One-Pot Transformation of Waste Toner Powder into 3D Graphene

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One-Pot Transformation of Waste Toner Powder into 3D Graphene Oxide Hydrogel Zhengshan Tian, Kesheng Cao, Suzhen Bai, Guoxu He, and Jitao Li ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b03997 • Publication Date (Web): 23 Nov 2018 Downloaded from http://pubs.acs.org on November 23, 2018

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ACS Sustainable Chemistry & Engineering

One-Pot Transformation of Waste Toner Powder into 3D Graphene Oxide Hydrogel Zhengshan Tian,*,† Kesheng Cao,† Suzhen Bai,† Guoxu He,† and Jitao Li*,‡ †

School of Chemistry and Environmental Engineering, Pingdingshan University, Weilai Road,

Pingdingshan 467000, People‟s Republic of China ‡

School of Physics and Telecommunications Engineering, Zhoukou Normal University, Wenchang

Dong Road, Zhoukou 466001, People‟s Republic of China Corresponding Authors: *E-mail: [email protected] and [email protected].

ABSTRACT: Waste toner powder is considered not only a recyclable resource but also a hazardous material, because it has a unique microstructure and complex compositions, so it should be properly disposed by an effective way. Herein, we selected waste toner powder as a precursor to synthesize three-dimensional (3D) porous graphene oxide (GO) hydrogel by a one-pot transformation based on the improved Hummers‟ method. A series of detection equipments such as scanning electron microscope and Raman spectrometer,

can

be

employed

to

probe

the

microstructure

and

formation mechanism of 3D GO hydrogel. Our experimental results show that 3D porous GO hydrogel with its excellent microstructure can be prepared by using waste toner powder as the precursor. It provides an effective way to dispose waste toner powder for functional applications.

KEYWORDS: One-pot, Waste toner powder, Improved Hummers‟ method, Ultrasonic treatment, Graphene oxide hydrogel 1

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INTRODUCTION Due to the office automation, there would be lots of waste toner powder in use,1 especially when printer toner powder needs to be added again, the residual toner powder in the toner cartridge and waste powder storage box should be eliminated and probably discarded. Therefore, the waste toner powder should be properly disposed by an effective way, it has attracted great attention at home and abroad. In fact, the waste toner powder was considered a recyclable resource with many functional applications.1-6 Although there are many types of printer toners, the waste toner powder is generally considered to be a granular mixture and comprise of carbon black, polyacrylate, polystyrene, Fe3O4 and SiO2. 1-3, 7 On the other hand, if the waste toner powder is not properly disposed, it is also considered a hazardous material.8-14 Due to its fine particle size and complex components, the waste toner powder leads to many undesirable physiological effects in the human body through the respiratory system.1 Moreover, with its size smaller and smaller, it can easily cause a dust explosion.4, 10 In the past, the waste toner powder has generally been disposed by the manners of incineration and landfill. In the landfill process, the waste toner powder can cause critical contamination, it will pollute soil and underground water, and it also release gases such as methane and carbon dioxide. While the incineration is not a proper method

for

treating

waste

toner

powder,

which

also

leads

to

release

other harmful gases and waste solids. Additionally, the incineration and landfill will lose the valuable resources of waste toner powder. 2


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With the increasing importance of environmental sustainability,5 the waste toner powder should be properly disposed. Fortunately, significant efforts have been previously made to the development of the disposing technology of waste toner powder. For examples, Ruan et al. designed a recovery technology of vacuum-gasification-condensation.1 Using this recovery technology, industrial chemicals were obtained in the pyrolysis process of waste toner. Moreover, abundant nanomaterials of SiO2 and Fe3O4 were also produced. Gaikwad and his colleagues designed a recovery technology through a thermal transformation process.3, 4 This process leveraged high-temperature reactions to obtain 98% Pure iron. Fu et al.6 prepared novel carbon nanospheres from printer toner powder to design an ultrasensitive label-free immunosensor. The fabricated immunosensor shows excellent improvement of sensitivity. Although the above methods suggest many ways to recycle waste toner powder for various functional applications, an effective way to recycle carbon resource of waste toner powder on a large scale should be explored. Recently,

graphene

and

graphene

derivative

materials

with

many excellent properties 15-19 have attracted considerable attention in the world, and the preparation of them needs lots of carbon resources. While the waste toner powder contains high quality carbon resource with unique microstructure, whether it can be employed to synthesize graphene-derivative nanomaterials, but so far, no such literature has been reported. Therefore, using waste toner powder to prepare 3D porous GO hydrogel through a one-pot process is highly needed. In this study, we investigated the potential application of waste toner powder as 3



the precursor for preparing 3D porous GO hydrogel by a one-pot strategy based on the improved Hummers‟ method. The experimental results show that the waste toner powder can be used to prepare 3D porous GO hydrogel with its excellent morphology.

