chen, G.; Raston, C. L. Role of Hydroxyl Radicals and
46
47 Mechanism of Escherichia coli Inactivation on Ag/AgBr/TiO2 Nanotube Array Electrode under
48
49 Visible Light Irradiation. Environ. Sci. Technol. 2012, 46, 4042-4050.
50
51
52
53
54
55
56
57
58
59
39
1
2
3
4
5
6 For Table of Contents Use Only
7
8
9 A bifunctional material of graphene aerogel supporting highly-dispersed Ag and CeO2 NPs with
10
11
12 organic pollutant removing and antimicrobial properties was prepared by a facile method. Such
13
14 bifunctional properties are attributed to the improved photocatalytic activity by synergistic effect
15
16 of Ag and CeO2. The good recycling stability and biocompatibility suggest that such material has
17
18
19 a great promise in water purification applications.
20
21 SYNOPSIS
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
40

Bifunctional Material With Organic Pollutant Removing and

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Bifunctional Material With Organic Pollutant Removing and

Uploaded by

Copyright:

Available Formats

Subscriber access provided by UNIV OF NEW ENGLAND ARMIDALE

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

You might also like