Abbaspour 2018

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General Research
Investigation of possible formation of Au@M (M= Cu, Ir,
Pt, and Rh) core-shell nanoclusters in a condensation-
coalescence process using molecular dynamics simulations
Mohsen Abbaspour, Hamed Akbarzadeh, Sirous Salemi, and Samira Lotfi
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b03724 • Publication Date (Web): 08 Oct 2018
Downloaded from http://pubs.acs.org on October 8, 2018
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Page 1 of 26 Industrial & Engineering Chemistry Research
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4 Investigation of possible formation of Au@M (M= Cu, Ir, Pt, and
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6 Rh) core-shell nanoclusters in a condensation-coalescence process
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8 using molecular dynamics simulations
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13 Mohsen Abbaspour,* Hamed Akbarzadeh, Sirous Salemi, Samira Lotfi
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15 Department of Chemistry, Hakim Sabzevari University, 96179- 76487Sabzevar, Iran
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21 Abstract
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In this work, the possible formation of Au@Pt, Au@Cu, Au@Rh, and Au@Ir clusters during the
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25 vapor condensation-coalescence process has been investigated by inserting icosahedral gold
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27 nanocluster into copper, platinum, rhodium, and iridium vapor environments. We have studied
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29 some properties of the created nanoclusters at different simulation times. Our results showed that
30 the stability of the formed core-shell structures obeys the following order: Pure Au >Au@Cu >
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32 Au@Rh> Au@Ir which means that the positioning of rhodium, iridium, and copper on the gold
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34 cluster is unfavorable. The Au@Pt cluster was also the most stable cluster. The results also
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showed that the Au@Pt and Au@Rh are not pure core-shell structures but they are (Au/Pt
37 mixed)@Pt and (Au/Rh mixed)@Rh structures. The structural investigations also indicated that
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39 the initial icosahedral morphology of the gold cluster was disappeared whereas the formed core-
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41 shell nanoclusters had fcc-like and hcp-like morphologies. The thermal investigations showed
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that the nanoclusters become more spherical by increasing the temperature. The gold atoms also
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44 migrate to the cluster surface but the metal surface atoms diffuse to the inner cluster layers by
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46 increasing the temperature.
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56 *Correspondence addressed: Email: m.abbaspour@hsu.ac.ir
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60 ACS Paragon Plus Environment
Industrial & Engineering Chemistry Research Page 2 of 26
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1. Introduction
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6 Core-shell bimetallic clusters, with the different metals in the core and the shell, have recently
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8 received a significant amount of interest due to their unique chemical and physical properties
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10 which are different from those of the monometallic components.1-4 According to the benefits of
11 the core-shell nanoclusters, core-shell Au-based nanoclusters can achieve high stability and
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13 activity by controlling their electronic, composition, shape, and geometric properties.5 Gold is
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15 a good candidate to stabilize the catalysts in the fuel cell systems.6 It has been shown that the
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gold nanocluster can stabilize platinum to decrease dissolution in the acidic environment.7,8
18 Moreover, the positioning of gold atoms in clusters cores can increase Raman scattering because
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20 of its surface plasmon resonance in the surface enhanced Raman scattering (SERS) which is
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22 used for electrochemical reaction observations and bio-applications.9-12 The Au-based core-
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shell nanoclusters (especially, by using Pt as the catalytic) are used for oxygen reduction
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25 reactions.5 Au-Rh core-shell nanoclusters are used as catalyst for hydrogenation which is more
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27 efficient and affordable than pure Rh. In addition to this, bimetallic nanoclusters of Au-Cu have
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29 also many applications but are mainly used in medical sensors and biomedicine.13
30 One of the commonly used techniques of nanocluster synthesis is to evaporate metal atoms and
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32 condensate them into a vapor atmosphere. Theoretically, we can synthesize nanoparticles with
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34 special chemical composition, size, and structure. The factors of the experimental vapor
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36
condensation process can be also controlled.14-16 However, the nanoclusters formed in the gas
37 condensation are multi-structured and non-spherical and their shapes are also discontinuous.
