Materials Letters 314 (2022) 131864

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Cesium-decorated reduced graphene oxide for photocatalytic

hydrogen generation
N. Gnanaseelan a, Latha Marasamy b, A. Mantilla c, S.K. Kamaraj d, F.J. Espinosa-Faller e,
F. Caballero-Briones a, *
a
Instituto Politécnico Nacional, CICATA Altamira, 89600 Altamira, Mexico
b
Facultad de Química, Universidad Autónoma de Querétaro, 76010 Querétaro, Mexico
c
Instituto Politécnico Nacional, CICATA Legaria, 11500 CdMx, Mexico
d
Tecnológico Nacional de México, Instituto Tecnológico El Llano, 20330 El Llano, Mexico
e
Universidad Marista de Mérida, 97310 Mérida, Mexico

A R T I C L E I N F O A B S T R A C T

Keywords: Cs-decorated reduced graphene oxide (CsRGO) was synthesized by addition of a CsOH solution to a GO sus­
Decorated GO pension. The resulting material is amorphous, while GO reduces upon Cs incorporation as Cs2O-like clusters.
Cs Structure modelling indicates that Cs atom replaces hydrogen in hydroxyl and carboxyl groups in the graphene
Hydrogen photogeneration
plane. CsRGO exhibits transitions associated to the π-to-π*, remanent C––O groups and Cs2O absorption. The
Work function
material is n-type semiconductor, with a direct optical band gap of 2.85 eV. Carrier injection from the Cs2O to
RGO enhances H2-evolution. Stable photocatalytic generation of hydrogen after three four-hour cycles, is
attributed to work function reduction, high conductivity, and high optical absorption upon Cs-incorporation.

1. Introduction 2. Methodology

Photogenerated hydrogen would play major role in a low carbon
future [1]. Hydrophilic GO is suitable for photocatalytic hydrogen
generation due to its unique 2D carbon structure with tunable electronic
properties through functional group modification, decoration with
nanoparticles, doping with heteroatoms or attaching functionalities to
the carbon skeleton [2,3]. Heteroatom doping enhances photocatalytic
hydrogen generation through widening GO light absorption in the
visible range, enhancing carrier mobility and increasing the population
of active binding or catalytic sites [4–6]. On the other hand, cesium is
known for catalyzing reactions [7,8]. J. Liu et al. reported Cs-based GO
derivative for bulk heterojunction solar cell, where H is replaced by Cs in
–COOH groups. The material performed remarkably in charge extraction
properties due to reduction of work function [9]. Herein, for the first
time, Cs2O-decorated RGO was evaluated for photocatalytic H2-
generation.
2.1. Synthesis of Cs2O decorated graphene oxide
GO was synthesized using a modified Hummer’s method reported
elsewhere [10]. For CsRGO, 500 mg of GO were suspended in 300 mL of
H2O. Another solution made of 2 mL of CsOH 50% in water and 48 mL of
deionized water H2O was added drop-by-drop to GO until pH 12.34. The
resultant powder was washed with water and dried at 50 ◦ C.
2.2. Characterization
The photocatalytic activity was determined by suspending CsRGO in
a Pyrex reactor in 1:1 water with methanol as hole scavenger. The re­
action system was illuminated with a pen lamp in a quartz tube at 254
nm and 4400 µW cm− 2. Hydrogen was measured by online gas chro­
matography. Electrochemical properties are described in Supplementary
Information. The model structure was made using ChemBio 3D.

* Corresponding author.
E-mail address: fcaballero@ipn.mx (F. Caballero-Briones).

https://doi.org/10.1016/j.matlet.2022.131864
Received 19 October 2021; Received in revised form 25 January 2022; Accepted 1 February 2022
Available online 5 February 2022
0167-577X/© 2022 Elsevier B.V. All rights reserved.
N. Gnanaseelan et al. Materials Letters 314 (2022) 131864

Fig. 1. Characterization of CsRGO a) XRD, b) FTIR, c) Raman spectra, d) survey XPS, e) HRXPS O1s f. HRXPS O 1s, g) HRXPS Cs 3d, h) HRTEM and i) simulated
model structure.

