Article

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Solar-Light Harvesting Bimetallic Ag/Au Decorated Graphene

Plasmonic System with Efficient Photoelectrochemical Performance
for the Enhanced Water Reduction Process
Saikumar Manchala,†,‡ Lakshmana Reddy Nagappagari,§ Shankar Muthukonda Venkatakrishnan,§
and Vishnu Shanker*,†,‡
†
Department of Chemistry, National Institute of Technology, Warangal, Telangana 506004, India
‡
Centre for Advanced Materials, National Institute of Technology, Warangal, Telangana 506004, India
§
Nanocatalysis and Solar Fuels Research Laboratory, Department of Materials Science and Nanotechnology, Yogi Vemana
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University, Kadapa, Andhra Pradesh 516005, India

*
S Supporting Information
Downloaded via 93.179.90.240 on July 26, 2019 at 23:58:42 (UTC).

ABSTRACT: Nowadays, surface plasmon resonance (SPR) induced

hot-electron transfer from noble metals to host materials has been a
widely used concept in solar energy conversion. On the other hand, the
development of graphene-based photocatalytic systems for photo-
catalytic water reduction has attracted tremendous interest. In the
present article, we develop a novel efficient photocatalytic system for
clean energy production, i.e., semiconductor-free, solar-light harvesting
graphene sensitized Ag/Au-bimetallic plasmonic system, by cost-effective
and eco-friendly one-pot in situ green reduction process. Here, graphene
oxide (GO) reduced well under the reflux conditions approximately at
90 °C with vitamin C, and simultaneously the Ag and Au nanoparticles
(NPs) deposited on the graphene sheet. The reduction of GO to
graphene and deposition of an alloy of Ag and Au nanoparticles on
graphene sheet have been analyzed by UV−vis and PXRD. These results
revealed that bimetallic Ag/Au-graphene has all the characteristic peaks of graphene and Ag and Au NPs. Morphological studies
(SEM, TEM) clearly show that the alloys of Ag and Au NPs are well orderly deposited on the graphene sheet. The synthesized
bimetallic Ag/Au-graphene plasmonic system was applied for photocatalytic water reduction process for the first time, and it
affords a superior photocatalytic performance for H2 evolution from water reduction than Ag-graphene and Au-graphene
plasmonic systems under sunlight illumination and further supported by photocurrent experiments. The rate of H2 evolution of
bimetallic Ag/Au-graphene plasmonic system is 1.4- and 2-fold more than that of Au-graphene and Ag-graphene plasmonic
systems. For enhanced photocatalytic H2 evolution, a mechanism has been proposed. Here graphene serves as an electron
mediator/acceptor and light absorber, and the Ag and Au NPs alloy serves as reaction center for H2 evolution.
KEYWORDS: bimetallic Ag/Au-graphene, plasmonic system, water reduction, green synthesis, H2 evolution,
photoelectrochemical performance

■ INTRODUCTION
Energy crisis and environmental consequences such as global
warming and pollution have been ringing the alarm bell to the
upcoming generation. In the past 10 years, the large growth in
the world population led to a significant rise in the emission of
greenhouse gases from conventional fossil fuels. Finding ways
to solve this problem, clean, sustainable, and renewable energy
from especially the conversion of sunlight energy to hydrogen
(H2) energy through photocatalytic water splitting is the most
pivotal approach.1−3
Over a century, noble-metal nanostructures have attracted
the scientific community because of their SPR with respect to
visible light, since the discovery of interaction of light with
spherical particles present in the air by Mie in 1908.4 However,
bimetallic NPs of noble metals, constituted of two different
metals with core−shell structure and alloy nanostructures, have
captured enormous attention because of their unique physical
properties like optical, magnetic, electronic, and particularly
chemical, catalytic properties,5−7 along with their diverse and
wide range of applications in catalysis, photonics, surface
enhanced Raman scattering (SERS), chemical and biological
sensing,8−14 and electrochemical water splitting.15 These
properties are distinctly superior to their homogeneous
Received: April 13, 2019
Accepted: July 15, 2019

