Journal Pre-proof

Fabrication of graphitic carbon nitride films by inkjet printing

Rocı́o Martı́nez-Flores (Conceptualization) (Methodology)

(Validation) (Formal analysis) (Investigation) (Writing - review and
editing), Geonel Rodrı́guez-Gattorno (Formal analysis) (Writing -
review and editing) (Funding acquisition), Sergio Obregón
(Conceptualization) (Methodology) (Validation) (Formal analysis)
(Investigation) (Writing - review and editing) (Funding acquisition),
Alejandro Vázquez (Conceptualization) (Methodology) (Validation)
(Formal analysis) (Investigation) (Writing - review and editing)
(Funding acquisition), Miguel A. Ruiz-Gómez (Conceptualization)
(Methodology) (Validation) (Formal analysis) (Investigation) (Writing
- review and editing) (Funding acquisition)

PII: S0927-7757(20)31512-0
DOI: https://doi.org/10.1016/j.colsurfa.2020.125919
Reference: COLSUA 125919

To appear in: Colloids and Surfaces A: Physicochemical and Engineering Aspects

Received Date: 12 September 2020

Revised Date: 16 November 2020
Accepted Date: 19 November 2020

Please cite this article as: Martı́nez-Flores R, Rodrı́guez-Gattorno G, Obregón S, Vázquez A,

Ruiz-Gómez MA, Fabrication of graphitic carbon nitride films by inkjet printing, Colloids and
Surfaces A: Physicochemical and Engineering Aspects (2020),
doi: https://doi.org/10.1016/j.colsurfa.2020.125919
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© 2020 Published by Elsevier.

Fabrication of graphitic carbon nitride films by inkjet printing
Rocío Martínez-Flores1,2, Geonel Rodríguez-Gattorno1, Sergio Obregón3, Alejandro
Vázquez4,5, Miguel A. Ruiz-Gómez1,6* miguel.ruiz@cinvestav.mx
1
Departamento de Física Aplicada, CINVESTAV-IPN, Antigua Carretera a Progreso km 6,
Mérida, Yucatán, 97310, México.
2
Tecnológico Nacional de México, TecNM, Instituto Tecnológico Superior de Monclova,
Carretera 57 Km. 4.5 Monclova, Coahuila 25733, México.
3
Universidad Autónoma de Nuevo León, UANL, CICFIM-Facultad de Ciencias Físico

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Matemáticas, Av. Universidad S/N, San Nicolás de los Garza, 66455 Nuevo León, México.
4
Universidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Av.

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Universidad S/N, San Nicolás de los Garza, 66455 Nuevo León, México.
5
Centro de Investigación en Biotecnología y Nanotecnología, Facultad de Ciencias Químicas,

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Universidad Autónoma de Nuevo León, Parque de Investigación e Innovación Tecnológica,
Km. 10 Autopista al Aeropuerto Internacional Mariano Escobedo, Apodaca, 66629 Nuevo
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León, México.
6
CONACYT-Departamento de Física Aplicada, CINVESTAV-IPN, Antigua Carretera a
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Progreso km 6, Mérida, Yucatán 97310, México.

Corresponding Author
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*E-mail: (Miguel A. Ruiz-Gómez).

Telephone: +52 999-942-9427
CINVESTAV-IPN, Antigua Carretera a Progreso km 6, Mérida, Yucatán, 97310, México.
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Graphical abstract

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Abstract

Graphitic carbon nitride (g‐ C3N4) has recently arisen at the forefront of researching in many
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areas. For this reason, the establishment of attractive and functional methodologies for the
preparation of g‐ C3N4 films and coatings to develop novel applications is very important.
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Therefore, this paper is focused on taken advantage of the functionalities of ultrasound-

assisted liquid-phase exfoliation (UALPE) process and inkjet printing (IJP) technique for the
fabrication of g‐ C3N4 films. By an integral analysis, a stable and printable colloidal ink
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containing exfoliated g‐ C3N4 with an average particle size of 263 nm was formulated.
Reproducible and well-defined g‐ C3N4 films with 10, 20 and 30 printing-passes have been
obtained where the distinctive characteristic related to the automatic droplets’ deposition
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provided by IJP technique allowed an easy control on the spatial uniformity, thickness and
transparency. Additionally, the inkjet printed g‐ C3N4 films were evaluated as a fluorescence
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sensor exhibiting a good response in the presence of Ag+ aqueous solution. The strategy here
reported can be exploited for the deposition of large-area and complex patterns of g‐ C3N4
onto a variety of rigid and flexible substrates through the simple and low-cost UALPE and
IJP approaches.

Keywords: inkjet printing; graphitic carbon nitride; ultrasound-assisted exfoliation;

colloidal ink.

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1. Introduction

Since the discovery in the past decade of graphene, the first two-dimensional (2D) atomic
crystal, significative research breakthroughs in this field have been successfully developed
[1,2]. The family of 2D crystals represents a new class of nanomaterials that feature a variety
of distinct physical and chemical properties [3,4]. Among various 2D nanomaterials, g‐ C3N4
has recently emerged as a promising nitrogen-rich carbon compound with a layered structure

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that resembles graphite [5–8]. Particularly, g-C3N4 has been synthesized in powder form by
polycondensation using various precursors [9–17], exhibiting extensive applications in many

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fields ranging from photocatalysis until biomedical [3,6,8,12–20].

