BANDGAP ENGINEERING OF MELON

USING HIGHLY REDUCED GRAPHENE

OXIDE FOR ENHANCED
PHOTOELECTROCHEMICAL
HYDROGEN EVOLUTION

Presented by
 OVERVIEW
03
01 02
BACKGROUND PROBLEM INTRODUCTION

04 05 06
LITERARY SYNTHHESIS PROPERTIES
REVIEW

07
CONCLUSION
 BACKGROUND
In times of climate change, renewable energy sources are being extensively studied in order to address the problems of global energy supply and
environmental sustainability. Among the renewable energies, H2 fuel (green hydrogen), produced from water with solar energy, is preferred
because of its natural occurrence and ecological compatibility.To this end, photocatalytic,photoelectrochemical and photoreforming generation
of green H2 fuel by water splitting with solar energy are being investigated. Because (i) make optimal use of the solar spectrum (especially in
the visible range of sunlight), (ii) are chemically stable, (iii) inexpensive, and (iv) efficiently separate photoexcited charge carriers.
 THE PROBLEMS
The uncondensed form of polymeric carbon nitrides (PCN),
generally known as melon, is a stacked two-dimensional structure
of poly(aminoimino)heptazine. Melon is used as a photocatalyst
in solar energy conversion applications, but suffers from a poor
photoconversion efficiency due to weak optical absorption in the
visible spectrum, high activation energy, and inefficient separation
of photoexcited charge carriers.
 INTRODUCTION
Experimental and theoretical studies to engineer the bandgap of melon with highly reduced graphene oxide (HRG) were carried out.
Three HRG@melon nanocomposites with different HRG:melon ratios (0.5%, 1%, and 2%) were prepared. The 1% HRG@melon
nanocomposite showed a higher photocurrent density (71 μA cm-2 ) than melon (24 μA cm-2 ) in alkaline conditions. The addition
of a hole scavenger further increased the photocurrent density to 630 μA cm-2 relative to the reversible hydrogen electrode (RHE).
 LITERARY REVIEW
Transition metal oxides/-chalcogenides in combination with noble
metals are usually the photocatalysts of choice.Major disadvantages
that prevent commercialization are the lack of chemical stability under
working conditions, the insufficient absorption of sunlight in the
visible spectral range,the high demand for precious metals i.e.
platinum.
Graphitic carbon nitride (g-C3N4) was explored for a variety of
photocatalytic applications. Melon, uncondensed form of g-C3N4,
attracted attention . It has been used as precursor for the synthesis of
graphitic carbon nitride (g-C3N4).It resembles g-C3N4 in terms of its
composition and but differs by having terminal -NH2 groups.
For practical implementation, metal-free photocatalysts would be
much more favorable, particularly carbonaceous materials, as
they are naturally abundant, inexpensive, environmentally
friendly, and chemically and mechanically stable.Carbon nitride
polymers and reduced graphene oxide are utilized in various
photocatalytic applications
Frequently, attempts are made to overcome the shortcomings of
metal-free carbon nitride photocatalysts
by substitution with nonmetals,by copolymerization, or
with hybrid heterostructures or nanocomposites. These composites
with conductive materials are option improve
the charge separation efficiency of semiconductors.
 SYNTHESIS AND PROPERTIES OF
HRG@MELON.
The oxidation of graphite to graphene oxide (GO) followed by reduction to highly reduced graphene oxide
(HRG) (Scheme S2) was monitored by X-ray diffraction (XRD) and Raman spectroscopy. The diffractogram
for GO showed a reflection at a lower Bragg angle 2θ = 12.5 (Figure 1a, blue line).

After reduction to HRG, it appeared as a broad reflection between 2θ = 20o and 30o , centered at 25o . This
indicates a removal of the O-containing functional groups (Figure 1a, black line). The X-ray diffractogram
(Figure 1a, red line) of as-synthesized melon shows two reflections around 2θ = 12.32 o and 27.45o ,
respectively
SYNTHESIS AND PROPERTIES OF
HRG@MELON.
The Raman spectrum of as-synthesized HRG (Figure 1b, black line) shows two well-defined bands centered
at 1345 cm-1 (D band) and 1585 cm-1 (G band). There were significant variations in the intensity ratio for
the D and G bands of HRG during oxidation and reduction steps (Figure 1b).This indicates that the reduction
process increases the average size of the sp2 domains.

Raman spectra of pristine melon (Figure 1b, red line)showed broad band between 1100 cm-1 and 2200 cm-1
due to fluorescent background. The broadened D band at 1345 cm-1 in case of the HRG@melon
nanocomposite (Figure 1b, blue line) from overlapping bands like the D band of graphene, the C–N
vibration mode at 1285 cm-1 ,the C=N vibration mode of melon at 1400 cm-1 .
 SYNTHESIS AND PROPERTIES OF
HRG@MELON.
The structure of melon was further confirmed by solid-state 13C and 15N NMR spectra.The 13C cross
polarization-magic angle spinning spectrum of melon (Figure 1c) showed two sharp signals with peak
maxima at δ = 166 and 157 ppm. The low field signal at δ = 166 ppm was assigned to the carbon atoms, the
high field signal at δ = 157 ppm corresponds to CN3 moieties in heptazine ring.

