Monodisperse CuPt alloy nanoparticles assembled on reduced graphene oxide as catalysts in the transfer hydrogenation of various functional organic groups

Article abstract of DOI:10.1002/aoc.4863

We present herein a new nanocatalyst, namely binary CuPt alloy nanoparticles (NPs) supported on reduced graphene oxide (CuPt-rGO), as a highly active heterogeneous catalyst for the transfer hydrogenation (TH) protocol that is demonstrated to be applicable over the reduction of various unsaturated organic compounds (olefins, aldehydes/ketones and nitroarenes) in aqueous solutions at room temperature. CuPt alloy NPs were synthesized by the co-reduction of metal (II) acetylacetonates by borane-tert-butylamine (BTB) complex in hot oleylamine (OAm) solution and then assembled on reduced graphene oxide (rGO) via ultrasonic-assisted liquid phase self-assembly method. The structure of yielded CuPt NPs and CuPt-rGO nanocatalyst were characterized by TEM, XRD and ICP-MS. The activity of Cu₇Pt₃-rGO nanocatalysts were then tested for the THs that were conducted in a commercially available high-pressure tube using water as sole solvent and ammonia borane as a hydrogen donor at room temperature. The presented catalytic TH protocol was successfully applied over nitroarenes, olefines and aldehydes/ketones, and all the tested compounds were converted to corresponding reduction products with the yields reaching up to 99% under ambient conditions. Moreover, the Cu₇Pt₃-rGO nanocatalyst was also reusable in the TH by providing 99% yield after five consecutive runs in TH of nitrobenzene as an example.

Full text of DOI:10.1002/aoc.4863

Received: 24 October 2018
DOI: 10.1002/aoc.4863
Revised: 2 January 2019
Accepted: 25 January 2019
F U L L P A P E R
Monodisperse CuPt alloy nanoparticles assembled on
reduced graphene oxide as catalysts in the transfer
hydrogenation of various functional organic groups
Khadijeh Ganjehyan1 | Bilal Nişancı2 | Melike Sevim1 | Arif Daştan1 | Önder Metin3
1 Department of Chemistry, Faculty of
We present herein a new nanocatalyst, namely binary CuPt alloy nanoparticles
(NPs) supported on reduced graphene oxide (CuPt‐rGO), as a highly active
heterogeneous catalyst for the transfer hydrogenation (TH) protocol that is
demonstrated to be applicable over the reduction of various unsaturated
organic compounds (olefins, aldehydes/ketones and nitroarenes) in aqueous
solutions at room temperature. CuPt alloy NPs were synthesized by the
co‐reduction of metal (II) acetylacetonates by borane‐tert‐butylamine (BTB)
complex in hot oleylamine (OAm) solution and then assembled on reduced
graphene oxide (rGO) via ultrasonic‐assisted liquid phase self‐assembly
method. The structure of yielded CuPt NPs and CuPt‐rGO nanocatalyst were
characterized by TEM, XRD and ICP‐MS. The activity of Cu7Pt3‐rGO
nanocatalysts were then tested for the THs that were conducted in a commer-
cially available high‐pressure tube using water as sole solvent and ammonia
borane as a hydrogen donor at room temperature. The presented catalytic
TH protocol was successfully applied over nitroarenes, olefines and
aldehydes/ketones, and all the tested compounds were converted to corre-
sponding reduction products with the yields reaching up to 99% under ambient
conditions. Moreover, the Cu7Pt3‐rGO nanocatalyst was also reusable in the
TH by providing 99% yield after five consecutive runs in TH of nitrobenzene
as an example.
Science, Atatürk University, 25240
Erzurum, Turkey
2 Narman Vocational Training High
School, 25530 Narman, Erzurum, Turkey
3 Department of Chemistry, College of
Sciences, Koç University, 34450 Sarıyer,
Istanbul, Turkey
Correspondence
Önder Metin, Department of Chemistry,
College of Sciences, Koç University, 34450
Sarıyer, Istanbul, Turkey.