© XXXX American Chemical Society A DOI: 10.1021/acsanm.9b00684

ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
Scheme 1. Pictorial Illustration for the Synthesis of Ag-Graphene, Au-Graphene, and Bimetallic Ag/Au-Graphene Plasmonic
Systems
monometallic counterparts (constituted of single metal NPs),
resulting from the synergistic effects of both metal atoms.
On another hand, from the past 3 decades, carbon
nanostructures have played a dominant role in the photo-
catalysis. They can be used either as supports for arresting/
immobilizing bimetallic nanoparticles from conglutination or
as metal-free cocatalysts.16−19 Over the reported carbon
nanostructures, graphene became the prominent material for
the scientific community since the single layer of graphene was
successfully made in 2004 via micromechanical cleavage by
Novoselov. The interest in graphene originates from its unique
properties such as high electrical and thermal conductivity,
large specific surface area, and chemical stability.20,21
Innumerable studies have been investigated on graphene
supported monometallic nanoparticles such as Ag,22,23 Au,24,25
Pt,26 Pd27 and bimetallic nanoparticles including Ag/Au,28 Au/
Pt,29 Pd/Pt,30 Ag/Pd,31 Au/Pd,32 Au/Ag33 for sensing,
antimicrobial activity, fuel cells, hydrogen-energy storage, and
organic transformation applications. The making of graphene-
based bimetallic NPs composite is an effectual strategy to
develop highly efficient composite hybrids. The smart
intercalation of mono- and bimetallic nanoparticles into sheets
of graphene can not only prevent the coalescence of both
graphene sheets and metal nanoparticles but also offer the
superior hydrophilicity by improving the aqueous dispersibility,
which increases mass transit in the catalytic reaction.34 The
feasibility of tuning the specific bimetal−graphene interactions
and synergistic effects in the nanospace of the graphene sheets
B DOI: 10.1021/acsanm.9b00684
Article
via intercalation can directly influence the photocatalytic and
electrochemical properties.35
Recently, some of the researchers have reported photo-
catalytic H2 evolution from Pt-decorated graphene nano-
composites.36,37 However, the high cost and limited sources of
Pt greatly hindered its large-scale commercial application. As a
member of noble metals, Au is more frequently used in
photocatalytic water splitting as a cocatalyst in order to
improve the performance of photocatalyst, mainly because of
its high work function as well as the lowest activation energy.
In the present work, bimetallic Ag/Au decorated graphene
nanosheets are designed for photocatalytic water reduction
from glycerol−water solution. As for our literature knowledge,
the present work is the first report on the photocatalytic water
reduction over the bimetallic Ag/Au-graphene plasmonic
system without any semiconductor and dye sensitizer. This
makes the approach cost-effective and shows high H 2
production compared to most of the reported nanocarbon-
based semiconductor materials. Herein, we have looked at
using this strategy in synergy to improve photocatalytic H2
evolution via water reduction. Furthermore, the plausible
mechanism for enhanced photocatalytic reaction in the
bimetallic Ag/Au-graphene plasmonic system has been
proposed.
■ EXPERIMENTAL DETAILS
Materials. Nanographite powder (Sisco Research Laboratories Pvt
Ltd., 99 wt %), potassium permanganate (KMnO4, Sisco Research
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials Article