The distinguished signals (Figure 1d) contain a broad intense signal from δ = –171 to –205 ppm due to a
continuous slow reduction in polarization confirming the presence of tertiary N atoms (Ntert). The
resonance at δ ~ –224 ppm showing a moderate intensity loss can be ascribed to the central N atom.
 OPTICAL AND ELECTRONIC PROPERTIES.
The optical properties and the bandgaps of pristine HRG,
melon, and the 1% HRG@melon nanocomposite were
determined by UV-visible diffuse reflectance spectroscopy.
Figure 4a shows the diffuse reflectance absorption spectra of
HRG, melon, and the 1% HRG@melon nanocomposite.
HRG shows a very weak absorption, mostly in the UV region
(Figure a, black line).. Melon shows a broad absorption in
the UV-visible region with an absorption edge at ~480 nm
(Figure 4a, red line). However, with 1% HRG@melon, the
absorption edge is red-shifted (~520 nm) to the visible region
(Figure 4a, blue line)
The bandgap energies for melon and the 1% HRG@melon
nanocomposite are 2.6 and 2.4 eV, respectively (Figure
4b). The enhancement of the visible light utilization and
narrowing of the bandgap in the nanocomposite can be
attributed to the contact of the HRG nanosheets with the
melon lamella which results in an electronic redistribution
at the interface between HRG and melon. The VB and CB
potentials of pristine melon, HRG and its nanocomposite
were calculated byequations (i, ii):
𝐸𝐶𝐵 = 𝑋 − 𝐸𝑒 − 1 2 𝐸𝑔 (i)
𝑋 = [𝑋(𝐶) 𝑎 × 𝑋(𝑁) 𝑏 × 𝑋(𝑂) 𝑐 ] 1 (𝑎+𝑏+𝑐) ⁄ (ii)
 PHOTOELECTROCHEMICAL SPLITTING OF
WATER.
The photoelectrochemical water splitting performance of the as-fabricated photoelectrodes using melon in combination with
different ratios of HRG was measured in a 3-electrode cell under AM 1.5 G illumination. The results are shown in Figure 5a.
The conductive character of HRG (a zero bandgap material) facilitates charge transfer in many optoelectronic
applications.The I-V behavior of the as-fabricated melon and HRG@melon photoelectrodes (Figure 5a, Table S2) under
illumination indicates the solar light impact on the photoelectrochemical behavior of the asfabricated photoelectrodes.

The photostability of the photoelectrodes in terms of the I-t plots was analyzed by chronoamperometry. The
chronoamperometric curves (Figure 5b) declined initially slightly due to the possible charge recombination behavior. [66]
However, the photocurrent was sustained up to 2000 s with only minimal loss. All samples showed recoverable photocurrent
density levels under solar illumination, indicating a typical photocatalyst behavior. As expected, the photocurrent density
level is sustained after multiple transient cycles, specifically for 1% HRG@melon.
 PHOTOELECTROCHEMICAL SPLITTING OF
WATER.
Electrochemical impedance The enhanced activity of
In (Figure 5d), the pristine samples
spectroscopy (EIS) analysis was HRG@melon in photocatalytic
showed larger radii than the 1%
carried out to understand the effect applications results from the fact
HRG@melon. The order of
of HRG on the resistances and the that(i) the assembly of HRG and
decreasing semicircle radii is melon
separation efficiency of the charge melon reduces the bandgap of
> HRG > 1% HRG@melon. Upon
carriers. The EIS analysis was melon from 2.6 to 2.4 eV and (ii)
illumination, the 1% HRG@melon
performed using 0.1 M KOH the peripheral amino groups of
nanocomposite showed a higher
aqueous solution as electrolyte melon enhance the wettability of
charge transfer than melon.
under visible light. photoanode and improve HER.
 CONCLUSION
Highly reduced graphene oxide (HRG), melon, and HRG@melon nanocomposites with
different HRG:melon ratios was synthesized. The nanocomposites were tested for
photoelectrochemical water splitting.The findings were corroborated by first-principles
calculations. Both experimental and theoretical results indicate that the enhanced HER
activity is due to the (i) high surface area of HRG, (ii) presence of πconjugated
heptazine moieties of melon, and (iii) charge redistribution at the interface of HRG and
melon.
.Importantly, the designed photocatalyst (1% HRG@melon nanocomposite) has
excellent potential for efficient HER even without the use of expensive metals or metal
oxides. The HRG@melon nanocomposites can also be applied as green, cost-effective,
and efficient photocatalysts for related applications such as photoreforming, light-
induced organic reactions, and solar energy conversion.
 THANK YOU
Hydrogen is a clean fuel that, when consumed in a fuel cell, produces only water.
Hydrogen can be produced from a variety of domestic resources, such as natural gas,
nuclear power, biomass, and renewable power like solar and wind