3. Results and discussion
In Fig. 1a) the diffraction peak attributed to the (0 0 1) plane of GO
was observed around 11.7◦ . In contrast, CsRGO featureless diffracto­
gram indicates it is amorphous [11]. GO FTIR spectra in Fig. 1b) shows
bands at 3290, 1720, 1640, 1569, 1380 and 1054 cm− 1 related with
hydroxyl/adsorbed H2O, carboxyl, carbonyl, C– – C stretching of sp2
carbon atoms, hydroxyl and epoxy functional groups respectively [10].
The FTIR spectra of CsRGO presents a small band related to carbonyl
group as well as the C– – C band, indicating the reduction of GO. In
Fig. 1c), the Raman spectra show the D and G bands at 1600 cm− 1 and
1300–1355 cm− 1 related with the E2g degenerative mode of graphite,
and the defect-activated A1g mode [12]. The calculated crystallite size
(La) [13] of the samples was 3.4 nm for GO and 2 nm for CsRGO and its
decrease reflects the disorder induced by the incorporation of Cs, that
hinders the increase of the sp2 dominion [14].
CsRGO XPS spectra in Fig. 1d) confirms the presence of ca. 90 at. %
C, 7 at. % O and 3 at. % Cs [9]. The HR-XPS of C 1 s shown in Fig. 1e),

Fig. 2. a) UV–vis spectrum and Tauc plot, and b) PL spectrum.