Email: ometin@ku.edu.tr
Bilal Nişancı, Narman Vocational
Training High School, 25530 Narman,
Erzurum, Turkey.
Email: bnisanci@atauni.edu.tr
Funding information
Türkiye Bilimler Akademisi
KEYWORDS
alloy nanoparticles, copper, nanocatalyst, platinum, transfer hydrogenation
1 | INTRODUCTION
spent on this topic and new routes are being developed
every day, the direct hydrogenation (DH) of unsaturated
Reduction of unsaturated organic compounds bearing
nitro, nitrile or carbonyl groups is one of the most funda-
mental transformations in synthetic organic chemistry,
which has found a wide‐range of applications in industry
spanning from the synthesis of fine chemicals to drug
synthesis.[1] Therefore, a broad array of methodologies is
continuously being developed by the researchers for this
essential transformation.[2] Despite the notable efforts
organic compounds has been still employed as feasible
method to yield the relevant reduction products.
However, the conventional DH reactions are often con-
ducted in elaborated reactors under pressurized hydrogen
gas and high temperature in the presence of transition
metal‐based catalysts, which makes them unpractical to
apply in regular research laboratories.[3] On the other
hand, in order to minimize or eliminate wastes, the use
Appl Organometal Chem. 2019;e4863.
wileyonlinelibrary.com/journal/aoc
© 2019 John Wiley & Sons, Ltd.
1 of 8
https://doi.org/10.1002/aoc.4863

2 of 8
GANJEHYAN ET AL.
of environmentally benign reagents and solvents become
a hot topic environmental issue for the growing concern
of safety and sustainability in green chemistry concept.[4]
In this respect, transfer hydrogenation (TH) reactions
comprising the generation of hydrogen gas in situ from
suitable hydrogen donor molecules and transfer of the
generated hydrogen to substrates via the help of metal cat-
alysts have been emerged as an attractive alternative to
DH reactions. Moreover, TH has recently become a popu-
lar topic in synthetic organic chemistry/catalysis and it is
well‐documented by several comprehensive review arti-
cles in the literature.[5] The selection of a metal catalyst
and hydrogen donor molecule are the key for the success-
ful application of THs in organic synthesis and thus a vari-
ety of hydrogen donor molecules have been tested for
them so far including isopropanol[6] hydrazine hydrate[7]
and glycerol.[8] However, the THs with these hydrogen
donor molecules have certain drawbacks such as the need
of high temperature for the activation of hydrogen release
and slow hydrogen generation kinetics even in the
presence of noble metal catalysts. In this respect, we have
recently postulate ammonia borane (AB, H3NBH3) as an
appealing hydrogen storage media both as a chemical
hydrogen storage material[9] and hydrogen donor com-
pound for THs[10] owing to its favorable characteristics
such as being a solid with a high hydrogen content and
releasing fast hydrogen in various solutions under ambi-
ent conditions.[11] In our recent papers, we have reported
several Pd‐based bimetallic alloy NPs (CoPd[12] and
NiPd[13]) and core/shell NPs (Ag/Pd[14]) supported on
reduced graphene oxide (rGO) as catalysts for the tandem
dehydrogenation of AB and hydrogenation of nitroarenes
(Ar‐NO2) to anilines (Ar‐NH2). After these successful
studies with Pd‐based nanocatalysts, we turned our direc-
tion to study the catalysis of Pt‐based NPs for the TH using
AB as hydrogen donor molecule because Pt is another
metal of choice for the hydrogenation reactions.[15] How-
ever, Pt is a precious metal, and thus its practical use in
industrial applications is limited. In this regard, binary
MPt alloy NPs in which M is a cheap first row transition
metal with a low % Pt ratio are promising catalysts com-
pared to the monometallic Pt NPs. In this regard, upon
the results of our research direction, addressed herein is
the performance of binary Cu7Pt3 alloy NPs assembled
on reduced graphene oxide (Cu7Pt3‐rGO) as catalyst for
the TH using AB as a hydrogen donor molecule and water
as sole solvent performed in a commercially available
high‐pressure glass tube at room temperature. It should
be noted that this study differs from our previous studies
not only using CuPt‐rGO as the catalyst but also utiliza-
tion of water as the sole solvent instead of aqueous
methanol solution, which is considered to be important
in terms of green chemistry.[10,16–20]
2 | EXPERIMENTAL
2.1 | Materials
Oleylamine (OAm) (>70%), 1‐octadecene (ODE, 90%),
platinum (II) acetylacetonate (Pt (acac)2, 99%), copper
(II) acetylacetonate (Cu (acac)2, 97%), borane tert‐butyl‐
amine (BTB, 95%), hexanes (99%), ethanol (99%), acetone
(97%), potassium permanganate (KMnO4), hydrogen
peroxide (H2O2, 30%), sodium nitrate (NaNO3, 99%),
sulphuric acid (H2SO4, 98%), and, ammonia‐borane (AB,
97%), were purchased from Sigma‐ Aldrich and used as
received. Natural graphite flakes (average particle size:
325 mesh) were purchased from Alfa‐Aesar.
2.2 | Instrumentation
All transmission electron microscope (TEM) images were
obtained by FEI Technai G2 Spirit BiO (TWIN) at 120 kV.
X‐ray diffraction (XRD) patterns were recorded on a
Panalytical Empyrean diffractometer with Cu‐Kα radia-
tion (40 kV, 15 mA, 1.54051 A°) over a 2θ range from
10°‐ 90° at room temperature. Elemental analysis mea-
surements were carried out on an Agilent Technologies
7700 inductively coupled plasma‐mass spectroscopy
(ICP‐MS) after each sample was completely dissolved in
aqua‐regia (HCl/HNO3: 3/1 v/v ratio).
2.3 | Synthesis of monodisperse Cu7Pt3
alloy NPs
Monodisperse CuPt alloy NPs were synthesized by using
our established protocol.[21] In a typical synthesis of
Cu7Pt3 NPs, 54 mg (0.2 mmol) of Cu (acac)2 and 121 mg
(0.3 mmol) of Pt (acac)2 were mixed with 3 mL of OAm
and 7 mL of ODE at room temperature and heated to
80 °C under continuous nitrogen gas flow and magnetic
stirring. In a separate vial, 200 mg of BTB was dissolved
in 3 mL of OAm and this solution was injected into the
metal precursor mixture at 80 °C. A gradual color change
from yellow‐green to dark‐brown was observed during
the synthesis indicating the nucleation and following
particle growth. The temperature was increased to
100 °C and was maintained at this temperature for one
hour. The NP product was separated from the reaction
mixture by adding acetone (40 mL), followed by centrifu-
gation (9000 rpm, 10 min). This procedure was repeated
by using ethanol twice and the resultant NPs collected
by dispersing them into hexane. The composition of the
yielded NPs was determined by ICP‐MS analysis.

GANJEHYAN ET AL.
3 of 8
By using the recipe described above and using only
0.3 mmol of Pt (acac)2 as the metal precursor, monome-
tallic Pt NPs were also synthesized.
2.7 | Reusability test for the Cu7Pt3‐rGO
catalyst in the transfer hydrogenation
reaction
The reusability of the Cu68Pt32‐rGO catalysts in the hydro-
genation reactions was studied by performing the cata-
lytic reaction for five consecutive runs. A typical
reusability test was initiated by using nitrobenzene as
the model substrate under the optimized reaction
conditions. After the completion of each catalytic run,
the Cu7Pt3‐rGO catalysts were separated from the reaction
solution via centrifugation and then washed with an
aqueous methanol solution to remove the residuals. Next,
the typical procedure was started for hydrogenation reac-
tion with the purified and regained Cu7Pt3‐rGO catalyst.
The reusability test was continued for five runs.
2.4 | Preparation of rGO
rGO synthesized according to the our well‐established
two‐step procedure published at several times in
elsewhere.[22] The reduction of graphene oxide by DMF
refluxing is the most important difference in our two‐step
procedure, but it is very important for the application and
higher catalytic activity of the presented nanocatalyst.
2.5 | Assembly of NPs on rGO
3 | RESULT AND DISCUSSION
To use of Cu7Pt3 alloy and monometallic Pt NPs as
catalysts for the transfer hydrogenation reactions, they
were first assembled on support material by using liquid
self‐assembly method. In a typical procedure, 50.0 mg of
the dried NPs were dissolved in 10 mL of hexane and
mixed with 100.0 mg of rGO in ethanol. The
ethanol/hexane mixture was sonicated for 2 hr to ensure
complete adsorption of NPs onto rGO. Then, the resultant
mixture was centrifuged at 7500 rpm for 10 min and the
separated catalyst was washed with ethanol.
3.1 | Synthesis and characterization of
Cu7Pt3 alloy NPs and Cu7Pt3‐rGO
nanocatalyst
Binary CuPt alloy NPs were synthesized by using our
established recipe reported elsewhere recently.[21] In our
previous report, we tested CuxPt1‐x alloy NPs assembled
on commercially available carbon black (CB) as catalysts
for the hydrolytic dehydrogenation of AB and hydrazine
borane (HB).[21] After observing a record activity with
Cu7Pt3/CB for the hydrolytic dehydrogenation of AB and
HB, we have then decided to extend its application for
our established TH protocol utilizing AB as a hydrogen
donor considering Pt as a metal of choice for the hydroge-
nation reactions. Although we reported the detailed syn-
thesis and structural analysis of colloidal Cu7Pt3 alloy
NPs in our previous publications,[21] a new representative
TEM image and XRD pattern were presented herein as
well (Figure 1). Figure 1A shows a representative TEM
image of Cu7Pt3 NPs taken their hexane dispersion reveal-
ing the monodisperse particle size distribution with an
average particle diameter of 2.5 nm. The NPs are mostly
spherical in shape and do not touch each other. The com-
position of these NPs was found to be Cu7Pt3 with ICP‐MS
analysis as expected by the presented recipe according to
our previous study.[21] Figure 1B shows the XRD pattern
of colloidal Cu7Pt3 taken their thin films formed over an
amorphous glass and a comparison to the pattern of face
centered cubic structured metallic Pt (JCPDS Card No:
04–0802). The solid solution (alloy) formation between
Cu and Pt is readily concluded by comparing two XRD
patterns in which a clear shift towards to large angle is
observable for the (111) plane of face centered cubic
2.6 | General procedure for the transfer
hydrogenation reactions catalysed by
Cu7Pt3‐rGO catalysts
Cu7Pt3‐rGO catalysts (4 mg) were suspended in water
(3 mL) and sonicated (Branson 1510MTH ultrasonic
bath) for 10 min in a glass pressure tube. Next, 0.35 mmol
benzonorbornadiene, 1.05 mmol NH3BH3 were added to
the reaction mixture. The resultant mixture was stirred
for 2 hr at room temperature. Next, the catalyst was
removed by filtration and the filtrate was extracted by
washing with diethyl ether. The organic phase was dried
over anhydrous Na2SO4 and the solvent was removed by
rotary evaporation. The yields of the reduced compounds
were determined by 1H NMR. All hydrogenated
compounds are well‐known compounds in the literature
and their characterization data were in a good agreement
with literature.[23–29]
The experimental part for the synthesis of Cu7Pt3
alloy NPs, their assembly on rGO and the catalysis of
Cu7Pt3‐rGO in the transfer hydrogenation of various
organic compounds is summarized by the Scheme 1.

4 of 8
GANJEHYAN ET AL.
SCHEME 1 Illustration of the experimental processes
Cu7Pt3 NPs. It should be noted that shape of the pattern is
due to either a poor crystallinity of Cu7Pt3 NPs or their
thin film structure over amorphous glass.
conditions for the THs. Firstly, reaction time dependent
experiments were conducted and the results showed that
the conversion gradually increased by increasing reaction
time until reaching its maximum within 2 hr (Table 1,
entries 1–4). Next, the catalytic TH was carried out in
the absence of a catalyst, and no conversion was observed
by even at longer reaction times (Table 1, entry 5). Then,
solvent effect was monitored by changing water with
methanol. Although the TH went smoothly, and stoichio-
metric conversion was obtained by using methanol in 2 hr
as well (Table 1, entry 7), due to the increasing interest in
green chemistry rules has led us to concentrate on
performing reactions in water. Additionally, Pt‐rGO
nanocatalyst was tested for the comparison, and it
provided ≥99 conversion as well in 2 hr, but it was not
preferred considering the atom economy supplied by
Cu7Pt3 NPs in which only 30 mol% Pt is present (Table 1
, entry 8). As a result of optimization experiments, it was
concluded that benzonorbornadiene was quantitatively
converted into the reduction product when catalytic TH
was conducted by using 0.35 mmol of substrate, 4.0 mg
of Cu7Pt3‐rGO nanocatalyst, 1.05 mmol of AB and
3.0 mL water at room temperature (Table 1).
Next, Cu7Pt3 alloy NPs were assembled on rGO via a
simply sonicating the hexane dispersion of the NPs and
ethanol dispersion of rGO for 2 hr. This liquid phase
self‐assembly process was yielded to Cu7Pt3‐rGO
nanocatalysts of which two representative TEM images
are depicted by Figure 2 As clearly be seen by the TEM
image, Cu7Pt3 alloy NPs were nicely assembled over
rGO nanosheets without any observable aggregation or
clumps formation. They preserved their initial particle
size and morphology over rGO nanosheets. The Pt load-
ing ratio of Cu7Pt3‐rGO nanocatalyst was determined as
8.3 wt% by ICP‐MS analysis.
3.2 | Catalytic transfer hydrogenation
reactions
After the synthesis and structural characterization of
Cu7Pt3‐rGO nanocatalyst,[21] they were tested as catalysts
in the TH reactions. Initially, a series of optimization
experiments were conducted on benzonorbornadiene as
a model compound to establish the optimized reaction
Having the optimized reaction conditions in hand,
we studied the substrate scope of the Cu7Pt3‐rGO

GANJEHYAN ET AL.
5 of 8
catalyzed THs over a variety of selected olefins (7 exam-
ples) under optimized conditions and the results were
depicted in Table 2. As clearly be concluded by Table 2
that all the catalytic THs carried out smoothly and the
related reduction products yielded quantitatively within
the reaction times of 2–4 hr (Table 2, entries 1–8).
Moreover, the successful reduction of 4‐cholorostyrene
to 4‐chloroethylbenzene by the presented TH protocol
confirms the selectivity of this method because ‐Cl
TABLE 1 Optimization of the reaction conditions for the Cu7Pt3‐
rGO catalysed THs using benzonorbornadiene as a model
compounda
Entry
Solvent
H2O
t (min)
30
Conversionb
Selectivityb
≥99
1
2
50
H2O
60
85
≥99
3
H2O
80
87
≥99
4
H2O
120
120
60
≥99
‐
≥99
5
H2O
‐
6
MeOH
MeOH
H2O
82c
≥99c
≥99d
83e
95f
≥99
7
120
120
120
120
≥99
8
≥99
9
H2O
≥99
10
H2O
≥99
aGeneral Reaction conditions: 0.35 mmol benzonorbornadiene, 1.05 mmol
NH3BH3, 4.0 mg CuPt‐rGO, 3 mL of water and room temperature.
b1H‐NMR yields.
c3 mL MeOH was used.
dPt‐rGO catalyst
e0.35 mmoL NH3BH3 was used.
f2.0 mg CuPt‐rGO was used.
FIGURE 1 (a) a representative TEM image and (b) XRD pattern
of as‐prepared Cu7Pt3 NPs
FIGURE 2 Two representative TEM images of Cu7Pt3‐rGO nanocatalysts taken at different magnifications

6 of 8
GANJEHYAN ET AL.
TABLE 2 Substrate scope for the Cu7Pt3‐rGO catalysed THs of
TABLE 3 Substrate scope for the Cu7Pt3‐rGO catalysed THs of
olefinsa
nitroarenesa
Time Conversion
[h]
Entry
1
Substrate
Conversion (%)b
Selectivity
Entry Substrate
1
(%)b
Selectivity
>99d
>99
2
>99
>99
2
4
>99
>99
2
3
>99c
88d
>99
>99
3
4
4
4
>99
>99
>99
>99
>99d
>99
5
4
>99
>99
4
6
7
4
2
>99
>99
80
5
6
>99d
>99c
>99
>99
>99
aReaction conditions: 0.35 mmol olefin, 1.05 mmol NH3BH3, 4.0 mg
Cu7Pt3‐rGO nanocatalyst, 3.0 mL of water and room temperature.
b1H‐NMR yields.
7
>99c
>99
substituents were remained intact and only styrene group
was hydrogenated to ethyl group (Table 2, entry 2).
Styrene and substituents (Entry 2–5, Table 2) could also
be generally reduced to the corresponding alkanes excel-
lent conversions and selectivity (>99%).
aReaction conditions: 0.35 mmol of nitroarene, 4.0 mg Cu7Pt3‐rGO
nanocatalyst, 3 mL of water, 30 mins and room temperature.
bH NMR yields.
After having the optimum reaction conditions for the
Cu7Pt3‐rGO catalyzed THs of olefins in hand, the further
efforts were made to extend the scope of this method for
the reduction of other unsaturated compounds. When
nitroarenes are submitted to transfer hydrogenation, the
corresponding aniline derivatives can be obtained. The
reactions resulted in excellent yields, with quantitative
conversions in just 30 min, as tabulated in Table 3. Both
steric hindrance (Table 3, entry 2) and orientation effect
(Table 3, entries 5 and 6) of the substituted groups did
not affect the hydrogenation rate of corresponding com-
pounds. Moreover, no dehalogenation was observed like
as we observed for the reduction of olefins (Table 3,
entry 3). Nitroarenes bearing electron‐donating and
electron‐withdrawing substituents were also transformed
into the related reduction products with the excellent
yields (Table 3, entries 4 and 8). In order to obtain the
best conversion and selectivity, different amounts of
NH3BH3 were used. Nitroarenes derivatives such as
entries 2, 6 and 7 needed 1.05 mmol NH3BH3 and
1.4 mmol AB for the other conversions.
c1.05 mmol AB was used.
d1.4 mmol AB was used.
(aldehydes and ketones) under the same optimized
reaction conditions used for the reduction of olefins and
nitroarenes (Table 4). Because of the higher reactivity of
benzaldehydes in TH reactions, the reactions of alde-
hydes were yielded into corresponding products in less
than 30 mins compared to ketone analogues (Table 4,
Entries 1–4). Although the reaction time is increased to
30 mins, acetophenone analogues needs 4 equivalents of
AB in order to get quantitative yield, most probably
due to the both its less solubility in water and less
reactivity (Table 4, Entries 5–7). Considering 3,4‐
dimethoxyacetophenone as a strong electron donating
substrate for the THs, the corresponding hydrogenated
product yielded as a moderate yield compared to the
other derivatives (Table 4, Entry 7). As a result, in the last
part of our study, alcohols were synthesized just in water
with effective and reusable catalyst by the help of AB as a
hydrogen donor.
The last part of the presented work was devoted to the
Cu7Pt3‐rGO catalyzed THs of carbonyl compounds

GANJEHYAN ET AL.
7 of 8
TABLE 4 Substrate scope for the Cu7Pt3‐rGO catalysed THs of
After presenting applicability of the Cu7Pt3‐rGO
nanocatalysts catalyzed THs for the reduction of a variety
of unsaturated organic compounds, we then studied their
reusability, which is another important criterium for
showing the practicability of a heterogeneous catalyst.
Figure 3 shows the results of a five‐run reusability test
of Cu7Pt3‐rGO nanocatalyst in the transfer hydrogenation
of nitrobenzene as a model compound. As can be easily
concluded by the reusability test, Cu7Pt3‐rGO
nanocatalyst provided 99% yield after five consecutive
runs in the transfer hydrogenation of nitrobenzene,
indicating their high durability.
carbonyl compoundsa
Time
Conversion
Entry Substrate
1
[min] (%)b
Selectivity
30
30
30
>99c
>99c
>99c
>99
2
3
>99
>99
4
30
>99c
>99
4 | CONCLUSIONS
5
6
60
60
>99d
>99d
>99
>99
Developing new strategies for the conversion of unsatu-
rated organic compounds into their reduced forms
continues an important task with the increasing interest
of researchers working in synthetic organic chemistry
all over the world because of their wide‐range of applica-
tions in industry. In this respect, we have reported herein
that Cu7Pt3‐rGO nanocomposites can be effectively and
selectively applied as catalyst for the transfer hydrogena-
tion of olefins, carbonyl compounds and nitroarenes in
sole water at room temperature. The methodology
tolerates a variety of functional groups and is a green
and easy to perform alternative to classic transfer hydro-
genation methods. Major advantages of the described
method over the conventional hydrogenation might be
as follows: (i) Cu7Pt3‐rGO is an atom economical and
cost‐effective catalyst, (ii) the transfer hydrogenation
process can be performed in a commercially available
pressure tube using water as sole solvent at room temper-
ature with no need of pressurized hydrogen tank and
expensive apparatus, (iii) the Cu7Pt3‐rGO is reusable
catalysts without losing their activity at least for five con-
secutive runs (iv) the catalytic transfer hydrogenation
method is halogen selective that allows the synthesis of
halogen‐substituted reduction products. Therefore, we
believe that the current study will open a new avenue
for the application of binary MPt alloy NPs not only for
THs but also for other organic reactions. Our studies on
this direction is going on with other MPt alloy NPs (M:
Co, Ni) supported on rGO or other 2D materials.
7
60
85d
>99
aReaction conditions: 0.35 mmol aldehyde or ketone, 4.0 mg of Cu7Pt3‐
rGO, 3.0 mL of water, room temperature.
b1H‐NMR yields.
c1.05 mmol AB was used.
d1.4 mmol AB was used.
ACKNOWLEDGEMENTS
Ö. Metin thanks to Turkish Academy of Sciences (TÜBA)
for the financial support.
FIGURE 3 The reusability test of Cu7Pt3‐rGO nanocatalyst in the
presented THs by using nitrobenzene as a model substrate

8 of 8
GANJEHYAN ET AL.
[17] H. Göksu, S. F. Ho, Ö. Metin, K. Korkmaz, A. M. Garcia, M. S.
ORCID
G, S. Sun, ACS Catal. 2014, 4, 1777.
Önder Metin https://orcid.org/0000-0003-1622-4992
[18] Y. Çetinkaya, Ö. Metin, M. Balcı, RSC Adv. 2016, 6, 28538.
[19] B. Nişancı, M. Turgut, M. Sevim, Ö. Metin, Chem. Select 2017,
2, 6344.
REFERENCES
[20] P. Eghbali, B. Nişancı, Ö. Metin, Pure Appl. Sci. 2018, 90, 327.
[21] T. Karaca, M. Sevim, Ö. Metin, ChemCatChem 2017, 9, 4185.
[1] P. G. Andersson, I. J. Munslow (Eds), Modern Reduction
Methods, Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
2008.
[22] Ö. Metin, E. Kayhan, S. Özkar, J. Schneider, Int. J. Hyd. Energy
2012, 37, 8161.
[2] A. Kulkarni, W. Zhou, B. Török, Org. Lett. 2011, 13, 5127.
[23] T. S. Carter, L. Guiet, D. J. Frank, J. West, S. P. Thomas, Adv.
Synth.Catal. 2013, 355, 880.
[3] L. Cerveny (Ed), Catalytic Hydrogenation, Amsterdam, Elsevier
1986.
[24] M. Flinker, H. Yin, R. W. Juhl, E. Z. Eikeland, J. Overgaard, D.
U. Nielsen, T. Skrydstrup, Angew. Chem., Int. Ed. 2017, 56,
15910.
[4] C. Schäfer, C. J. Ellstrom, H. Cho, B. Török, Green Chem. 2017,
19, 1230.
[5] D. Wang, D. Astruc, G. Brieger, T. J. Nestrick, Chem. Rev. 1974,
74, 567.
[25] S. R. Tamang, M. Findlater, J. Org. Chem. 2017, 82, 12857.
[26] B. S. Kumar, A. J. Amali, K. Pitchumani, J. Mol. Catal. 2018,
448, 153.
[6] F. Alonso, P. Riente, J. A. Sirvent, M. Yus, Appl. Catal., a: Gen
2010, 378, 42.
[27] P. A. Pourjavadi, N. Keshavarzi, F. M. Moghaddam, S. H.
[7] F. Li, B. Frett, H. Y. Li, Synlett 2014, 25, 1403.
Hosseini, ChemistrySelect 2018, 3, 2716.
[8] A. Azua, J. A. Mata, E. Peris, F. Lamaty, J. Martinez, E.
[28] M. Kashihara, M. R. Yadav, Y. Nakao, Org. Lett. 2018, 20, 1655.
Colacino, Organometallics 2012, 31, 3911.
[29] M. U. Hung, S. T. Yang, M. Ramanathan, S. T. Liu, 2018, 32,
[9] H. Kahri, M. Sevim, Ö. Metin, Nano Res. 2017, 10, 1627.
e3976.
[10] Ö. Metin, A. Mendoza‐Garcia, D. Dalmızrak, M. S. Gültekin, S.
Sun, Catal. Sci. Technol. 2016, 6, 6137.
[11] B. Peng, J. Chen, Energy Environ. Sci. 2008, 1, 479.
How to cite this article: Ganjehyan K, Nişancı
B, Sevim M, Daştan A, Metin Ö. Monodisperse
CuPt alloy nanoparticles assembled on reduced
graphene oxide as catalysts in the transfer
hydrogenation of various functional organic
groups. Appl Organometal Chem. 2019;e4863.
https://doi.org/10.1002/aoc.4863
[12] D. Sun, V. Mazumder, Ö. Metin, S. Sun, ACS Catal. 2012, 2, 1290.
[13] N. S. Çiftçi, Ö. Metin, Int. J. Hyd. Energy 2014, 39, 18863.
[14] Ö. Metin, H. Can, K. Şendil, M. S. Gültekin, J. Colloid Interface
Sci. 2017, 498, 378.
[15] H.‐U. Blaser, H.‐P. Jalett, M. Müller, M. Studer, Catal. Today
1997, 37, 441.
[16] H. Göksu, H. Can, K. Şendil, M. S. Gültekin, Ö. Metin, Appl.
Catal. A. 2014, 488, 176.