The UALPE process has been very attractive for the preparation of colloidal dispersions from

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2D materials [21–23]. In fact, UALPE [3,18,24–30] and chemical protonation [31–34] have
been principally used for obtaining exfoliated g-C3N4 and its further deposition by several
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methodologies [13,18,30,33,34]. In recent years, the modification of g-C3N4 with organic
compounds and polymers has been reported as strategy to improve its dispersibility and
processability [35,36]. Therefore, the main challenge is the development of advanced
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deposition methods as well as new strategies in order to obtain g-C3N4 films in an

uncomplicated and reproducible way with a high scalability potential, free of restacking and
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agglomeration for maintaining its nanostructured features [20,37,38].

IJP is considered an additive manufacturing technique enabling the fabrication of small and
large-scale thin film and complete devices. For it, stable and high-quality inks fulfilling the
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printability criteria are required. This technique can overcome several difficulties presented
by traditional routes, generating new functionalities and performance; it is digital and allow
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to print instantly any design and size of the desired pattern without using masks, while its
drop-on-demand characteristic avoids a significantly materials waste [39–49].

Recently, the preparation of carbon nitride films by using a commercial inkjet printer was
reported [35], however, details about ink properties and printing conditions were not
presented. For this reason, this paper has been focused on the fabrication of g-C3N4 films by

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using IJP technique where the dispersions containing exfoliated g-C3N4 were prepared by
UALPE process. The most suitable dispersion, further used as colloidal ink, resulted from an
integrated analysis considering the solvent, amount of initial g-C3N4 powder, sonication time
and centrifugation time. The optimization of printing parameters and the number of passes
resulted in the reproducible fabrication of g-C3N4 films onto glass slides with a uniform
surface coverage of 1 cm2. Besides, the fluorescence response of inkjet printed g-C3N4 films
for detection of Ag+ in aqueous solution has been evaluated for their promising application
as a sensor coating.

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2. Materials and Methods

2.1 Synthesis of g-C3N4 powder

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The g-C3N4 was synthesized by polycondensation of urea. For it, 10 g of urea (Sigma-
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Aldrich) was submitted to thermal treatment at 500 °C for 4 h under air atmosphere. The g-
C3N4 powder was characterized by several techniques, as described in the supplementary
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material.

2.2 Preparation and characterization of g-C3N4 inks

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Several dispersions of g-C3N4 were prepared by UALPE process using non-hazardous

solvents such as deionized water (18.2 MΩ), ethylene glycol (J.T. Baker 99.9 %), isopropyl
alcohol (Sigma Aldrich ≥ 99.5 %), and glycerol (CTR Scientific 99.9%) as suspension media.
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First, 5 mg of g-C3N4 powder were weighted in 15 mL centrifuge tubes and dispersed

separately using 10 mL of each solvent, afterward, they were sonicated using a Branson 3800
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ultrasonic bath (40 kHz and 115 V) for 6 h. After sonication, the stability of each dispersion
was monitored visually as a function of time in order to select the more suitable solvent. Once
the better exfoliating and stabilizing media was defined, the initial amount of g-C3N4 (5 mg
and 10 mg), sonication time (2 h, 4 h and 6 h) and centrifugation time (1 h and 2 h) were
optimized in order to obtain a printable g-C3N4 colloidal ink. In all tests, 10 mL of the optimal
solvent was used, varying the above mentioned parameters. After sonication, the dispersions

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were centrifuged at 4000 rpm for 1 h and 2 h using a centrifuge (Thermo Scientific, Sorvall
ST8) where ~ 8.5 mL of supernatant was recovered, and from it ~ 2.5 mL was used for
characterization. All obtained supernatant (g-C3N4 dispersions) were characterized by using
different physicochemical techniques as mentioned below. The concentration was
determined by UV-vis measurements using an Agilent Instruments apparatus where ~ 1 mL
of dispersion was placed in a quartz cell for analysis, then the Lambert-Beer equation (A =
αCL) was used, where A is the absorbance value at 660 nm, α is the extinction coefficient at
660 nm (5.4 ± 0.2 x 102 mL/m mg) for g-C3N4 [30], and L is the optical path length (0.01 m).

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The particle size and zeta potential (ZP) were measured based on dynamic light scattering
(DLS) analysis by using a Zetasizer Nano ZS 3600 apparatus (λ = 633 nm, Malvern

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Instruments), where ~ 1 mL of dispersion was placed in acrylic cuvettes (10 mm path length)
at 25 ± 1 °C whereas for ZP measurements a dip cell (ZEN1002) was used.