Laboratories Pvt Ltd., 98 wt %), hydrochloric acid (HCl, SDFCL, 37

wt %), sulfuric acid (H2SO4, SDFCL, 98 wt %), hydrogen peroxide
(H2O2, SDFCL, 30 wt %), silver nitrate (AgNO3, Merck, 99 wt %),
■ RESULTS AND DISCUSSION
Characterization of As-Synthesized Photocatalysts.
and tetrachloroauric acid (HAuCl4, Sigma-Aldrich, 99.9 wt %) were
To monitor the reduction of GO, HAuCl4, and AgNO3 by
purchased. Double distilled (DD) water was used in all experiments. vitamin C, UV−visible spectroscopy was performed and the
Synthesis of Bimetallic Ag/Au-Graphene. Initially, GO was results were presented in Figure 1. As presented in Figure. 1,
prepared by using commercially available nanographite powder
through a modified Hummers method.38 Eventually, bimetallic Ag/
Au decorated graphene nanocomposite was synthesized by using the
following method. In brief, the GO solution (1 mg/mL) was prepared
by dispersing 0.1 g of GO in 100 mL of DD water. Then add 20 mM
vitamin C and warm the reaction flask up to 90 °C. To this warmed
solution is sequential addition of 1:1 ratio of AgNO3 and HAuCl4
with the interval of 30 min, and the stirring was continued for 24 h
under reflux conditions. For comparative study, Ag-graphene and Au-
graphene were also synthesized through a similar procedure in the
absence of HAuCl4 and AgNO3. Pure graphene and bimetallic Ag/Au
nanoparticles were also synthesized under similar conditions in the
absence of both the metal salts and graphene. The total synthesis
procedure was represented in Scheme 1.
Characterization. The as-prepared samples were characterized
with powder X-ray diffraction (PXRD) studies by using PANalytical
Advance X-ray diffractometer using Ni-filtered Cu Kα (λ = 0.154 06
nm) radiation. The surface morphology and chemical composition
were investigated by using scanning electron microscope (SEM), Figure 1. UV−visible spectra of as-synthesized GO, graphene, Ag-
VEGA3, Tescon, USA, integrated with an energy dispersive X-ray graphene, Au-graphene, and bimetallic Ag/Au-graphene.
spectrometer (EDS). Further, it has been analyzed under a high-
resolution transmission electron microscope (HR-TEM), JEOL, JEM-
2100F operated at 200 kV. X-ray photoelectron spectroscopy (XPS)
was performed using Al Kα radiation, on a PHI 5000 Versaprobe the UV−visible spectra of all nanocomposites showed a peak at
instrument, ULVAC-PHI, Chigasaki, Japan. FT-IR spectra were 270 nm assigned to the π−π* transition that designates that
recorded from 4000 to 400 cm−1 in transmission mode on a the conjugation remains stored and the majority of oxygen
PerkinElmer Spectrum 100 FT-IR spectrometer using KBr pellet. moieties are eliminated from the GO.39 In the spectra of Ag-
Raman spectra were noted on a Horiba Scientific confocal Raman graphene and Au-graphene, the peaks at 420 and 585 nm are
microscope with the laser power of 2−5 mW at 532 nm laser due to the formation of Ag and Au NPs on the graphene
excitation. The optical properties were analyzed by using Analytikjena surface. Furthermore, the spectra of bimetallic Ag/Au-
SPECORD 205 UV−visible (UV−vis) spectrophotometer. graphene showed the small and broad peak at 550 nm which
Photoelectrochemical Experiments. Photoelectrochemical ex-
was between the 420 and 585 nm due to the formation of
periments were performed on IVIUM Technologies electrochemical
workstation to measure photocurrent response in a conventional
bimetallic Ag/Au-alloy NPs on the graphene surface.40
three-electrode photoelectrochemical cell, and Na2SO4 (0.1 M) was PXRD was carried out to know the structures of the GO,
employed as the electrolyte solution. The working electrode was made graphene, Ag-graphene, Au-graphene, and bimetallic Ag/Au-
up of photocatalyst which was deposited on ITO (indium tin oxide) graphene as shown in Figure 2a,b. And the PXRD pattern of
substrate, while the “Pt” wire and Ag/AgCl (in saturated KCl) served bimetallic Ag/Au nanoparticles is displayed in Figure S1. The
as a counter and reference electrodes. To evaluate the performance of nanographite powder displays a sharp and strong peak at 26.6°
synthesized photocatalysts, a Xe-lamp (300 W) was utilized as the (dspacing = 0.335 nm) with a basal reflection (002). In the case
light source under several on−off cycles of photocurrent experiments. of GO, the diffraction peak moves to a lower angle of 12.2°
Photocatalytic Activity. The photocatalytic water reduction (dspacing = 0.725 nm), due to the oxidation of graphite. And in
experiments were carried out in a 180 mL of airtight sealed quartz the case of graphene, the diffraction peak at 12.2° vanished
reactor with silicone rubber septum under natural solar-light while a broad peak centering at 25° (dspacing = 0.356 nm) was
irradiation at ambient conditions in the Kadapa city. The intensity noticed. However, the larger dspacing of GO than that of pristine
of light was measured with a digital lux meter (LT Lutron LX-101A) graphite after oxidation is corresponding to the intercalation of
for every hour between 11:00 a.m. and 3:00 p.m. The average light water molecules and the formation of oxygen-containing
intensity was approximately 9.5 × 104 lx during the photocatalytic functional groups between the layers of graphite, and the
experiments. In an ideal experiment, photocatalyst powder was placed lower dspacing of graphene than that of GO after reduction is
into 5 vol % aqueous glycerol (used as a hole scavenger) mixtures at a
due to the removal of oxygen-containing groups from the
concentration of 5 mg/100 mL. Dark experiments were carried out
for at least 30 min to acquire adsorption equilibrium and ensure equal
GO.41 PXRD patterns of the black composite powders clearly
dispersion. The reactor containing solution mixture was evacuated by show the presence of silver and gold NPs in the products, and
using high pure nitrogen (N2) gas for at least 30 min to remove the four strongest diffraction peaks can be indexed as (111),
dissolved oxygen (O2). Subsequently, the evacuated reactor was (200), (220), and (311) of the cubic silver structure (JCPDS
exposed to natural solar light, and magnetic stirring was continued. 04-0783) and cubic gold structure (JCPDS 04-0784).
Finally, the evolved gaseous sample was collected at regular time Additionally, the average crystallite size can be calculated by
intervals with an airtight syringe. The evolved H2 gas was quantified using the Scherrer from the PXRD pattern,
with Shimadzu GC-2014 offline gas chromatograph equipped with a kλ
thermal conductivity detector (TCD) by using N2 as a carrier gas at D=
70 °C. β cos θ