2
N. Gnanaseelan et al.
Fig. 3. a) Cyclic voltammograms, b) Mott-Schottky plots and, c) photocatalytic H2-evolution of GO, CsRGO and blanks; d) electronic diagram for photocatalytic
H2– evolution.
shows peaks at 284.6 eV, 285.6 eV and 286.6 eV assigned to C– – C, C–O/
C–OH and C– – O respectively [15]. HR-XPS of O 1s depicted in Fig. 1f)
shows peaks at 533.1 eV, 531.8 eV and 530.8 eV assigned to Cs2O, C– –O
and C–O/C–OH. The HRXPS Cs 3d peaks at 726.4 eV (Cs 3d3/2) and 739
eV (Cs 3d5/2) in Fig. 1g) confirm Cs in the form of Cs2O [16]. The TEM
micrograph in Fig. 1h) inset depicts folded and wrinkled sheets [17]; the
high resolution image shows both crystalline graphitic dominion (red)
and nanoparticles about 5 nm and smaller (blue). We suggest that Cs is
bonded to the GO sheet as shown in the model structure of CsRGO in
Fig. 1i), where COOH groups in the GO periphery, are replaced by
COOCs giving rise to Cs2O-like clusters or small nanoparticles. The
epoxy ring near the hole in the graphene lattice is broken during GO
reduction, and the C–O–C groups are replaced with C–O–Cs. Cs may also
replace hydrogen atoms in OH groups forming C–O–Cs [9,18]. The
partial reduction of graphene oxide during Cs decoration is related to
highly alkaline pH 12.34 [19]
4. Optical, and electronic properties
In the absorbance spectra of CsRGO at Fig. 2a) the peak at 230 nm is
due to π-π* transition, while the peaks at 290 nm and 350 nm are due to
optical absorption of C═O and C− O moieties [20]. The Tauc plot (αhν)2
vs (hv) at Fig. 2a) inset shows a direct bandgap of 2.85 eV. The extended
absorption at the lower energy is attributed to structural defects and
provides evidence of charge injection from the Cs2O-like clusters to the
RGO sheet. The PL spectra with 350 nm excitation shown in Fig. 2b)
depicts an emission peak at 390 nm assigned to σ*→n transitions. The
emission at 461 nm was attributed to the π*→π transition of the sp2
carbon atoms but also to direct band-to-band recombination in the Cs2O-
like clusters. The groups associated with C– – O cause σ*→n electronic
transitions at 550 nm [21].
The cyclic voltammograms shown in Fig. 3a) present the potential
onset of hydrogen evolution E = -0.5 V and E = -0.95 V vs Pt, for GO and
CsRGO respectively, which correspond to an electronic energy of –4.0
and − 3.55 eV. Fig. 3b) presents the Mott-Schottky plots 1/C2 vs E where
the flat band potential values, i.e. when 1/C2 = 0, were − 0.05 V and
− 0.5 V vs Pt for GO and CsRGO respectively; the slope indicate both
materials behave as n-type semiconductors [22].
The hydrogen evolution from GO and CsRGO is plotted in Fig. 3c). To
3
Materials Letters 314 (2022) 131864
assess photocatalyst stability three four-hour cycles were done. After
each cycle, the system was purged with N2 for two minutes. The H2-
evolution for CsRGO reached 1701 µmolg− 1 in CsRGO in the first 4-hr
cycle and increased up to 2000 µmolg− 1 at the end of the fourth cycle.
For comparison, reported photocatalytic H2-generation for N-doped
RGO, B-doped RGO and MoS2–TiO2-RGO are 64.6 µmolg− 1h− 1, 66.7
µmolg− 1h− 1 and 165.3 µmolg− 1h− 1 after one cycle [4 23]. The photo­
catalyst showed good stability without any degradation of the photo­
catalytic activity, which indicates the activation of the reaction centers,
although the nature of this activation will be subject of a future work.
The enhanced photocatalytic hydrogen evolution rate in CsRGO is
attributed to an increased charge extraction due to reduction of work
function upon Cs addition, and improved charge separation upon GO
reduction. The proposed band diagram for photocatalytic H2-evolution
of CsRGO is shown in Fig. 3d). The presence of nanoparticles was
confirmed by TEM; then, the conduction band (CB = − 1.53 eV) and
valence band (VB = 0.44 eV) values of Cs2O taken from reference [24],
are compared with the work function of RGO, which is around –4.0 eV
and with the values from Fig. 3a and b); CsRGO donor level energy ED is
higher that the work function of GO and H+/H− reduction potential. The
photogenerated electrons are then injected from Cs2O CB and ND to RGO
and to the solution, increasing the H2-evolution rate. Holes created in VB
are scavenged by methanol [25]. The effect of different hole scavengers
on the H2-generation will be studied in a future work. Due to its high
conductivity, RGO assists in the fast charge separation and acts as
cocatalyst to produce hydrogen during the process [26].
5. Conclusions
Cesium-decorated graphene oxide was synthesized using facile
titration-based technique. Cs is present as Cs2O-like clusters, replacing
the hydrogen atoms in carboxyl and hydroxyl groups. Cs would also
break epoxy ring and form the C-O-Cs groups. The material is n-type
semiconductor, amorphous, exhibits an electrical conductivity of 10− 4
S.cm and a direct band gap of 2.85 eV. Cs-doping contributes with one
electron to graphene plane and the reduction of the work function of
RGO, resulting in an enhanced photocatalytic activity. A maximum H2
photocatalytic generation of ca. 2000 µmolg− 1 was achieved after three
four-hour cycles of H2-generation, indicating the synthesized material
N. Gnanaseelan et al.
has a stable activity upon cycling.
CRediT authorship contribution statement
N. Gnanaseelan: Conceptualization, Methodology, Writing – orig­
inal draft. M. Latha: Validation, Resources. A. Mantilla: Validation,
Resources. S.K. Kamaraj: Validation, Resources. F.J. Espinosa-Faller:
Validation, Resources. F. Caballero-Briones: Conceptualization,
Methodology, Validation, Resources, Writing – review & editing,
Supervision.
Declaration of Competing Interest
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
Financed by CONACYT 2019-40798, CONACyT CB-285711 and SIP-
20210702 projects. XPS measurements at LANNBIO-CINVESTAV-
Merida, were financed thru FOMIX-CONACYT. A.C. Espindola-Flores
and S. Pacheco are acknowledged for FTIR and XRD measurements. J.
E. Samaniego is acknowledged for H2-evolution measurements. LM was
partially financed by CONACyT and UAQ.
Appendix A. Supplementary data
FESEM/TEM images, EDS mapping, electrical conductivity, Raman
Materials Letters 314 (2022) 131864
parameters, electrochemistry. Supplementary data to this article can be
found online at https://doi.org/10.1016/j.matlet.2022.131864.
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