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2.3 Inkjet printing and characterization of g-C3N4 films

Before printing, the glass slides used as substrate were cleaned with 15 mL of piranha
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solution for 5 min. Then, they were rinsed with deionized water and dried at 80 °C for 15
min. The printing process was carried out by a drop-on-demand Dimatix materials printer
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DMP-2831 (Fujifilm) with an available area for printing of about 20 x 30 cm, allowing handle
substrates of 0.5-25 mm thickness with an adjustable Z height, while the vacuum platen that
secures the substrate in place can be heated up to 60 °C. A DMC-11610 piezoelectric
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cartridge (nozzle diameter of 21.5 µm, 16 nozzles with 254 µm nozzle spacing and 10 pL
nominal drop volume) was filled with 1.5 mL of the g-C3N4 colloidal ink. For optimization
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of inkjet printing instrumental parameters, several values of jetting voltage (JV) and drop
spacing (DS) were evaluated. Based on the visualization of the colloidal ink droplets using
the drop-watcher camera system, the proper JV for the printing process was established;
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while considering the homogeneity and definition of the printed patterns the appropriate DS
was selected. Then, square patterns of 1 cm2 were inkjet printed with 10, 20 and 30 passes
onto cleaned glass slides. During the process, the cartridge temperature was set at 30 °C and
it was placed at 1,000 μm above the substrate while the temperature of the printer platen was
maintained at 60 °C. After every printing-pass, it was dried at 60 °C for 3 minutes directly

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on the printer platen, besides, a cleaning cycle (spit-purge-blot) was run and the proper ink
jetting was checked by using the drop-watcher camera system to ensure reproducibility.
Then, after printing the desired number of passes, the films were thermally treated in an air
atmosphere at 250 °C for 1 h with a heating ramp of 2 °C/min. The morphology of inkjet
printed g-C3N4 films was characterized by Atomic Force Microscopy (AFM) using an MFP-
3D AFM (Asylum Research) equipment and Scanning Electron Microscopy (SEM) using a
JEOL JSM-7600F field-emission microscope. The AFM images were imported to the
professional image processing open software Gwyddion, which is an effective modular

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program for scanning probe microscopy data visualization and analysis [50]. The root mean
square roughness (RMS) of the surface was obtained directly from the 10 x 10 μm AFM

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images using the default method of the Gwyddion software. The UV-Vis spectrophotometry
analysis was carried out with an Agilent Instruments apparatus in the range of 300-800 nm

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using an identical glass substrate as reference. X-ray photoelectron spectroscopy (XPS)
analysis was performed using a K-Alpha Thermo Scientific spectrometer with Al Kα X-ray
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monochromatic source (1486.6 eV) at 12 kV and 40 W. The analyzed area was 400 μm2
using a relative incident angle of 30°. Before analysis, the surface of the samples was cleaned
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by argon erosion (30 s at 3 kV and 30 W). Survey spectra were obtained from 0 to 1350 eV
(1 eV/step and 100 eV pass energy), whereas for high-resolution spectra, 0.1 eV/step and 50
eV pass energy were used. The binding energies were referenced to adventitious carbon (C1s)
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at 284.8 eV.

2.4 Fluorescence sensing tests

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The photoluminescence properties of the inkjet printed g-C3N4 films were investigated at
several excitation wavelengths ranging from 250-350 nm in a Perkin-Elmer LS 55
Spectrometer. After that, g-C3N4 films were impregnated with an aqueous solution
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containing 6 x 10-8 mol of AgNO3 for 3 min and then the solution excess was removed, and
the films were dried in air at room temperature. Finally, the photoluminescence response was
recorded at an excitation wavelength of 350 nm.

3. Results and Discussion

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3.1 Characterization of g-C3N4 powder

The pale-yellow powder was characterized to corroborate the obtaining of the g-C3N4
material. Figure 1(a) shows the XRD pattern of the sample, which can be assigned to the
graphitic carbon nitride according to the JCPDS No. 87-1526 [51]. The diffraction peak at
13.1° (2θ) is related to the (100) diffraction plane and is attributed to the interplanar distance
of the tris-s-triazine condensed units of g-C3N4. Furthermore, the peak at 27.3° (2θ)
corresponds to the (002) diffraction plane associated with the stacking of the aromatic
structure in the material. The wide peak centered at 46.6° (2θ) could be ascribed to the

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presence of non-condensed g-C3N4 intermediates formed during the polymerization of the
urea precursor [52]. The powder sample was also characterized by UV-vis diffuse reflectance

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spectroscopy (DRS), see Figure 1(b). It is worth noting that g-C3N4 exhibits strong absorption
in the UV-vis region related to the intrinsic electronic transitions (π → π*) with an edge close

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to 440 nm. From Tauc plot, inset of Figure 1(b), the band gap energy was estimated at 2.93
eV. The Fourier transform infrared spectroscopy (FTIR) analysis of the g-C3N4 is shown in
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Figure 1(c). A broad band is displayed in the region of 2900-3600 cm-1 which can be assigned
to the stretching vibration modes of the N-H bonds, indicating the presence of primary and/or
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secondary amino functional groups in the layers of the g-C3N4 [53]. The bands at 1244, 1319,
1408, 1456, 1558 and 1628 cm-1 are related to the stretching and rotation vibrations of the C-
N and C=N bonds of the heptazine rings [54]. In addition, the band located at 810 cm-1 is
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associated with the breathing mode of the triazine units in the material. The surface properties
were examined by nitrogen adsorption-desorption measurements, see Figure 1(d). The g-
C3N4 exhibits a type-IV isotherm with a type H3 hysteresis loop, which indicates the
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mesoporous features of the sample [55]. From the above measurements, the BET surface area
was estimated at 52.6 m2/g. Furthermore, the Barrett-Joyner-Halenda (BJH) pore size
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distribution is displayed in the inset of Figure 1(d). As seen, the g-C3N4 shows a broad pore
size distribution with a mean size of 25 nm. The sample was also analyzed by scanning
electron microscopy. Figure S1 shows representative SEM images of the material, where
particles with irregular shapes and micrometer size are observed. In fact, this morphology
has been reported previously for the g-C3N4 prepared from urea [56].