C DOI: 10.1021/acsanm.9b00684
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Figure 2. (a) PXRD patterns of graphite and as-synthesized GO, graphene and (b) Ag-graphene, Au-graphene, and bimetallic Ag/Au-graphene
plasmonic systems. (c) Raman spectra of as-synthesized GO and graphene and (d) Ag-graphene, Au-graphene, and bimetallic Ag/Au-graphene
plasmonic systems.
where D = crystallite size (nm), β = fwhm (radians), k = 0.9
(Scherrer constant), λ = wavelength of X-rays (0.154 06 nm),
and θ = Bragg’s angle/peak position (radians). The measured
“D” values for nanoparticles in Ag-graphene, Au-graphene, and
bimetallic Ag/Au-graphene are 34, 42, and 32 nm.
Raman spectroscopy is a robust nondestructive technique
and significantly differentiates the nature (ordered and
disordered) of nanocarbon materials. As represented in Figure
2c, the Raman spectra of GO displayed two major character-
istic peaks. The first one is at 1330 cm−1 for the D band
corresponding to A1g symmetry breathing mode, and the
intensity of the D band depends upon the staging disorder and
population of defects. The second one is at 1582 cm−1 for the
G band corresponding to E2g symmetry phonon mode of in-
plane vibrations of all sp2 carbon atoms.42 After reduction, the
intensity ratios of both D and G bands obviously increased
from 0.98 (GO) to 1.12 (graphene), and one more peak
appeared at 2662 cm−1 for 2D band corresponding to the two-
phonon mode with opposite wave vectors that confirms the
formation of graphene.43,44
Furthermore, the Raman spectra of synthesized mono-
metallic (Ag and Au) decorated graphene and bimetallic Ag/
Au decorated graphene plasmonic systems (Figure 2d) showed
an increase in the D and G band intensities compared to GO.
This might be arising from the surface enhanced Raman
scattering of noble metal NPs (Ag, Au) present in the
composites45 and further confirms the reduction of GO to
graphene.
After reduction, as represented in SEM images in Figure 3a−
c, the silver and gold NPs are nicely separated from each other
D DOI: 10.1021/acsanm.9b00684
Article
and equally distributed on the graphene sheet. In the case of
Ag/Au-graphene composite system shown in SEM image
Figure 3c, the bimetallic silver and gold alloy NPs are mixed
uniformly and well orderly dispersed on the surface of the
graphene sheet. The elemental dispersive X-ray spectroscopy
(EDS) discloses the presence of silver, gold, carbon, and
oxygen elements in the respective synthesized plasmonic
systems.
As presented in HR-TEM images Figure 4a−f, the bimetallic
Ag/Au NPs in the Ag/Au-graphene plasmonic system are well
decorated on the surface of a graphene sheet and appeared as a
spherical shape and morphologically look like core−shell. In
Figure 4c, the size of Ag core is 22 nm and thickness of the
shell is 1.5 nm. It means the size of bimetallic Ag/Au core−
shell is 23.5 nm, which is approximately close to that of average
size calculated from the Scherrer equation. As exhibited in
Figure 4f, the lattice fringes and dspacing = 0.24 nm are in good
agreement with the (211) plane of cubic phase of Ag core of
bimetallic Ag/Au-graphene plasmonic system in the PXRD
pattern.46
XPS analysis was carried out in order to confirm the surface
elemental composition and elemental chemical status of as-