EXPERIMENTAL SECTION Materials. Waste toner powder was retrieved from the toner cartridge and waste powder storage box of the laser printer (HP1020). Other chemicals such as KMnO4, NaNO3, H2SO4, H2O2, and HCl, were analytically pure. Deionized water was used for all experiments. Preparation of the Samples. The waste toner powder acted as the precursor to prepare 3D porous GO hydrogel by a one-pot transformation based on the improved Hummers‟ method. The mechanism of Hummers‟ method is introduced briefly as follows. Graphite is firstly oxidized into graphite oxide in the strong oxidation process of the improved Hummers‟ method, and then GO sheets with a layered structure can be obtained by exfoliating graphite oxide in deionized water.20, 21 In a typical procedure, the preparation details are described as follows. Firstly, the waste toner powder was oxidized into powder oxide based on the modified Hummers‟ method. (1) Waste toner powder (3 g) was mixed with NaNO3 (1 g) in a beaker, after adding H2SO4 (69 mL) into the beaker under an ice bath and magnetic stirring, KMnO4 (9 g) was added stage by stage. (2) When the addition of KMnO4 was finished, a hot water bath was used to heat the above mixture from 0 °C to 35 °C, and the above mixture was kept at this 4


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temperature for 30 min under magnetic stirring. (3) After adding 138 mL of deionized water into the beaker, it was heated to about 98 °C and kept at this temperature for 30 min. Secondly, the above mixture containing powder oxide was obtained and purified to remove the impurities. That is, the above mixture containing powder oxide was mixed with moderate amounts of deionized water and H2O2, after natural cooling, the above mixture was purified by filtration, multiple washings, centrifugations and decanting. During the filtration process, mixed cellulose ester microporous membrane (0.45 μm) was selected as a filter tool. In order to improve the filtration efficiency, a decompressional filtration was carried out by using circulating water vacuum pump (SHB-III). Thirdly, a homogeneous aqueous GO hydrogel was obtained from the exfoliation of powder oxide in deionized water at room temperature. The sample of GO hydrogel was further purified by filtration, multiple washings, centrifugations and decanting after washing with 200 mL of 37% HCl. Finally, the product of GO hydrogel can be obtained by vacuum drying at 60 °C. Waste Disposal. In order to obtain pure GO hydrogel, the samples will be purified by the filtration, multiple washings, centrifugations and decanting, so there will invariable be a significant amount of „effluent‟, and appropriate waste disposal will be of great importance. In our experiments, to improve the efficiency and reduce the amount of water, the decompressional filtration was carried out by using circulating water vacuum pump (SHB-III), and the centrifugation process was carried 5



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out by a high-speed refrigerated centrifuge (Neofuge1600R, 16000 r/min). Moreover, SiO2 can be retained in the filtrate and recycled by centrifugation. In the strong oxidation process of the improved Hummers‟ method, Fe3O4 solid particles can be dissolved into in the filtrate, which can be recycled through the transformation into Fe(OH)3 under alkaline condition, and finally into Fe2O3 under heating condition. Other components in the filtrate, such as Mn2+ (originating from KMnO4), can also be recycled by an appropriate way. Characterization. A series of detection equipments such as a scanning electron microscope

(SEM),

Fourier

transform

infrared

spectrum

(FTIR)

and

Raman spectroscopy, can be employed to probe the microstructure and complex compositions

of

waste

toner

powder,

and

the

microstructure

and

formation mechanism of 3D GO hydrogel.

RESULTS Structural Analysis. The waste toner powder regained from the toner cartridge and waste powder storage box of the laser printer (HP1020) were collected in a beaker (Figure 1a), and the waste toner powder was for black color (Figure 1b). To reveal its microstructure, SEM images of waste toner powder were carried out. Seen from the SEM images in Figure 1c-d, the waste toner powder was a granular mixture with good grain shape and fine particle size (5-15μm).

6


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Figure 1．(a, b) Optical photographs of waste toner powder and (c, d) SEM images of waste toner powder with different magnifications.

There are many different types of toner powder, and they have different structures and morphology. The waste toner powder is generally considered to be a mixture, including carbon black, polyacrylate, polystyrene, Fe3O4 and SiO2.1-3 In our experiments, the waste toner powder was retrieved from the toner cartridge and waste powder storage box of the laser printer (HP1020), and its energy dispersive X-ray spectroscopy (EDS) mapping was carried out to analyze its structure. The corresponding distribution and atomic percent (C, O, Fe and Si atoms) were shown in Figure 2. The C atoms originate from carbon black, polyacrylate and polystyrene, the O atoms come from polyacrylate, Fe3O4 and SiO2, the Si atoms only originate from SiO2, and the Fe atoms only originate from Fe3O4.

7



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Figure 2．(a) Waste toner powder SEM image in a selected region, (b-e) C, O, Fe and Si mappings.

Graphene-based macrostructures with 3D porous networks,22-25 such as aerogels,26 hydrogel,27 foams,28 frameworks29 and sponges,30 have been prepared by various methods. These 3D graphene-based materials can prevent inter-sheet restacking and provide high surface area, fast ion/electron transport for various applications. Moreover, graphene-based materials have different microstructures and functions,31

because

they

originate

from different

carbon

resources

and

preparation conditions. In our experiments, GO hydrogel was readily obtained from the waste toner powder based on a modified Hummers‟ method, so they should have their own microstructure. GO hydrogel was served in a reagent bottle and shown in Figure 3a. Figure 3b shows that GO hydrogels present dark grey. SEM images were also carried out to demonstrate the morphological differences between the waste toner powder and GO hydrogel. SEM images of GO hydrogel were shown in Figure 3c and 3d, it can be found that numerous GO sheets are well-assembled and interconnected to form a „cotton-like‟ 3D structure with wrinkling and‘waviness‟.32 GO hydrogel also has numerous micro- and nano-pore structures, as well as micro- and nano-crosslinking 8


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structures. While the waste toner powder has the granular and solid structure, which is apparently different from that of 3D porous GO hydrogel.

Figure 3. (a, b) Optical photographs of GO hydrogel and (c, d) SEM images of 3D porous GO hydrogel with different magnifications.

SiO2 and Fe3O4 are a part of the waste toner powder, which can also be retained in the GO hydrogel, so it is very important to establish what impurities remain in the GO hydrogel after the purification process. To analyze what impurities are retained in the hydrogel, the SEM-EDS mapping of the GO hydrogel for elements (C, O, Fe and Si) has been carried out, as shown in Figure 4. The elemental mapping of a selected region demonstrates clearly the corresponding distributions and atomic percents (C, O, Fe and Si atoms). A very small amount of Fe and Si atoms was retained in the GO hydrogel, and it was very less than that of the waste toner powder (Figure 2a).

9



Figure 4．(a) 3D porous GO hydrogel SEM image in a selected region, (b-e) C, O, Fe and Si mappings.

In order to further explore the microstructure of GO hydrogel, an aqueous solution of GO hydrogel was obtained through a strong ultrasonic treatment process, and this ultrasonic treatment process can peel off 3D GO hydrogel to few-layered GO sheets for easy measurement by a transmission electron microscope (TEM). Figure 5 shows that few-layered GO sheets are closely intertwined. These GO sheets originate from the exfoliation of GO hydrogel (Figure 3c and 3d) in deionized water.

Figure 5. (a, b) TEM images of ultrasonic exfoliating few-layered GO sheets with different magnifications.

Another measurement analysis of GO hydrogel was performed by the X-ray diffractometer (XRD), and the result was demonstrated (Figure 6a). From the XRD analysis of GO hydrogel, a characteristic diffraction peak (2θ = 10.06º) is consistent 10


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with a lamellar distance of ~ 8.78 Å.33 The interlayer spacing of GO hydrogel is larger than that of graphite (3.35 Å), arising from a intercalation of oxygen-containing groups between GO sheets.33-35 From Raman analyses in Figure 6b, it can be seen that 3D hydrogel has characteristic D peak (~1345 cm-1) and G peak (~1593 cm-1). Moreover, the intensity ratio (the former band/the latter band) presents 0.85, consistent with the literature reported. 33-35

(a)

(b) 10.06 (8.78 Å)

D 1345

G 1593

800

Intensity

Intensity (a.u.)

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


600

400

200 8

16

24

32

40

2 (degree)

48

56

1000

1500

2000

-1

2500

3000

Raman shift (cm )

Figure 6. (a) XRD patterns of 3D porous GO hydrogel, (b) Raman spectra of 3D porous GO hydrogel.

From the FTIR spectra analyses in Figure 7a, it can be proved that lots of functional groups are present in GO hydrogel, such as C=O, C=C, C–OH and so on.33-35 The chemical compositions of GO hydrogel were further investigated by X-ray photoelectron spectroscopy (XPS). From the XPS survey spectra analyses, it can be found that GO hydrogel has carbon and oxygen atoms (Figure 7b). Figure 7c reveals it has functional groups such as O–C=O (carboxyl, ~288.4 eV), C–O (hydroxyl and epoxy, ~285.8 eV), C=O (carbonyl, ~286.7 eV), and C=C/C–C (~284.7 eV).36 Moreover, Figure 7d demonstrates functional groups such as C–O (533.0 eV), O–C=O (532.2 eV), and C=O (531.3 eV).37 11



(a)

(b)

O1s

3430 (-OH)

1405 (-CH)

890 1250 (C-OH)

2980 (-CH) 3600

3000

1050

2400

1800

1200 -1

Wavenumber (cm

(c)

Intensity (a.u.)

1620 (C=C)

1720 (C=O)

560

(d) C=C/C-C

C=O

O-C=O

C-O

288

640

285

480

400

320

240

160

Binding energy (eV)

C1s

291

720

600

)

282

O1s

Intensity (a.u.)

Intensity (a.u.)

C1s

Intensity (a.u.)

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

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279

Binding energy (eV)

C-O

O-C=O C=O

540

537

534

531

528

Binding energy (eV)

Figure 7. (a) FTIR spectra of GO hydrogel. (b) Survey spectra of GO hydrogel investigated by X-ray photoelectron spectroscopy, (c-d) C1s and O1s high-resolution spectra of GO hydrogel investigated by X-ray photoelectron spectroscopy.

The aforementioned SEM and TEM images, XRD, Raman, FTIR and XPS analyses are consistent with the literature reported,34, 35, 38, 39 which strongly confirm that the waste toner powder can be utilized to prepare 3D GO hydrogel based on the improved Hummers‟ method.20, 21 The 3D GO hydrogel contains lots of GO sheets, which are well-assembled and interconnected to form a „cotton-like‟ 3D structure. The 3D porous structure of GO hydrogel is very different from the granular and solid structure of the waste toner powder. Formation Analysis. To probe the formation mechanism of 3D porous GO hydrogel, four important factors should be considered as follows. 12


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(1) The complex components and 3D granular structure of waste toner powder should be taken into consideration. Because of the structure and function of toner powder, it has components of carbon black, polyacrylate, polystyrene, Fe3O4 and SiO2, which constitute together the 3D granular and solid structure.1-3 In general, carbon black is color adjusting agent, polyacrylate is the main imaging material, polystyrene can control the melting point of toner powder, Fe3O4 can modify the magnetic property, SiO2 can be used for the lubricant and charge-control agents.2 (2) The waste toner powder with inherent 3D granular and solid structure can serve as a template. In fact, polystyrene and SiO2 are commonly used as template and filler to control the structures of nanometer and micro-sized materials. For example, Zhang and his colleagues utilized polystyrene microspheres as templates to fabricate 3D macroporous graphene architectures for functional application.40 Ni et al. designed a novel 3D nanostructure of graphene hollow spheres, that is, SiO2 spheres were

wrapped

by GO

sheets,

subsequently

these composite structures were

carbonized, finally SiO2 spheres were etched to obtain 3D hollow nanostructure.41 According to the morphological evolution from waste toner powder (Figure 1d) to GO hydrogel (Figure 3d), the microstructure of GO hydrogel is distinctly different from that of waste toner powder. The waste toner powder is the granular and solid structure, while GO hydrogel contains numerous GO sheets, which are well-assembled and interconnected to form a „cotton-like‟ 3D structure with wrinkling and‘waviness‟. It is reasoned that the waste toner powder serves as a template, and its 3D

structure

is reserved,

while

its

inside

13


is hollowed

out

during


Page 14 of 23

the preparation process. (3) The harsh oxidization of the modified Hummers‟ process20,

21

plays

a significant role in the “hollowing-out” process. Carbon black can be oxidized to GO sheet, polyacrylate and polystyrene can be oxidized and removed. Fe3O4 can be oxidized and mostly removed. SiO2 can almost be removed by filtration, multiple washings and centrifugation after ultrasonic treatment. (4) Ultrasonic

treatment

has played an

active role in

the

process

of

“hollowing-out”. Ultrasonic treatment can not only strip off the toner powder oxide into three-dimensional porous GO hydrogel, but also facilitate dramatically the cleaning and removal of the impurities of GO hydrogel.

DISCUSSION In our experiments, the waste toner powder was firstly oxidized into the toner powder oxide based on the improved Hummers‟ method. Subsequently, the toner powder oxide was exfoliated into GO hydrogel in deionized water. The waste toner powder with inherent 3D granular and solid structure can serve as a template to prepare 3D GO hydrogel, but its inside maybe be hollowed out to leave numerous interconnected GO sheets during the preparation process. Moreover, 3D GO hydrogel have numerous micro- and nano-pore structures, as well as micro- and nano-crosslinking structures, so that 3D GO hydrogel could have many applications, such as adsorbent, catalyst support and filters. Recently, the recycling of waste toner is gaining importance. Discarded waste toner powder was used as raw material to prepare GO hydrogel, and the 14


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procedure and equipment were simple, so the production cost was very low. Although some wastes have been produced in the preparation process of GO hydrogel, the transformation of waste toner powder into GO hydrogel is very interesting. Other components of waste toner powder can also be recycled by an appropriate way.

CONCLUSION In this work, we demonstrated that the waste toner powder was used as the precursor for preparing 3D porous GO hydrogel by a one-pot strategy based on the improved Hummers‟ method. The resulting experimental results show that the waste toner powder can be used to prepare 3D porous GO hydrogel with its excellent morphology and microstructure. It provides options for developing new disposal methods of waste toner

powder

for

functional

applications.

Our

team

is studying

the

simultaneous recovery of Fe3O4 and SiO2 of waste toner powder. AUTHOR INFORMATION *E-mail: [email protected] (Z.S.T). *E-mail: [email protected] (J.T. L). ORCID Zhengshan Tian: 0000-0002-2486-2452 ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (11604395), the Program for Science＆Technology Innovation Talents in Universities of Henan Province (18HASTIT032), the Scientific Research Foundation of Pingdingshan University (PXY-BSQD2016010 and PXY-PYJJ2017001), the Science 15



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and Technology Project of Pingdingshan City (201700611), and the High School Key Scientific Research Project of Henan Province (16A150040) in China. REFERENCES (1) Ruan, J.; Dong, L.; Huang, J.; Huang, Z.; Huang, K.; Dong, H.; Zhang, T.; Qiu, R. Vacuum-gasification-condensation of waste toner to produce industrial chemicals and nano materials. ACS Sustainable Chem. Eng. 2017, 5, 4923-4929, DOI 10.1021/acssuschemeng.7b00328. (2) Dong, L.; Huang, Z.; Ruan, J.; Zhu, J.; Huang, J.; Huang, M.; Kong, S.; Zhang, T. Pyrolysis routine of organics and parameter optimization of vacuum gasification for recovering hazardous waste toner. ACS Sustainable Chem. Eng. 2017, 5, 10038-10045, DOI 10.1021/acssuschemeng.7b02024. (3) Ruan. J.; Qin, B.; Huang, J. Controlling measures of micro-plastic and nano pollutants: a short review of disposing waste toners. Environ. Int. 2018, 118, 92-96, DOI 10.1016/j.envint.2018.05.038. (4) Gaikwad, V.; Kumar, U.; Pahlevani, F.; Piadasa, A.; Sahajwalla, V. Thermal transformation of waste toner powder into a value-added ferrous resource. ACS Sustainable

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TOC For Table of Contents Use Only

SEM image

One-pot transformation

20 μm

Waste toner powder

SEM image

2 μm

GO hydrogel

A one-pot transformation strategy was designed to synthesize 3D porous graphene oxide hydrogel by using waste toner powder as a precursor based on the improved Hummers‟ method.

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One-Pot Transformation of Waste Toner Powder into 3D Graphene

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