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39 Therefore, production of clusters with specific structure and shape is an important stage toward
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41 the more versatile application of the nanoclusters. But, the generation of the clusters with
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specific morphology is a formidable technical task.16
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45 Molecular dynamics (MD) simulation is a real solution to study the structure, dynamics, shape,
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47 and growing nanoparticle and thus, it can specify the important atomistic processes occur in this
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process.17 Several simulations have been applied to the process of vapor condensation procedure
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50 consisting of production of monometallic clusters and nanoalloys.18-22 However, a complete
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52 study of nucleation process from the vapor phase is not currently available.23 Many of these
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54 simulation studies have also reported that they could not generate core-shell structures.20-22 There
55 is no or very rarely simulation or experimental gas condensation work which claims that the
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58 2
59
1
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3 core-shell nanoparticles have been obtained during the condensation process. Just recently, we
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5 reported the formation of Rh@Au, Ir@Au, Pt@Au, and Cu@Au core-shell nanoclusters into the
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7 gas-phase condensation process using MD simulations.23 In this paper, the possible formation of
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9
Au@Pt, Au@Cu, Au@Rh, and Au@Ir clusters during the vapor condensation process has been
10 investigated by inserting icosahedral gold nanocluster into the metal vapor environments. In fact,
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12 the positioning of gold atoms as the cluster core (which has smaller surface energy than the other
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14 metals) would be very interesting. We have studied structure and some thermodynamic
15
properties of the nanoclusters created at different simulation times.
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21 2. Simulation Details
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23
In these simulations, the cubic cells with dimensions of 100×100×100 Å3 were constructed with a
24 homogeneous gas including 2000 atoms of vapor Cu, Rh, Ir, or Pt. The initial density of metal
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26 vapor was 0.00198 (Å-3). The gold icosahedral cluster with 309 atoms set up in the center of the
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28 cells at 300 K. We have selected the icosahedra structure as the initial geometries of the gold
29
nanoclusters because the icosahedral morphologies are constructed based on to the magic numbers
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31 which are more stable than other morphologies for different metal nanoclusters24,25 . Some studies
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33 have shown that the fcc and decahedral structures of gold clusters are more stable than other
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35 structures.26,27 We have shown in the next sections (in accordance with our previous study23 ) that
36 the initial morphology of the gold cluster positioned into the different metal vapors is vanished
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38 after some initial simulation times and therefore, it has negligible effect on the obtained simulation
39
40 results.
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42 The snapshots of the gold nanocluster into the Cu, Rh, Ir, and Pt vapor atoms have been presented
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44 at 2.25, 2.5, 3, 4, and 20 ns in Figure1 and in Figures S1 to S3 in the supporting information.
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46 Unlike the conventional gas-phase condensation process, we have not used an inert gas in the
47
48
condensation process. Our previous investigations showed that the final obtained results of the
49 core@shell clusters with and without an inert-gas are almost similar.23
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58 3
59
1
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17 After 2.25 ns 2.5 ns
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33 3 ns 4 ns
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6 ns 20 ns
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51 Figure 1. Snapshots of the Au nanocluster into the Ir vapor at various simulation times.
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58 4
59
1
2
3 As Figures1, S1, S2, and S3 show, some of the vapor atoms of Rh, Ir, Cu, and Pt encounter to the
4
5 gold nanocluster by increasing the time which results in the enlargement of the gold nanocluster.
6
7 Some of the vapor atoms also strike and join together which results in the condensation procedure
8
9
and the production of the pure metal clusters. Thus, the pressure of the metal vapor reduces by the
10 simulation time. By increasing the time, the Au-metal core-shell nanocluster grows. The number
11
12 of formed pure gold clusters also reduces and their size increases by the time. These observations
13
14 are in good agreement with the experimental and theoretical works on the condensation of the
15
metal vapors.28 In this study, we will concentrate only on the Au-metal core-shell clusters.
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18 All of the MD simulations have been carried out in the NVT ensemble by DL_POLY code29 .