synthesized bimetallic Ag/Au-graphene plasmonic system. As
represented in Figure 5a, the survey XPS spectrum divulges the
existence of C, O, Ag, and Au elements. In the C 1s high-
resolution spectrum (Figure 5d) situated at the binding energy
(BE) of 284.7 eV was the characteristic peak of the sp2 C C
bonds of graphene. In addition, the peaks situated at BEs of
83.9 and 87.6 eV were the characteristic peaks of Au NPs
present at the surface of graphene which are attributed to the
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
Figure 3. SEM images and corresponding EDS of as-synthesized (a) Ag-graphene, (b) Au-graphene, and (c) bimetallic Ag/Au-graphene plasmonic
systems.
Au 4f7/2 and Au 4f5/2 peaks (Figure 5b), and the peaks situated
at BEs of 368.4 and 374.4 eV were the characteristic peaks of
Ag NPs present at the surface of graphene which are attributed
to the Ag 3d5/2 and Ag 3d3/2 peaks (Figure 5c). The splitting
energy of the Ag 3d doublet (6.0 eV) and Au 4f doublet (3.7
eV) was also confirming the metallic nature of Ag and Au.47 In
contrast, the Au 4f7/2, Au 4f5/2, Ag 3d5/2, Ag 3d3/2, and C 1s
peaks for the bimetallic Ag/Au graphene plasmonic system
shifted to the lower binding energy values compared with the
standard BE peaks for pure Au0 (Au 4f7/2 84.0 eV and Au 4f5/2
87.7 eV), Ag0 (Ag 3d5/2368.2 eV, Ag 3d3/2 374.2 eV), which
clearly confirms the successful anchoring/deposition of Ag and
Au NPs onto the surface of the graphene sheet and also
confirms the effective electron transfer between the graphene
and metal NPs.48 There were no other peaks noticed, which
indicates the high purity of the Ag/Au-graphene plasmonic
system.
As presented in Figure 6 the FT-IR spectra of GO reveal the
characteristic broad band between 3000 and 3700 cm−1 and
simultaneously a sharp band at 1628 cm−1 that are correlated
to the stretching and bending frequencies of OH groups
present on the GO surface. The bands observed at 2922 and
E DOI: 10.1021/acsanm.9b00684
Article
2853 cm−1 correspond to the symmetric and asymmetric
stretching frequencies of CH. And another major band noticed
at 1720 cm−1 corresponds to the stretching frequency of CO
of carboxylic acid and carbonyl groups present at the edges of
GO. Finally, the bands at 1248 and 1021 cm−1 are attributed to
the stretching frequencies of phenolic C−O and epoxy C−O−
C groups, respectively. However, after the reduction of GO to
graphene there is an apparent decrease in the intensity of the
absorption bands of the oxygen-containing functional groups.
Furthermore, the FT-IR spectra of synthesized monometallic
(Ag and Au) deposited and bimetallic Ag/Au-graphene
plasmonic systems reveal that the decrease in the intensity of
the absorption bands can be ascribed to both reductions of GO
to graphene by vitamin C and deposition of noble metal
nanoparticles on the GO surface. Also, the decrease in the
intensity of OH stretching frequency in nanocomposites can be
attributed to the interactions between noble metal NPs (Ag
and Au) and OH groups of GO. The shape and appearance of
all other peaks of plasmonic systems disclose the interaction
between noble metal NPs (Ag and Au) and the surface of
graphene.49 From FT-IR spectra of plasmonic systems, it can
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ACS Applied Nano Materials Article