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3.2 Preparation and characterization of g-C3N4 inks

In the case of colloidal inks, stability is one of the most important criteria to ensure their
successful performance during the entire IJP process. Therefore, the stability to
sedimentation of the obtained g-C3N4 dispersions was tested; in Figure 2(a) clearly can be
seen that after 6 h of sonication all solvents are able to exfoliate g-C3N4 micrometric particles.
However, those dispersions prepared with deionized water (W) and isopropyl alcohol (IPA)

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showed instability after only 2 h, see Figure 2(b), and almost all the particles settled after 24
h under static conditions, see Figure 2(c). Oppositely, using ethylene glycol (EG) and

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glycerol (GL) very stable dispersions were obtained even for more than one month without
showing sedimentation to the naked eye.

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It is important to note that a comparative analysis with previous works about the stability to
sedimentation of exfoliated g-C3N4 dispersions is difficult to carry out because many
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variables such as synthesis of g-C3N4 powder as well as sonication and centrifugation time
influence significantly, as can be seen in Table 1 that summarizes some previous reports
about exfoliation of g-C3N4 by means of UALPE process. Particularly, in this report the
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dispersions were obtained at shorter sonication time but longer centrifugation time compared
to most of them. Moreover, our stability to sedimentation results agree to [3,28] regarding
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the exfoliating performance of EG, however, differ from those using water and isopropanol
[3,18,24,26,27].

The efficiency of liquid-phase exfoliation depends on the interfacial energy between the
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solvent and 2D materials. Thus, an efficient first approach to identify suitable solvents is
consider the proper balance of surface energies. This is based on approximations related to
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enthalpy of mixing and Hildebrand solubility parameter which is associated with the total
cohesive energy density of the solute or solvent [21,22,28]. The surface energy of a solvent
can be estimated directly considering its surface tension plus an entropy-related term
approximately constant for all solvents at room temperature that corresponds to ~ 29 mJ/m2
[21,28]. Table 2 depicts surface tension, estimated surface energy, viscosity and Hansen
solubility parameters (HSP), reported in the literature for the used solvents [57–59] and g-

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C3N4 [18,28]. According to Ayán-Varela et al. [28] the suitable solvents for obtaining stable
dispersions of exfoliated g-C3N4 have surface tension about 35-55 mJ/m2, while those close
to 48 mJ/m2 maximized the amount of dispersed g-C3N4. It is worth noting that EG presents
a surface tension value of 48 mJ/m2 and this could be the reason for the dispersion stability
shown according to Figure 2; however, that criterion disagrees with the excellent stability to
sedimentation of the dispersion containing GL (surface tension of 62.5 mJ/m2), indicating
that other physicochemical aspects should be considered.

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HSP theory has provided an acceptable explanation regarding the proper solvents for
exfoliation and stability of dispersions, indicating that materials with similar HSP have high
affinity for each other [21,22,26,28]. In fact, HSP are related to the dispersion (δD, van der

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Waals), polar (δP, dipole moment) and hydrogen-bonding (δH) contributions to the cohesive
energy density; thus HSP and Hildebrand solubility parameter are correlated. By comparison

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of the HSP values presented in Table 2, it is observed that δD and δP of g-C3N4 match better
to those of both GL and EG, while δH of g-C3N4 is more similar only for IPA. Ayán-Varela
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et al. also reported [28] that suitable solvents for exfoliation of g-C3N4 powder show values
around 17-19, 9-15 and 10-20 MPa1/2 for δD, δP and δH, respectively. Thus, in the case of W
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none of its three components match within the ranges, for IPA only δH whereas for EG and
GL both δD and δP. These correlations based on HSP agree very well with the stability to
sedimentation analysis of our g-C3N4 dispersions depicted in Figure 2, that is, EG and GL
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dispersions are the most stable, while those using IPA and W were stable for less than 24 h
and 2 h, respectively.
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As mentioned above EG and GL form the most stable dispersions and coincidently, these
solvents present high viscosity values, being by far the highest for GL, see Table 2. Hence,
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it seems that the viscosity of solvents could be considered as another important parameter on
the stability of exfoliated g-C3N4, this is because solvents having high viscosity limit mobility
and interactions among exfoliated material avoiding their rapid sedimentation due to gravity
as stated by Stokes’ law. Therefore, HSP and viscosity provide an acceptable explanation
about the excellent performance of EG and GL for exfoliation and stabilization of g-C3N4.
However, for a drop-on-demand piezoelectric printer the recommended values of viscosity

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and surface tension of the ink are in the range of 1-30 cP and 28-70 mN/m, respectively
[45,49]. Thus, EG presents more adequate values than GL for being used as a solvent in the
inkjet printing process. While the functionalities presented by GL could be used for inks and
pastes in the deposition of g-C3N4 by other routes such as spin-coating, doctor blade and
screen printing.

Once selected the EG as the most promising solvent for the preparation of a colloidal ink, the
effect of the initial amount of g-C3N4 powder, sonication time and centrifugation time on the
concentration of exfoliated g-C3N4 dispersions was carefully analyzed. Figure S2 presents

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the values of g-C3N4 concentration of all dispersions determined by UV-Vis analysis, where
it can be seen that those prepared using 5 mg of g-C3N4 powder (Figures S2(a) and S2(b))

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are less concentrated compared to those prepared using 10 mg of g-C3N4 powder (Figures
S2(c) and S2(d)). On the other hand, g-C3N4 concentration increased as sonication time also

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increased, independently of the initial amount of g-C3N4 powder. That trend can be better
observed for the case of dispersions obtained after 2 h of centrifugation, see Figures S2(b)
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and S2(d), in comparison to those with only 1 h of centrifugation (Figures S2(a) and S2(b)).
Finally, it is observed that centrifugation time affected considerably on the g-C3N4
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concentration principally to those dispersions prepared at 2 h and 4 h of sonication and

independently of the initial amount of g-C3N4 powder. This result suggests that after 2 h of
centrifugation, the larger exfoliated g-C3N4 particles were removed from dispersions and as
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consequence the concentration decreased importantly. So, based on results depicted in Figure
S2, dispersions prepared using initially 10 mg of g-C3N4 powder were chosen for further
analysis of the particle size distribution.
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In IJP process, the size of cartridge nozzle represents an important restriction for colloidal
inks, that is, the average size of the particles and aggregates contained in the ink must be ∼
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100x smaller than the nozzle diameter (∼ 22 μm) for avoiding that particles clog the nozzles
complicating the printing process. For this reason, through the optimization process, the
average particle size of g-C3N4 dispersed in EG was monitored where the obtained results
are depicted as chart box allowing to obtain a quick visual idea about the statistics summary,
see Figures 3(a) and 3(c). In the obtained chart box for the different sonication times, each

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black circle represents the average particle size resultant of 15 measurements, the dataset is
plotting on the left of each box and a curve corresponding to normal distribution is also
displayed. Figure 3(a) depicts the results of particle size for g-C3N4 dispersions sonicated at
different times and 1 h of centrifugation, showing a distribution of 364-416 nm, 362-525 nm
and 307-357 nm for 2 h, 4 h and 6 h, respectively. As observed, the smaller values were
reached for a sonication time of 6 h, while the length of the box for 2 h and 6 h was smaller
than for 4 h, indicating that those datasets are closer to their median value, 391 nm and 339
nm, respectively.

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As the key point that drives the optimization process for g-C3N4 dispersions is the average
particle size, 6 h of sonication was defined as the optimal time for this series, presenting a

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bell-shaped curve centered at 338 ± 19 nm, Figure 3(b). Also, to get a complete picture of
this g-C3N4 dispersion, the ZP was measured obtaining 41 ± 1 mV as a result, indicating a

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good stability because low ZP (0 ± 15 mV) means that agglomeration and sedimentation of
particles is rapid in dispersion.
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A parallel study of the effect of sonication time on the average particle size of dispersions
obtained after 2 h of centrifugation was carried out. According to the results presented in
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Figure 3(c), the distribution was 233-423 nm, 288-409 nm and 231-282 nm, for 2 h, 4 h and
6 h of sonication, respectively. In particular, the dispersion sonicated for 6 h presented the
lowest median value at 270 nm, which is close to third quartile value (271 nm); for this
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reason, the corresponding box only shows one division. Besides, the ZP value for this
dispersion was the same as with only 1 h of centrifugation (41 ± 1 mV), indicating that
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centrifugation time does not affect the ZP and the excellent stability is maintained. This
positive value of ZP agrees well to results about water dispersions of g-C3N4 synthesized
using urea [60] considering the slightly acidity difference between water and ethylene glycol.
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Again, the smaller average particle size was obtained for 6 h as observed previously for
dispersion with 1 h of centrifugation, however, applying 2 h of centrifugation the smallest
average particle size was achieved, 263 ± 19 nm (Figure 3(d)) compared to 338 ± 19 nm
(Figure 3(b)). The value of 263 ± 19 nm of our optimal g-C3N4 dispersion is smaller than
those reported for acid-treated (310 nm) [33] and it is larger than those reported by using

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ball-milling (138 nm) [6]. Therefore, the above results confirm that 6 h of sonication
improved the exfoliation process decreasing the g-C3N4 particle size, while 2 h of
centrifugation is essential for removing large particles, avoiding the possibility of blockage
the cartridge nozzles. It is important to highlight that these results provide real information
on the behavior of exfoliated g-C3N4 (particle size and stability) dispersed in EG. Therefore,
taking into consideration that the g-C3N4 dispersion obtained using 6 h of sonication and 2 h
of centrifugation presented the lowest average particle size, this dispersion is considered the
most suitable to be utilized as ink.

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Figure 4 depicts a photograph of the colloidal ink, which presents a yellowish white color
characteristic of exfoliated g-C3N4 [9,18,28], a pH value of ≈ 4 as well as colloidal properties

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demonstrated by the Tyndall effect when a red laser light (λ = 650 nm) passed through the
ink (image not shown). The corresponding UV-vis spectrum is displayed in Figure S3,

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exhibiting an extended absorption from UVA until near infrared region, particularly, the
intense band centered at 215 nm is assigned to π → π* transitions of C=N in tris-s-triazine
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condensed units [28], while the broad band at 400-600 nm could be derived from many
transitions that occur in this region [61,62]. Besides, from the UV-vis spectrum and using
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Lambert-Beer equation the calculated concentration of the colloidal ink is 0.18 mg/mL.
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3.3. Inkjet printing and characterization of g-C3N4

Firstly, the printing parameters related to the jetting voltage (JV) and drop spacing (DS) were
optimized taking into consideration the visual and microscopical examination. By applying
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a JV of 18 V, single and stable drops are obtained as shown in Figure 4, where can be
observed representative images about the sequence on distance vs time for ejected drops
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using the colloidal ink of g-C3N4. Here, the good compatibility between the EG and suitable
size of exfoliated g-C3N4 allowed the preparation of a stable colloidal ink, which produces
well-directed drops constantly jetted from the cartridge nozzles indicating the excellent
printability of the colloidal ink. Based on these observations, the average calculated drops
velocity is 6.8 m/s, within the recommended values for the IJP process (6-10 m/s) [49]. In
addition, considering the homogeneity and definition of the printed patterns, the optimized

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value for the DS was determined to be 40 µm corresponding to 625 drops/mm2. After
optimization of printing parameters, g-C3N4 square patterns of 1 cm2 were inkjet printed with
10, 20 and 30 passes onto glass slides, see photograph in Figure 5, where all samples are
well-defined, uniform and crack-free at naked eye.

The AFM micrographs also depicted in Figure 5 revealed that by increasing the number of
printed-passes a better surface covering and homogeneity was obtained as to be expected.
Besides, the thickness of the samples was maintained in a similar range value, being the
highest of 798, 822 and 1100 nm for samples with 10, 20 and 30 printed-passes, while the

of
RMS values are 87, 151 and 153 nm, respectively. These results indicate that by increasing
the printing-passes improved the surface covering instead of an excessive agglomeration of

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particles, this is because IJP technique allows the automatic deposition of droplets on a
specific site for the formation of designed patterns favoring a complete control over film

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uniformity, surface coverage and thickness. The cross-sectional SEM images depicted in
Figure S4 are in good agreement with the thickness range observed by AFM.
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In Figure 6 representative top-view SEM images of inkjet printed g-C3N4 are depicted,
confirming that the surface coverage increased as function of printing-passes as observed in
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AFM analysis. In particular, the deposited g-C3N4 particles are irregular in shape like those
observed in the powder (see Figure S1) but presenting nanometric sizes due to the exfoliation
process applied for colloidal ink preparation. All samples exhibit the presence of particles
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well-distributed on the surface without presenting an important agglomeration; showing both

isolated and connected particles with sizes ranging from 300 nm to 600 nm. According to the
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above results is expected that IJP technique can solve some problems such as the restacking
of isolated nanosheets into densely packed films, in order to maintain their distinctive and
unique features for practical applications.
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The morphological features observed by AFM and SEM correlate well with the optical
properties shown in Figure 6(d). The UV-vis spectra obtained for the inkjet printed g-C3N4
films show two bands centered at 320 nm and 385 nm characteristic of nanometric films
exhibiting thickness-dependent absorption spectra [38], which can be assigned to π → π* and
lone-pair states → π* transitions, respectively [63]. In addition, the absorbance rises with the

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number of printing-passes because more material was deposited increasing the surface
coverage. As seen, the absorbance values follow a linear almost trend (~ 0.05 a.u. at 300 nm
and ~ 0.01 a.u. at 800 nm) after each 10 printing-passes. So, thickness and transparency can
be easily modulated by the number of printed-passes, representing and important advantage
of IJP technique in comparison to other deposition methods.

The inkjet printed g-C3N4 films were also characterized by X-ray photoelectron
spectroscopy. Figure S5(a) displays the survey spectra of the samples, where it is possible to
elucidate the presence of the C and N elements from g-C3N4. Besides, other elements such

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as Si, Ca, Mg, Na and O are related to the glass substrate used. The high-resolution spectra
of the C 1s region exhibit a weak signal related to the g-C3N4 printed, see Figure S5(b). This

ro
signal can be deconvolved in three well-known peaks. The peak centered at 284.6 eV is
attributed to adventitious carbon which is used as a reference peak for any XPS analysis. The

-p
peak located at 286.2 eV is assigned to the C-O species in the samples, while the peak at
287.6 eV can be ascribed to the N-C=N species of the structural framework of g-C3N4 [12,
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64]. On the other hand, the high-resolution spectra of the N 1s region can be fitted in three
peaks located at 398.0, 398.8 and 401.0 eV, as shown in Figure S5(c). The main peak at 398.0
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eV is assigned to aromatic nitrogen bonded to carbon atoms (C=N-C) in the g-C3N4 [55]. The
peak located at 398.8 eV can be related to tertiary nitrogen atoms bonded to C atoms such as
N-(C)3 groups, while the negligible peak observed at 401.0 eV is attributed to the amino
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functional groups with a hydrogen atom (C-N-H) [65].

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3.4 Inkjet printed g-C3N4 for fluorescence sensing

Figure 7(a) shows the photoluminescence spectra of the g-C3N4 film with 30 printed-passes
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where regardless of the excitation wavelength, it can be observed two emission bands, one
centered at 371 nm with low intensity and another one more intense centered at 435 nm.
Some previous reports relate the emission band at 371 nm to electronic transitions between
lone pair of electrons of the N atoms and antibonding molecular orbitals [65]. While the
emission band at 435 nm can be ascribed to π-π* electron transitions in the conjugated

14/22
heterocyclic ring system [61], which is in good concordance with the band gap energy value
estimated for g-C3N4 powder, see inset in Figure 1(b).

The strongest emission was observed at an excitation wavelength of 350 nm, for this reason
the subsequent examinations were performed at this excitation wavelength value. Figure 7(b)
shows the photoluminescence emission spectra of the g-C3N4 films with 20 and 30 printed-
passes before and after the impregnation with AgNO3 solution, the film with 10 printed-
passes was discarded because a low response. It is evident that the presence of Ag+ ions
produces a decrease in the emission band intensity (i.e. a photoluminescence quenching),

of
resulting in an efficient method for silver detection. This behavior can be explained by the
photoinduced electron transfer from the inkjet printed g-C3N4 to silver ions, since the Ag+/Ag

ro
couple has a redox potential between the conduction band and valence band of g-C3N4 [67].
These results are similar to other reported g-C3N4 fluorescent probes tested in aqueous

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dispersion [67,68]. However, compared to a liquid probe, a solid fluorescent sensor has the
advantages to be more suitable for storage and ready-to-use applications, besides, it can be
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easily recovered for further analysis [69].
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4. Conclusions

It has been found that EG is an excellent exfoliating and stabilizing of g-C3N4 for the proper
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formulation of a high-quality colloidal ink by using UALPE process. The better matching in
the HSP of EG and g-C3N4 as well as the appropriate viscosity of EG were the key factors in
determining the outstanding stability to sedimentation and printability of the formulated
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colloidal ink. It was demonstrated by the first time that the combination of UALPE process
and IJP technique is an effective top-down strategy with a high scalability potential for easy
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and reproducible fabrication of g-C3N4 films. The inkjet printed g-C3N4 films are suitable
fluorescence probe for Ag+ detection, indicating their potential incorporation as an active
component for developing advanced sensors in the detection of metal ions in water. The
adaptability and flexibility of UALPE process, along with the reproducibility and
micrometric resolution achieved through IJP technique, open up new opportunities for future
developments of miniaturized devices based on exfoliated g-C3N4.

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Credit Author Statement
Rocío Martínez-Flores: Conceptualization, Methodology, Validation, Formal analysis,
Investigation, Writing - Review & Editing. Geonel Rodríguez-Gattorno: Formal analysis,
Writing - Review & Editing, Funding acquisition. Sergio Obregón: Conceptualization,
Methodology, Validation, Formal analysis, Investigation, Writing - Review & Editing,
Funding acquisition. Alejandro Vázquez: Conceptualization, Methodology, Validation,
Formal analysis, Investigation, Writing - Review & Editing, Funding acquisition. Miguel A.
Ruiz-Gómez: Conceptualization, Methodology, Validation, Formal analysis, Investigation,
Writing - Review & Editing, Funding acquisition.

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Declaration of interests

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The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

Acknowledgements
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re
To Consejo Nacional de Ciencia y Tecnología from Mexico (CONACYT) for funding through the
projects: postdoctoral scholarship of R. Martínez-Flores, INFR-2019-300046, INFR-2015-01-
252758, CB-2017-2018 A1-S-9529, CB-2015 255109 and Cátedra project 1710. A. Vázquez thanks
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UANL for the project PAICYT-2019 IT1020-19. Authors also are grateful for the use of the facilities
of LANNBIO Cinvestav-Mérida supported by the grants FOMIX Yucatán 2008–108160,
CONACYT LAB-2009-01-123913, 188345, 204822, 292692 and 294643; and the technical
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assistance of Dora Huerta and Wilian Cauich. We also thank Dr. Oscar Vega from Centro de
Investigación en Materiales Avanzados, Unidad Monterrey for AFM measurements.

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Efficient emission facilitated by multiple energy level transitions in uniform graphitic carbon nitride
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https://doi.org/10.1002/cphc.201402898.
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7842–7844. https://doi.org/10.1143/JJAP.47.7842.
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Figures

Figure 1. Characterization results of g-C3N4 powder: (a) XRD, (b) DRS and the inset is the
corresponding Tauc plot, (c) FTIR and (d) nitrogen adsorption-desorption isotherm and as
inset the BJH pore size distribution is shown.

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Figure 2. Photographs of prepared dispersions using 5 mg of g-C3N4 powder and 10 mL of

deionized water (W), isopropyl alcohol (IPA), ethylene glycol (EG) and glycerol (GL) as
solvents, respectively. They were taken (a) immediately after 6 h of sonication, and after let
standing for (b) 2 h and (c) 24 h.

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Figure 3. Effect of centrifugation time on the particle size distribution of exfoliated g-C3N4
(10 mg and 10 mL EG) sonicated for 2 h, 4 h and 6 h: (a), (b) 1 h and (c), (d) 2 h of
centrifugation. In (a) and (c) the inset indicates the description of the symbols, the 25th (Q1)
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and the 75th (Q3) percentile are the edges of the box, IQR is the interquartile range. In (b)
and (d) the DLS results of dispersions sonicated at 6 h are depicted, the inset shows the
average particle size and zeta potential (ZP).

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Figure 4. Photograph of the formulated colloidal ink based on exfoliated g-C3N4 obtained
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through UALPE process as well as images of ejected ink drops at different times during the
IJP process.
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Figure 5. Photograph of inkjet printed g-C3N4 films with different number of passes onto
glass substrates and their corresponding AFM micrographs.
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Figure 6. Representative SEM images of inkjet printed g-C3N4 films with (a) 10 printed-
passes, (b) 20 printed-passes and (c) 30 printed-passes, while in (d) their corresponding UV-
vis spectra are shown.

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Figure 7. (a) Photoluminescence emission spectra of inkjet printed g-C3N4 film with 30
printed-passes recorded at different excitation wavelengths and (b) photoluminescence
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sensing of Ag+ ions using the inkjet printed g-C3N4 films with 20 and 30 printed-passes.
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Tables
Table 1. Comparative summary regarding conditions and results of previous reports about
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exfoliation of g-C3N4 by means of UALPE process.

d
Particle size
a c Method for
g-C3N4 b Solvents Sonication Centrifugation and
Initial ratio film Ref.
powder used time (h) conditions concentration
fabrication
(mg/mL)
U
5:10 W, IPA, 4000 rpm 263±19 nm Inkjet This
500°C 2, 4 and 6
10:10 EG*, GL 1 and 2 h 0.18 printing work
4h

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 M W*, ET, 5000 rpm Vacuum
70-160 nm
600°C 100:100 ME, 16 Time not Filtrated 18
0.15
2h DMF, F reported. suspension
IPA*,
3000 rpm From 500 nm
C 30:10 NMP, W, 10 None 24
10 min Not reported
ET, AC
D
350°C BD*,
10,000 rpm 50-200 nm
2h 60:25 CH, MB, 24 None 25
5 min 0.35
600°C DMA
2h
3000 rpm
800 nm
C 30:10 IPA 10 Time not None 26
Not reported
reported.

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3000 rpm
M ET-W, sub-
10 min
550°C 500:150 IPA-W, 10 micrometric. None 27
10,000 rpm
4h DMF-W 3.0

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5 min
EA, PD,
500g 50-200 nm
C 30:10 BD, EG, 4 None 28e
10 min 1.0
TD

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Ca-M-Ba Electro-
1000 rpm Not reported.
550°C 10:100 T 5 phoretic 30
10 min Not reported.
4h deposition
M IPA*,
10,000 rpm Not reported.
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500°C 20:20 DMSO, 15 None 3
10 min Not reported.
4h EG, W
a
Conditions for the synthesis of g-C3N4 powder using the follow precursors: U = urea, M = melamine,
C = commercial product, D = dicyandiamide, Ca = cyanuric acid, Ba = barbituric acid. bRatio
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indicated as powder:solvent (mg:mL). cW = water, IPA = isopropyl alcohol , EG = ethylene glycol,

GL = glycerol, ET = ethanol, ME = methanol, DMF = N,N-dimethylformamide, F = formamide,
NMP = N-methyl-pyrrolidone, AC = acetone, BD = 1,3-butanediol, CH = cyclohexanone, MB =
methylbenzene, DMA = N,N-dimethylacetamide, T = toluene, EA = ethanolamine, PD = 3-
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pyridinemethanol, TD = thiodiglycol, DMSO = dimethyl sulfoxide. *indicates the most suitable

solvents. dAnalysis used for measurements: in this work dynamic light scattering and UV-vis
spectroscopy, AFM and not reported [18], SEM-TEM and not reported [24], SEM and not reported
[25], TEM-AFM and not reported [26], TEM and not reported [27], TEM and UV-vis spectroscopy
[28]. eThis table only reports the optimal conditions stated by the authors, note that they evaluated 35
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solvents (only the most suitable are indicated) as well as other variables regarding to initial ratio,
sonication and centrifugation.

Table 2. Physicochemical properties of used solvents and g-C3N4.

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a b
Surface Estimated a
c
HSP (MPa1/2)
Viscosity
Solvent tension surface energy
(cP) δD δP δH
(mN/m) (mJ/m2)
W 72.0 101.0 0.9 15.5 16 42.3
IPA 20.9 49.9 2.0 15.8 6.1 16.4
EG 48.0 77.0 16.1 17.0 11.0 26.0
GL 62.5 91.5 934 17.4 12.1 29.3

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 d
C3N4 ----- 115 ----- 17.8 10.8 15.4
a b
Reported at 25°C, all data were taken from [57] except viscosity of GL [58]. It was considered the
surface tension value plus 29 mJ/m2 [21,50], note that 1 mJ/m2 is equal to 1 mN/m. cData taken from
[59] for all solvents. dData taken from [18,28].

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