19
20 Also, several previous works have used the NVT ensemble in the gas condensation procedure
21
using MD simulations.30-33 We have recently used the NVT ensemble in the simulation of gas-
22
23 phase condensation procedure consisting of Pt, Rh, Ir, and Cu clusters into Au vapor.23
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25 We have also used the periodic boundary conditions at three dimensions. To solve the equations
26
27 of motions, the Verlet-Leapfrog algorithm were also used. The cutoff distance was 12 Å with 1fs
28 time-step. The simulation time for every condensation process was 20 ns. Many previous works
29
30 have also used the nanosecond scale 28,34 and the similar density ranges35 for their simulations of
31
32 the condensation process. The obtained results are not based on single trajectories and several
33
34
simulations were approved our results for the systems.
35
36 For the Au-Au, Au-M, and M-M interactions, the quantum Sutton-Chen (QSC) potentials have
37
38 been used36,37 . The QSC model has been successfully and widely applied in molecular dynamics
39
40
simulations of nanoclusters in good agreement with the experiments.38,39 The QSC model is:
41
42 1 n

a  1
43 U tot        c  i 2  (1)
44  2 i  j j  rij 
 i 
45  
46
47 The first term is the pair repulsion interaction model and the second term shows the metallic
48
49 bonding energy corresponding to the local density, ρi :
50
51 m
52 a 
53  i    

(2)
j  i  rij 
54
55
56
57
58 5
59
1
2
3 In Eq. (1), c is a dimensionless factor, rij is the distance between atoms i and j, and ε and a are
4
5 parameters related to energy and length, respectively. To compute the interaction between Au and
6
7 M, we have used the geometric mean for the energy parameter ε and the arithmetic mean for the
8
9
remaining parameters.
10
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12
13 3. Results and discussion
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15 3.1 Analysis of Thermodynamic parameters
16
17
Total energy (per atom) for Au@Ir, Au@Pt, Au@Cu, Au@Rh, and pure gold clusters formed in
18 the vapor condensation procedure have been given at 3, 4, 6, and 20 ns in Figure 2. For
19
20 comparison, the gold clusters produced in the pure gold vapor (without the inserted external
21
22 nanocluster) have been also given. The solid symbols in this figure indicate the biggest
23
core@shell nanoclusters in each system. According to Figure 2, the order of the absolute values
24
25 of total energy of the produced nanoclusters is as: EAu@Ir> EAu@Pt> EAu@Rh> EAu >EAu@Cu . This
26
27 trend is the same as the order of the cohesive energy values of the bulk metals40 : EIrcoh> EPtcoh >
28
29 ERhcoh > EAucoh > ECucoh. It is also shown in Figure 2 that the core-shell nanocluster in all systems
30 (with the exception of Au@Cu system) has smaller value of the total energy than the other pure
31
32 clusters. This is because of the fact that the cohesive energy of gold is smaller than bulk Ir, Pt,
33
34 and Rh metals but it is greater than Cu.
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58 6
59
1
2
3
-250
4 Au@Cu
-250
t= 4ns
5 -300
Au@Pt
Au@Rh -300
6 Pure Au
-350 Au@Ir
7 -350
8 -400
t=3ns -400
E (kJ/mol)
E (kJ/mol)
9
-450 -450
10
11 -500 -500
12
-550 -550
13
14 -600 -600
15
-650 -650
16 0 200 400 600 800 1000 1200 1400 1600 0 500 1000 1500 2000 2500
17 N N
18
19
20 -300 -300
21
22 -350
t= 6ns
-350
t= 20ns
23
24 -400 -400
E (kJ/mol)
E (kJ/mol)
25
26 -450 -450
27
28 -500 -500
29
30 -550 -550
31
32 -600 -600
1950 2000 2050 2100 2150 2200 2250 2300 2350
800 1000 1200 1400 1600 1800 2000 2200 2400
33 N N
34
35
36 Figure 2. Total energy for the different core-shell clusters created in the vapor condensation at
37
38 various times.
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40
41
42
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45 To study the relative stability of the formed nanoclusters in the vapor condensation, the Δ value
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47 was computed from the equation41,42 :
48
49
50 Etot  N Au Au
Coh
 N M  MCoh (3)

51 N surf
52
53
54
55
56
57
58 7
59
1
2
3
where Etot is the total energy of the clusters obtained by the MD simulations. NAu and  Au are
Coh
4
5
the number and the bulk cohesive energy of Au atoms and NM and  M are the number and the
Coh
6
7
8 cohesive energy of the M atoms (M= Cu, Pt, Ir, and Rh). Nsurf is the number of the cluster surface
9
10 atoms. As the nanocluster is more stable its Δ value becomes smaller42. The Δ value was
11
12
calculated for the created clusters at the various times in Figure 3. According to Figure 3, the Δ
13 for the pure metal nanoclusters obeys the order: ΔAu< ΔCu< ΔPt< ΔRh< ΔIr. The reason of this
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15 order of stability of the pure metal clusters can be interpreted using the surface energy. If we
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17 compare the experimental surface energy of the corresponding bulk metals43 : ESIr > ESRh > ESPt >
18 ESCu > ESCu, we can found that the smaller the surface energy the more stable the cluster. If we
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20 observe the stability of the core-shell nanoclusters at 3 ns, we can found that almost the same
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22 order of the stability of pure nanoclusters has been also existed for the core-shell clusters (with
23
24
the exception of the Au@Pt cluster): ΔAu< ΔAu@Cu< ΔAu@Rh< ΔAu@Ir. This means that the
25 existence of the Rh, Cu, and Ir metals on the Au cluster is unfavorable. It is also shown in each
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27 system that the ∆ parameter of the formed core-shell cluster is smaller (and thus is more stable)
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29 than the pure metal clusters. This result can be also interpreted using the surface energy. As we
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have presented the number of the produced clusters, the different number of atoms in cluster, and
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32 their percent of different surface atoms in Table 1 and Tables S1 to S3, the produced core-shell
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34 clusters are not really pure core-shell clusters and some of the gold atoms have been appeared on
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36 the clusters surfaces. Due to the smaller surface energy of Au than other metals, the resulted
37 core-shell clusters have smaller surface energy than the pure metal clusters and therefore, they
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39 are more stable. There is also another important point about the stability of Au@Pt cluster which
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41 is the most stable cluster than other clusters.
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58 8
59
1
2
3
4 300
300
5 Au@Cu
Au@Pt
6 250 Au@Rh t= 4ns
250
7 Pure Au
Au@Ir
8 200
9 t= 3ns
200
 (kJ/mol)
 (kJ/mol)
10 150
11 150
100
12
13 100
50
14
15 0 50
16
17 0
18 0 200 400 600 800 1000 1200 1400 1600
0 500 1000 1500 2000 2500
19 N N
20
21
22
300 300
23
24 t= 6ns t= 20 ns
25 250 250
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27 200 200
 (kJ/mol)
28
 (kJ/mol)
29 150 150
30
31 100 100
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33 50 50
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35
0 0
36 800 1000 1200 1400 1600 1800 2000 2200 2400 1950 2000 2050 2100 2150 2200 2250 2300 2350
37 N N
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40 Figure 3. The Δ value for the various created clusters at the different simulation times.
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58 9
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1
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3 Table 1. The number of total atoms, number of each kind of atom, their molar fractions, number
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5 of the surface atoms, and percent of the surface atoms for the Au@Cu nanoclusters (Copper
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7 atoms are in red and gold atoms are in yellow).
8
9 time Snapshot Ntot NCu NAu xCu xAu Nsur Nsur %Nsur %Nsur
10 (ns) Cu Au Cu Au
11
12
13
14 3ns 491 185 306 0.38 0.62 96 119 44.6512 55.3488
15
16
17
18
19
20 4ns 1969 1661 308 0.84 0.16 462 117 79.7927 20.2073
21
22
23
24
25
26
6ns 2309 2000 309 0.87 0.13 566 102 84.7305 15.2695
27
28
29
30
31
32
33
34 2309 2000 309 0.87 0.13 542 98 84.6875 15.3125
35 20ns
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37
38
39
40
41
42
43
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45 We have also computed the number of the clusters and their atoms in the different systems at
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47 different times and given in Figure 4. As Figure 4a illustrates, the number of the produced
48 nanoclusters in Au@Ir and Au@Pt systems is more than Au@Cu and Au@Rh systems. Almost,
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50 the reverse trend can be observed in Figure 4b for the number of the atoms in the nanoclusters in
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52 the different systems because when the more number of clusters are formed then, their number of
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54 atoms become smaller (the total number of atoms in the different systems is equal). The number
55 of atoms in the formed core@shell clusters of Au@Ir and Au@Pt is also less than the Au@Cu
56
57
58 10
59
1
2
3 and Au@Rh clusters (see for example compare the total number of atoms at 4 ns for the different
4
5 clusters in Tables 1, S1, S2, and S3). In Au@Ir system, the vapor Ir atoms have more tendency to
6
7 align together (rather than join to the Au cluster) to form the pure Ir nanoclusters. This is because
8
9
of the greater cohesive energy of Ir atoms than Au (and also other atoms) and therefore, the
10 number of the Ir nanoclusters is more than other systems in Figure 4a. It is also shown that by
11
12 increasing the time, the number of the produced nanoclusters decreases due to the coalescence
13
14 between the clusters and also their number of atoms increases. The rate of decreasing of the
15
number of Pt and Ir clusters become slower than the Cu and Rh nanoclusters by elevating the
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17 simulation time. This result is because of the slower coalescence process in Au@Ir and Au@Pt
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19 systems than Au@Cu and Au@Rh systems which is due to the greater interactions and heavier
20
21 masses of Ir and Pt than Cu and Rh atoms.
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58 11
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1
2
3
4
5 10
6 Au@Cu
7 a)
Au@Ir
8 Au@Pt
8 Au@Rh
9 No. of formed clusters
10
11
12 6
13
14
15 4
16
17
18
2
19
20
21
22 0
23 2 4 6 8 10 12 14 16 18 20 22
24 t (ns)
25
26
27
28 2500
29 b)
30
31 2000
32
No. of cluster atoms
33
34
1500
35
36
37
38 1000
39
40
41 500
42
43
44
0
45 2 4 6 8 10 12 14 16 18 20 22
46
47 t (ns)
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49 Figure 4. The number of the formed nanoclusters and their atoms in the different systems at
50 different simulation times.
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53
54
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58 12
59
1
2
3 3.2 Structural analysis
4
5 To investigate the structural characteristic of the formed clusters, the radial distribution function
6
7 (RDF or g(r)) for the nanoclusters has been calculated using the following formula44 :
8
9
  r  r  r 
10 1
g (r )  (4)
2
i j
11 i j i
12
13
14 In Eq. (4), the angle brackets indicate a configurational average. The Au-Au, M-M, and Au-M
15
16
RDFs for the last nanoclusters (N= 2309 atoms) produced have been given after the time of 20 ns
17 at 300 K in Figure 5. According to this figure, the Ir-Ir RDFs (in the g(r)MM plot) are higher than
18
19 other RDF peaks which is because of the stronger Ir-Ir interactions than other interactions.
20
21 Because the various atoms used in our simulations have the different lattice constants (sizes)
22 their positions of the RDF peaks are different43 : LCu (3.61 Å) < LRh (3.80 Å) <LIr (3.84 Å) <LPt
23
24 (3.92 Å) <LAu (4.08 Å).
25
26
27 In order to better understand the RDF results, we have presented the cross sections of the
28
different formed clusters after 20 ns in Figure 6. The formed clusters are not the pure core-shell
29
30 structures and some metal atoms have migrated to the gold clusters core and also some gold
31
32 atoms migrated from the core to the shell. These migrations have been more occurred for Au@Pt
33
34 and Au@Rh clusters and they less occurred for Au@Cu and Au@Ir clusters. These results are
35 due to some reasons. First, the surface energy of gold is less than other metals and therefore, the
36
37 gold atoms tend to migrate to the clusters shell and the other metals tend to migrate to the
38
39 clusters core. The bigger Au atom also tend to position to the cluster surface than other smaller
40
metal atoms. The less difference between the surface energy of two metals (Au and M), the less
41
42 migrations to the core and shell. Therefore, the Au@Cu system has the least migrations and also
43
44 it is more similar to a core-shell structure. Second, the cohesive energy of the metals. The Au@Ir
45
46 cluster also has less displacements because Ir atoms have strongest cohesive energy. Third, the
47 match or mismatch of the metal atoms in the cluster core. As Figure 6 shows, the Au@Pt is not a
48
49 core-shell structure but it is a (Au-Pt mixed)@Pt structure. The reason of the presence of more Pt
50
51 atoms into the cluster core can be due to the more match between the Au and Pt atoms than other
52
53
atoms. According to the order of size of the different atoms, this result is due to the more
54 similarity between the sizes of gold and platinum atoms than other systems. The reason of the
55
56 (Au-Rh mixed)@Rh structure shares between these three reasons.
57
58 13
59
1
2
3
4 300 300
5 250
6 250 200
g(r)M_M
7 150
8 200
100
9 50
g(r)M_M
10 150
0
2.0 2.2 2.4 2.6 2.8 3.0 3.2
11 r(A)
12 100 Au@Cu
Au@Ir
13 Au@Pt
14 50
Au@Rh
15
16 0
0 2 4 6 8 10 12 14 16
17
r(A)
18
19
20
21 200 200
22 180
180
23
160
140
g(r)Au_M
160
24
120
100
25 140 80
60
26 120 40
g(r)Au_M
20
27 100
0
2.2 2.4 2.6 2.8 3.0 3.2
28 80 r(A)
29
60
30
40
31
32 20
33 0
34 0 2 4 6 8 10 12 14 16
r(A)
35
36
37
38 800 800
39
40 600
g(r)Au_Au
41 600 400
42
43 200
g(r)Au_Au
44 400 0
45 2.2 2.4 2.6
r(A)
2.8 3.0 3.2
46
47 200
48
49
50 0
51 0 2 4 6 8 10 12 14 16
52 r(A)
53
54
Figure 5. The Au-M, M-M,and Au-Au RDFs for the core@shell nanoclusters created after 20
55
56 ns.
57
58 14
59
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Au@Cu Au@Ir Au@Pt Au@Rh
21
22
23
24
25 Figure 6. The snapshots of the cross sections of the various nanoclusters created after 20 ns.
26
27
28
29
30
31
32
33 The presence of the gold atoms into the platinum (and Rh) atoms strengthens the Au-Pt and Au-
34
Rh interactions whereas decreases the Au-Au, Pt-Pt, and Rh-Rh interactions more than other
35
36 nanoclusters. These results can be understood by observing the increase of the Au-M RDF and
37
38 the decrease of the Au-Au and M-M RDFs in the Au@Pt and Au@Rh clusters more than other
39
40 clusters in Figure 5. The opposite results were observed for the Au@Cu and Au@Ir clusters
41 because the cores of these nanocluster have less number of the gold atoms. Thus, the Cu-Au and
42
43 Ir-Au RDFs are smaller than other RDFs but their Au-Au RDFs are greater than other RDFs.
44
45
46 In order to investigate the structural changes of the initial icosahedral gold nanostructure inserted
47 into the metals vapors, the percentage of hcp, ico, bcc, and fcc atoms (ordered atoms) and other
48
49 atoms (disordered atoms) in the core@shell nanoclusters at various simulation times have been
50
51 computed using OVITO software45 and given in Table 2 and Tables S4 to S6. According to these
52
53
tables, the initial icosahedral morphology of the clusters was disappeared whereas the fcc and hcp
54 atoms are more than other ordered atoms and thus, the core@shell nanoclusters have fcc-like and
55
56
57
58 15
59
1
2
3 hcp-like morphologies. As these tables show, the atoms on the nanoclusters surfaces show
4
5 disordered structures because of their weaker cohesive energies.
6
7
8
9
10
11
12
13
14
15 Table 2. The Percentage of ordered and disordered atoms in Au@Cu clusters (fcc is in green,
16
17 hcp is in red, bcc is in blue, ico is in yellow, and other is in gray).
18
19
20
time Ntot Snapshot %fcc %hcp %bcc %ico %other
21 (ns)
22
23
24 3ns 491 13.0 24.4 4.9 0.4 57.2
25
26
27
28
29
30
31 4ns 1969 22.8 27.1 3.3 0.2 46.7
32
33
34
35
36
37 6ns 2309 25.1 34.1 3.3 0.2 37.3
38
39
40
41
42
43 20ns 2309 25.4 32.3 1.8 0.1 40.3
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 16
59
1
2
3 3.3 Thermal evolution
4
5
6 Effects of subsequent heating process (after the gas-condensation process) on the structure and
7
8 shape of the produced worm-like nanoclusters were recently investigated by Chepkasev et al.20
9 on the copper nanoclusters. They observed that the heating process leads to significant ordering
10
11 and also the spherical shape. In this work, to study the thermal evolution of the formed
12
13 nanoclusters in the condensation process, for example, the final formed Au@Ir nanoalloy has
14
15
been heated from 300 to 2600 K. The total energy of the Au@Ir nanoalloy has been given in
16 Figure 7. A sudden jump has been occurred between 2200 and 2300 K which corresponds to the
17
18 cluster melting point and is in good accordance with the experimental melting point of Ir
19
20 nanoparticles (2680 K46 ).
21
22
23 The percentage of the ordered and disordered atoms in the Au@Ir nanoalloy at various
24
25 temperatures have been also given in Table S7. As this table shows, the amount of disordered
26
27 atoms sharply increases from 2200 to 2300 K whereas the percent of the ordered atoms decreases.
28
29 We have also shown the amount of the surface atoms on the Au@Ir nanoalloy at various
30
31 temperatures in Table S8 in the supporting information. The percent of the Au surface atoms
32
33 increases whereas the amount of the Ir surface atoms decreases by elevating the temperature. This
34 is due to the diffusion of the Au atoms from the cluster core to the surface and also the diffusion
35
36 of the Ir atoms from the cluster surface toward the inner shells of the cluster because the surface
37
38 energy of gold is smaller than iridium. These results are in well accordance with the experimental
39
40
and literature results.47
41
42 It is also shown in Figures S2 to S6 that the smaller nanoclusters at the initial stage of the
43
44 condensation are more spherical than the bigger clusters formed at larger times. This decrease of
45
46
the nanocluster sphericity by the time is because of the coalescence of the smaller clusters to
47 form irregular and worm-like nanoclusters. The production of irregular nanoclusters are in good
48
49 accordance with the experimental values28,48 of production of metal clusters in the gas-phase
50
51 condensation process. It is also observed in Figure 7 and Table S8 that the nanocluster becomes
52
more spherical by increasing the temperature which is due to the more movement and diffusion
53
54 of the atoms to achieve the more stable structure (a sphere shape is the more energy-efficient
55
56 structure for the cluster atoms).
57
58 17
59
1
2
3
4
5
6
7
8
9 -500
10
11
12
13
14 -520
15
16
17
18
E (kJ/mol)
19 -540
20
21
22
23
24 -560
25
26
27
28
-580
29
30
31
32 0 500 1000 1500 2000 2500 3000
33
34 T (K)
35
36
37 Figure 7. The total energy of the Au@Ir nanoalloy at the different temperatures.
38
39
40
41
42
43
44 In this research, we do not want to study the initial nanocluster structure effect on the simulation
45
46 results. However, we have given the simulation results for the initial icosahedral, fcc, and
47
48 decahedral gold nanoclusters into the Rh vapor. The results have been given in Table S9. As can be
49
50
observed, the kind of initial structure of the cluster has small effect on the obtained results and the
51 morphology of the initial nanocluster is disappeared in the final simulated nanocluster of Au@Rh
52
53 after 4 ns. The number of the surface atoms is almost similar at the different structures. All of the
54
55 resulted core-shell nanoclusters have also fcc-like and hcp-like morphologies.
56
57
58 18
59
1
2
3
4
5
6 4. Conclusions
7
8
9 There is no or very rarely simulation or experimental gas condensation work which claims that
10
11
the core-shell nanoparticles have been obtained during the condensation process. In this work,
12 the possible formation of Au@Pt, Au@Cu, Au@Rh, and Au@Ir clusters during the vapor
13
14 condensation process has been investigated by inserting the 309 atoms gold cluster into the metal
15
16 vapor environments. In fact, positioning Au as the cluster core (which has smaller surface energy
17 than the other metals) would be very interesting. Such as this construction has not performed
18
19 theoretically or experimentally before. However, due to the last developments in the gas-phase
20
21 condensation techniques, the possibilities for mixing and coating various types, sizes, and
22
23
morphologies of clusters create significant potential for synthesis of such core-shell clusters
24 through new gas-phase system constructions49 .
25
26 Some structural and thermodynamics properties of the created clusters have been studied and the
27
28 following important results have been obtained:
29
(1) The core-shell nanocluster in all systems (with the exception of Au@Cu) has smaller
30
31 value of the absolute total energy than the other pure nanoclusters. This result is due to
32
33 the fact that the cohesive energy of gold is smaller than other metals (with the exception
34
35 of Cu).
36 (2) The Δ value of the pure metal clusters at the different systems obeys the following order
37
38 (the smaller the ∆ the more stable the cluster): ΔAu< ΔCu< ΔPt< ΔRh< ΔIr. The reason of
39
40 this order of stability of the pure metal clusters can be interpreted using the surface
41
42
energy of bulk metals (the smaller the surface energy the more stable the cluster)
43 (3) The Δ value of the formed core-shell nanoclusters follows the order: ΔAu< ΔAu@Cu<
44
45 ΔAu@Rh< ΔAu@Ir. This means that the existence of the Cu, Rh, and Ir metals on the gold
46
47 cluster is unfavorable.
48
(4) It is also shown in each system that the ∆ parameter of the formed core-shell cluster is
49
50 smaller (and thus is more stable) than the pure metal clusters. This result can be also
51
52 interpreted using the surface energy.
53
54
55
56
57
58 19
59
1
2
3 (5) The formed clusters are not the pure core-shell structures and some metal atoms have
4
5 migrated to the gold clusters core and also some gold atoms migrated from the core to the
6
7 shell. These results are due to the surface energy, cohesive energy, and size of the atoms.
8
9
(6) The Au@Pt and Au@Rh are not pure core-shell structures but they are (Au-Pt mixed)@Pt
10 and (Au-Rh mixed)@Rh structures.
11
12 (7) The reason of the presence of more Pt atoms into the cluster core can be due to the more
13
14 match between the Au and Pt atoms than other atoms which is due to the more similarity
15
between the sizes of gold and platinum atoms than other systems.
16
17 (8) The existence of gold atoms into the platinum (and Rh) atoms increases the Au-Pt and Au-
18
19 Rh interactions whereas decreases the Au-Au, Pt-Pt, and Rh-Rh interactions more than
20
21 other nanoclusters. These results have been approved by increasing the Au-M RDF and
22 decreasing the M-M and Au-Au RDFs in the Au@Pt and Au@Rh clusters more than other
23
24 clusters
25
26 (9) The initial icosahedral morphology of the nanoclusters was vanished whereas the amount of
27
28
the fcc and hcp atoms have been more than other ordered atoms and thus, these core-shell
29 nanoclusters have fcc-like and hcp-like morphologies.
30
31 (10) The thermal investigations of the obtained nanoclusters showed that the amount of
32
33 the surface gold atoms increases whereas the amount of the Ir surface atoms decreases by
34
the temperature. The cluster also becomes more spherical by increasing the temperature
35
36 which is due to the more movement and diffusion of the atoms to achieve the more stable
37
38 structure.
39
40
41
42 Supporting Information
43
44
45 The snapshots of the formation of Au@Cu, Au@Pt, and Au@Rh clusters at the various
46 simulation times; The number of various atoms, mole fractions, number of the cluster surface
47
48 atoms, and percent of the surface atoms for the Au@Ir, Au@Pt, and Au@Rh clusters; The
49 percentage of ordered and disordered atoms in Au@Pt, Au@Ir, and Au@Rh clusters; The
50 percentage of ordered and disordered atoms in Au@Ir nanoclusters at different temperatures;
51
52 The number of various atoms, mole fractions, number of the surface atoms, and percent of the
53 surface atoms for the Au@Ir nanoclusters at different temperatures; The percentage of ordered
54 and disordered atoms, also the percent of the surface atoms in Au@Rh nanoclusters with two
55
56
various morphologies of the initial structure.
57
58 20
59
1
2
3
4
5
6
7
8
9
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6 Table of Contents:
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21
The snapshots of the formation of Au@Cu cluster in the metal vapor condensation
22
23 process at different simulation times (Au is in yellow and Cu is in red).
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