Figure 4. HR-TEM images of as-synthesized (a−f) bimetallic Ag/Au-graphene plasmonic system.

Figure 5. (a) XPS survey spectrum of Ag/Au-graphene and (b) high-resolution spectra of Ag 3d, (c) Au 4f, and (d) C 1s.

be concluded that there are strong interactions between noble photocatalyst, and it was observed that there is no H2
metal NPs and graphene. production. The H2 production rates for all photocatalysts
Photocatalytic Activity. The photocatalytic capabilities of were displayed in Figure 7a. As shown in Figure 7a, for bare
the synthesized plasmonic systems were carried out under solar graphene and bimetallic Ag/Au system, no H2 production was
light illumination for H2 evolution by using glycerol as a hole detected. The rates of H2 evolution for the Ag-graphene, Au-
scavenger. The control experiments were performed without graphene, and bimetallic Ag/Au-graphene plasmonic systems
F DOI: 10.1021/acsanm.9b00684
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electron capturing and transporting properties of graphene,

Figure 6. FT-IR spectra of as-synthesized GO, graphene, Ag-
graphene, Au-graphene, and bimetallic Ag/Au-graphene.
were found to be 20, 28, and 40 μmol h−1 g−1. The typical time
courses of H2 evolution for Ag-graphene, Au-graphene, and
Ag/Au-graphene plasmonic systems were shown in Figure 7b.
As presented in Figure 7a,b, it is noticed that the introduction
of these plasmonic nanoparticles (Ag, Au, and Ag/Au) on the
surface of the graphene sheet is crucial for the H2 production.
The obtained H2 production for Ag-graphene and Au-
graphene plasmonic systems compared to graphene and
bimetallic Ag/Au system is due to combined effects of (1)
enhanced visible-light harvesting property, (2) the SPR
property of decorated noble metal nanoparticles, (3) the
and (4) the homogeneous distribution of noble metal
nanoparticles over graphene surface. Additionally, the bimet-
allic features of core−shell Ag/Au nanoparticles have triggered
the rate of H2 evolution of bimetallic Ag/Au-graphene
plasmonic system. In the case of Ag-graphene and Au-
graphene, the enhanced photocatalytic performance was
explained by the work function of metal atoms, i.e., for Ag
4.5 eV 50 and for Au 5.3 eV.51 The enhanced photocatalytic H2
evolution of bimetallic Ag/Au-graphene plasmonic system
compared to Ag-graphene and Au-graphene plasmonic systems
was further explained by photocurrent studies.
The effective charge transfer in the bimetallic Ag/Au-
graphene plasmonic system was detected by the photo-
electrochemical experiments, as shown in Figure 7d. As
noticed, the bimetallic Ag/Au-graphene plasmonic system
has shown the high amount of photocurrent response
compared to Ag-graphene and Au-graphene plasmonic
systems. This fact explains the formation of an active electron
transfer interface between the graphene, Ag and Au NPs, which
further leads to the enhanced photocatalytic performance of
the bimetallic Ag/Au-graphene plasmonic system.52 As
mention in Table 1, it can be seen that the bimetallic Ag/Au
graphene showed a high rate of H2 production than most of
the reported nanocarbon based semiconductor materials.53−60
Tentative Photocatalytic Mechanism. On the basis of
our experimental investigation, we propose a suitable photo-
catalytic mechanism for improved H2 evolution over bimetallic
Ag/Au-graphene and monometallic (Ag-graphene or Au-

Figure 7. (a) H2 production rates of as-synthesized (A) graphene, (B) Ag/Au-bimetallic system, (C) Ag-graphene, (D) Au-graphene, and (E) Ag/
Au-graphene plasmonic photocatalytic systems. (b) Analogical studies of photocatalytic H2 evolution during 4 h under solar light illumination for
synthesized Ag-graphene, Au-graphene, and bimetallic Ag/Au-graphene plasmonic photocatalytic systems. (c) H2 production of Ag-graphene, Au-
graphene, and bimetallic Ag/Au-graphene plasmonic photocatalytic systems under solar light illumination. (d) Transient photocurrent experiments
of the as-synthesized Ag-graphene, Au-graphene, and bimetallic Ag/Au-graphene plasmonic systems.

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Table 1. H2 Evolution Rates over Various Nanocarbon Based Semiconductor Photocatalysts

sample amount
no. photocatalyst (mg) rate of H2 evolution (μmol h−1 g−1) light source ref
1 Ag/Au-graphene 5 40 solar light present work
2 carbonnano fibers@ZnIn2S4 30 95 300 W Xe-lamp (λ > 420 nm) 53
3 RGO/ZnIn2S4 50 40.85 300 W Xe-lamp (λ > 420 nm) 54
4 MWCNT/g-C3N4 100 7.58 (Pt as cocatalyst) 300 W Xe-lamp (λ > 400 nm) 55
5 RGO/ZnIn2S4-hydrazine 50 27.8 300 W Xe-lamp (λ > 420 nm) 56
6 C-PDA/g-C3N4 100 81.1 (Pt as cocatalyst) 300 W Xe-lamp (λ > 400 nm) 57
7 g-C3N4-nanocarbon-ZnIn2S4 50 50.32 12 W UV-LED (λ = 420 nm) 58
8 CdS/graphene 100 70 200 W Xe-lamp (λ ≥ 420 nm) 59
9 NH2-MIL-125(Ti)/reduced graphene oxide 30 91 300 W Xe-lamp 60

Figure 8. Solar-light responsive proposed mechanisms regarding enhanced H2 evolution from water splitting over the (a) monometallic Ag-
graphene or Au-graphene and (b) bimetallic Ag/Au-graphene plasmonic systems.

graphene) plasmonic systems, shown in Figure 8a,b. It is very
well established that the capturing of visible light by plasmon
nanoparticles (Ag and Au) involves generation of the hot
electron−hole pair within the noble metal through Landau
damping/SPR excitation,52,61−63 according to the conventional
plasmon induced direct hot-electron transfer (PDHET)
mechanism. As displayed in Figure 8a, under sunlight
illumination the generated hot electrons from Ag or Au
transferred to the next Ag or Au nanoparticles through the
graphene and involved H+ reduction to H2 in the Ag-graphene
or Au-graphene plasmonic systems. But in the case of
bimetallic Ag/Au-graphene plasmonic system as shown in
Figure 8b, under sunlight illumination both Ag and Au in
core−shell nanoparticles produce hot electrons and the
generated hot electrons in d-bands of Ag core transfer to the
Au shell because the electronegativity of Au (2.54) is more
than that of the Ag (1.93). Subsequently, the solid electron
transporter such as graphene transfers those hot electrons to
the next bimetallic Ag/Au-nanoparticles through its extended π
electron skeleton64 and increases their availability for the H+
H DOI: 10.1021/acsanm.9b00684
reduction to H2. The enhancement in H2 evolution rate in
bimetallic Ag/Au-graphene plasmonic system is attributed to
both metal nanoparticles (Ag and Au) in core−shell structure
supply electrons continuously, those directly involved in the
reduction of 2H+ to H2.
■ CONCLUSIONS
In summary, the bimetallic Ag/Au graphene plasmonic system
was successfully fabricated by one-pot in situ green reduction
method for enhanced H2 production from solar-light
responsive water reduction. SEM and TEM results suggest
that the Ag and Au NPs were well deposited on the graphene
surface. XPS and EDS results confirm the formation of
bimetallic Ag/Au-graphene. The bimetallic Ag/Au-graphene
plasmonic system exhibits the highest photocatalytic H2
production, i.e., 40 μmol h−1 g−1, which is approximately 2
times greater than that of H2 produced by Ag-graphene
plasmonic system and 1.4 times greater than that of H2
produced by Au-graphene plasmonic system. The bimetallic
Ag/Au-graphene plasmonic system can effectively promote the
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ACS Applied Nano Materials
charge transfer, which results in the highest photocatalytic H2
production that was explained by photocurrent studies. It is
mentioned that the present work provides new insights into
the expansion and design of semiconductor-free, cost-effective,
and highly efficient nanostructured materials for multiple
photocatalytic applications.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsanm.9b00684.
Synthesis of graphene oxide and Figure S1 showing
PXRD pattern of bimetallic Ag/Au nanoparticles (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: vishnu@nitw.ac.in.
ORCID
Lakshmana Reddy Nagappagari: 0000-0002-3327-0184
Shankar Muthukonda Venkatakrishnan: 0000-0002-5284-1480
Vishnu Shanker: 0000-0002-1341-2448
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Saikumar Manchala thanks the MHRD, Government of India,
for providing a fellowship.
■
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K DOI: 10.1021/acsanm.9b00684
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX