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Article history: This work showed that chemically-synthesized gold nanoparticles, AuNPs, supported onto a Si (111) wafer elec-
Received 12 January 2017 trode, can be selectively modified with a copper adlayer through underpotential deposition (upd) conditions,
Received in revised form 28 February 2017 using both: potentiodynamic or potentiostatic electrochemical means. From analysis of experimental
Accepted 2 March 2017
potentiostatic current density transients, it is shown that Cu upd onto the AuNPs occurs by a mechanism involv-
Available online 4 March 2017
ing the simultaneous presence of a Langmuir-type adsorption-desorption and an instantaneous two-dimension-
Keywords:
al, 2D, nucleation process. The influence of the applied potential on the Cu upd kinetics and on the extent of Cu
Gold nanoparticles atoms coverage over the AuNPs was also reported. Furthermore, it is shown that the Cu overpotential deposition,
Si (111) wafer electrode opd, onto these AuNPs, starting from a potential in the upd region where the AuNPs surface is free from Cu atoms,
Cu upd-opd occurs through a 2D-3D mechanism, where the 3D nucleation is mass-transfer controlled. Notwithstanding,
Nucleation when Cu opd started at the equilibrium potential the mechanism solely involved 3D nucleation.
Kinetics © 2017 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jelechem.2017.03.003
1572-6657/© 2017 Elsevier B.V. All rights reserved.
2 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7
Fig. 2. SEM images of the AuNPs (one layer was stacked) electrostatically adsorbed on a Si (111) wafer electrode surface: a) 20,000× and b) 100,000×.
M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7 3
Fig. 3. CVs recorded in the systems: Si (111) / 0.5 M H2SO4 (red line) and Si (111)-AuNPs /
0.5 M H2SO4 (blue line), in both cases the potential scan started at − 420 mV in the
positive direction at 5.0 mVs−1. The inset shows a close up of the region
(0 ≤ E ≤ 400 mV) of the CVs.
Fig. 6. Comparison of the experimental (circles) i-t plots recorded in the system: Si (111)-
AuNPs / 5.0 mM CuSO4, 0.5 M H2SO4 stepping the potential from 400 mV to the different
potential values indicated in the Figure in mV, and the theoretical ones (solid lines)
obtained by non-linear fit of Eq. (3) to the experimental data. The inset shows the
individual contributions of the theoretical overall current, for the i-t plot recorded at
Fig. 4. Cyclic voltammogram recorded in system: Si (111)-AuNPs / 5.0 mM CuSO4, 0.5 M 60 mV due to an adsorption process (iad) and an instantaneous 2D nucleation process,
H2SO4. The potential scan started at 375 mV in the negative direction at 5.0 mVs−1. limited by ad-atoms incorporation (i2Di-LI).
4 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7
Table 1
Current maxima coordinates and best fitting parameters obtained through non-linear fitting of Eq. (3) to the experimental transients shown in Fig. 6.
100 6.05 ± 0.02 2.20 ± 0.04 8.65 + 0.31 1.02 ± 0.04 0.60 ± 0.01 11.6 ± 0.2 21.5 0.62
80 5.25 ± 0.01 5.53 ± 0.08 9.50 ± 0.39 0.91 ± 0.04 1.44 ± 0.02 13.9 ± 0.2 54.4 0.53
60 4.47 ± 0.04 9.21 ± 0.06 10.83 ± 0.68 0.90 ± 0.07 2.85 ± 0.05 19.2 ± 0.3 68.2 0.60
40 3.16 ± 0.02 19.92 ± 0.08 11.20 ± 0.44 0.71 ± 0.04 6.20 ± 0.02 40 ± 1 81.9 0.77
20 2.63 ± 0.01 24.82 ± 0.02 11.85 ± 0.56 0.32 ± 0.07 9.11 ± 0.27 55 ± 1 93.7 0.70
0 2.10 ± 0.02 29.58 ± 0.01 12.92 ± 0.52 0.30 ± 0.05 12.78 ± 0.30 72.6 ± 1.1 103.5 0.60
a
The uncertainty values were evaluated on the basis of 3 repetitions for each applied potential.
b
Obtained by integration of the cathodic branch of the CV reported in Fig. 4.
cathodic peaks which have been associated [32] with structural changes where θRe is the fractional area of Re, S is the electrode surface area, z is
on the Cu monolayer formation. The first one (occurring at more posi- the number of electrons transferred during the heterogeneous reaction,
tive potential values) to the transition from Cu randomly adsorbed to ð v is the potential scan rate, R, T and F are the universal gas constant, ab-
pffiffiffi pffiffiffi
3 3 ÞR30 ° , honeycomb-like superstructure, and the second one solute temperature and Faraday constant, respectively, Γο⁎ is the total
to the transition from the latter to that corresponding with the isomor- surface coverage, ε is the number of water molecules displaced from
phic (1 × 1) full Cu monolayer formation. Therefore, a plausible expla- the surfaces by absorption of Ox or Re, θT = θRe + θOx (with θOx being
nation in the case of Cu upd onto AuNPs is that it occurs through just the fractional area of Ox) and g = aOx + aRe − 2aOxRe (where aOxRe, aOx
one structural transition namely: from Cu randomly adsorbed to a and aRe are the Ox-Re, Ox-Ox and Re-Re interaction parameters
(1 × 1) adlayer structure. These features clearly indicate that the kinet- (dimensionless)).
ics and mechanism of the Cu upd onto Au are very sensitive to the struc- z2 F 2 Sv0
Eq. (2) is a parameterized form of Eq. (1) with P1 ¼ RT and
ture of the gold surfaces. The complexity of the Cu upd on Au flat P2 = 2εgθT
surfaces has been addressed by Rikvold and coworkers [26,27] and by
Oviedo et al. [31], by means of different simulations namely: numerical
θRe ð1−θRe Þ
studies of lattice-gas [26,27] and quantum mechanical methods models i ¼ P1 ð2Þ
1−P 2 θRe ð1−θRe Þ
[31].
Fig. 7. Potential variation of a) the current time's maxima (tm) of the experimental i-t transients reported in Fig. 5 and b) parameter k4 obtained by non-linear fit of Eq. (3) to the
experimental potentiostatic current transients. The lines and the equations correspond to the linear fitting of the data obtained (points).
M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7 5
with:
and
Fig. 8. Potential variation of the charge density (left y-axis) and the corresponding AuNPs
surface coverage with Cu atoms (right y-axis). The individual contributions to the total Cu
i2Di−LI ðt Þ ¼ k3 t exp −k4 t 2 ð5Þ
upd process (circles) due to 2D nucleation (squares) and the adsorption process
(triangles) were obtained from Eqs. (8) and (9) using the parameters reported in Table 1.
2πzSFMhN0 K 2g πM2 N0 K 2g
with k3 ¼ ρ and k4 ¼ ρ2
fitting of the Eq. (3) gives a good support to the model used to describe
where E is the applied potential, Rs is the solution's resistance, C the dou-
the mechanisms and kinetics of Cu upd on AuNPs. Moreover, for instan-
ble layer capacitance, Kg is the nuclei growth rate constant (mol cm−2- taneous 2D nucleation [38–39] the product im tm must be equal to 0.606
s− 1), M and ρ are the molecular mass and the deposit density,
respectively; h is the layer formed height and N0 is the overall number
density of active sites available for the nucleation process on the sub-
strate surface.
3.3.2.2. Influence of the applied potential on Cu upd onto AuNPs. Fig. 6 com-
pares the experimental potentiostatic current density transients obtain-
ed during Cu upd on the AuNPs surfaces, supported onto Si (111) wafer
electrode, for different applied potentials and those resulting from Eq.
(3) fitting to the respective experimental data. The best fitting parame-
ters are shown in Table 1. Note that Eq. (3) describes adequately the ex-
perimental evidence in all cases. Moreover, it is plain from the inset in
Fig. 6 that at very short times the adsorption process is the dominant
contribution. However, after a few seconds the 2D instantaneous nucle-
ation becomes the more important contribution to the total current.
This transition can be related to the structural changes observed during
Cu upd on Au(111) extended surfaces, namely: random adsorption of
pffiffiffi pffiffiffi
Cu atoms to ð 3 3ÞR30 ° or honeycomb structure, and eventually,
if the applied potential corresponds to the equilibrium potential, to a
(1 × 1) isomorphic structure corresponding to the formation of a full
monolayer [18].
As can be noted from Fig. 6 all these current transients possess well-
resolved current maxima with tm, im coordinates, see Table 1. At this
current maximum, see inset in Fig. 6, the contribution associated to
the double layer charging is negligible, thus at this point the current is
practically due to the 2D nucleation process and then the temporal de-
rivative of Eq. (5) must be equal to zero. Thus, differentiation of Eq. (5)
with respect to time yields:
1=2
1 ρ
tm ¼ ¼ ð6Þ
2k4 ð2πN0 Þ1=2 MK 2g
Taking the logarithm of Eq. (6) and then its partial differentiation
with respect to E yields:
Fig. 9. a) Comparison of the experimental (circles) j-t plot recorded in the system: Si
(111)-AuNPs / 5.0 mM CuSO4, 0.5 M H2SO4 stepping the potential from 400 to −60 mV
∂ logt m 1 ∂ logk4
≅− ð7Þ (upd-opd), and the theoretical one (solid line) obtained by non-linear fit of Eq. (10) to
∂E 2 ∂E the experimental data. The individual contributions of the theoretical overall current
density due to adsorption (iad), instantaneous (i2Di-LI) and progressive (i2Dp-LI) 2D
Fig. 7 shows the potential dependence of the logarithm of current nucleation, limited by ad-atoms incorporation and a 3D nucleation process mass
time's maxima (tm), Fig. 7a, and the logarithm of parameter k4, Fig. 7b. transfer-controlled (i3D-dc) are also shown. b) Comparison of experimental (points) j-t
plots recorded in the system: Si (111)-AuNPs / 5.0 mM CuSO4, 0.5 M H2SO4 stepping the
In both cases, the observed behaviors were linear. The slopes were potential from 400 to −60 mV (upd-opd) (triangles) and from 0 to −60 mV (points)
0.004 (for log (tm) vs. E) and −0.008 (for log (k4) vs. E). This agreement with the theoretical j-t traces generated by Eq. (10) and (17), respectively. For both
between direct experimental evidence (tm) and that (k4) obtained by cases the best fit parameters obtained are reported in Table 2.
6 M. Romero-Romo et al. / Journal of Electroanalytical Chemistry 791 (2017) 1–7
Table 2
Adsorption and nucleation parameters obtained through non-linear fitting of Eqs. (10) or (17) to the experimental transients shown in Fig. 9.
400 to −60 mV 0.81 ± 0.02 6.6 ± 0.3 0.002 ± 0.001 0.00005 ± 0.00002 1.3 ± 0.2 0.00004 ± 0.00001 1582 ± 8
0 to −60 mV 1.56 ± 0.05 4.0 ± 0.3 – – 1.3 ± 0.1 0.27 ± 0.01 4.45 ± 0.01
a
The uncertainty values were evaluated on the basis of 3 repetitions for each applied potential.
qM, where qM is the monolayer charge. As can be noted from Table 1, the with
value of this product, calculated from the experimental transients, and
divided by the charge of the monolayer, obtained by integration of the
2FD1=2 c0
cathodic branch of the CV reported in Fig. 4, adequately agrees with P1 ¼ ð13Þ
the theoretical value of 0.606, for any of the applied potentials π1=2
considered.
From analysis of Eqs. (4) and (5) it is possible to estimate the charge P 2 ¼ N 0 πkD ð14Þ
densities due to adsorption, qad and 2D nucleation, q2D, processes re-
spectively as:
P3 ¼ A ð15Þ
jðt Þ ¼ jad ðt Þ þ j2Di−LI ðt Þ þ j2Dp−LI ðt Þ þ j3D−DC ðt Þ ð10Þ jðt Þ ¼ jad ðt Þ þ j3D−DC ðt Þ ð17Þ
Acknowledgements active surface area of Au nanoparticles supported onto an ITO electrode by means
of Cu upd, Electrochem. Commun. 56 (2015) 70–74.
[17] H. Tang, J.H. Chen, M.Y. Wang, L.H. Nie, Y.F. Kuang, S.Z. Yao, Controlled synthesis of
The authors like to thank CONACyT for projects 258487 and 237327 platinum catalysts on Au nanoparticles and their electrocatalytic property for meth-
and SEP-PRODEP for RedNIQAE. MTRS thank CONACyT for the cathedra anol oxidation, Appl. Catal., A 275 (2004) 43–48.
[18] J. Zhang, Y.E. Sung, P.A. Rikvold, A. Wieckowski, Underpotential deposition of Cu on
2159. JAG and LEB thanks CONACyT for the support given to undertake a Au(111) in sulfate-containing electrolytes: a theoretical and experimental study, J.
postdoctoral stay at UAMA and the scholarship granted to pursue post- Chem. Phys. 104 (1996) 5699–5712.
graduate studies at UAMA, respectively. JAG, MGMY, MTRS, SCA, MRR [19] M. Palomar-Pardavé, I. González, N. Batina, New insights into evaluation of kinetic
parameters for potentiostatic metal deposition with underpotential and
and MPP wish to thank the SNI for the distinction of their membership overpotential deposition processes, J. Phys. Chem. B 104 (2000) 3545–3555.
and the stipend received. MGMY is indebted to Bristol University and its [20] A. Martínez-Ruiz, M. Palomar-Pardavé, N. Batina, Overpotential deposition of copper
Electrochemistry group for her Ph.D. formation, CONACyT for paying the on an iodine-modified Au(111) electrode, Electrochim. Acta 53 (2008) 2115–2120.
[21] M. Palomar-Pardavé, E. Garfias-García, M. Romero-Romo, M.T. Ramírez-Silva, N.
corresponding tuition fees and L'oreál-UNESCO-CONACyT-AMC for the
Batina, Influence of the substrate's surface structure on the mechanism and kinetics
grant Woman in Science 2016. We also like to express our gratitude to of the electrochemical UPD formation of a copper monolayer on gold, Electrochim.
the anonymous reviewers of this paper for their criticisms and sugges- Acta 56 (2011) 10083–10092.
tions that contributed to improve our work. [22] P. Vélez, A. Cuesta, E.P.M. Leiva, V.A. Macagno, The underpotential deposition that
should not be: Cu(1 × 1) on Au(111), Electrochem. Commun. 25 (2012) 54–57.
[23] O.A. Oviedo, L. Reinaudi, E.P.M. Leiva, The limits of underpotential deposition in the
Appendix A. Supplementary data nanoscale, Electrochem. Commun. 21 (2012) 14–17.
[24] A. Milchev, Electrocrystallization: Fundamentals of Nucleation and Growth, Kluwer
Academic Publishers, The Netherlands, 2002 (Chap. 5).
Supplementary data to this article can be found online at http://dx. [25] M.H. Hölzle, U. Retter, D.M. Kolb, The kinetics of structural changes in Cu adlayers on
doi.org/10.1016/j.jelechem.2017.03.003. Au(111), J. Electroanal. Chem. 371 (1994) 101–109.
[26] J. Zhang, Y.-E. Sung, P.A. Rikvold, A. Wieckowski, Underpotential deposition of Cu on
Au(111) in sulfate-containing electrolytes: a theoretical and experimental study, J.
References Chem. Phys. 104 (1996) 5699–5712.
[27] G. Brown, P.A. Rikvold, M.A. Novotny, A. Wieckowski, Simulated dynamics of
[1] I.P. Batra, Metallization and Metal-Semiconductor Interfaces, Springer-Verlag, New
underpotential deposition of Cu with sulfate on Au(111), J. Electrochem. Soc. 146
York Inc., 2011
(1999) 1035–1040.
[2] S.-H. An, T.-H. Lim, Y.-H. Kim, S.-E. Bae, J.-H. Yoon, C.-W.J. Lee, EC-STM studies on
[28] Y. Li, J.T. Cox, B. Zhang, Electrochemical responses and electrocatalysis at single Au
copper electrodeposition at n-Si(111):H electrodes, Colloids Surf. A Physicochem.
nanoparticles, J. Am. Chem. Soc. 132 (2010) 3047–3054.
Eng. Asp. 313–314 (2008) 339–342.
[29] S.W.T. Price, J.D. Speed, P. Kannan, A.E. Russell, Exploring the first steps in core-shell
[3] J.C. Ziegler, A. Reitzle, O. Bunk, J. Zegenhagen, D.M. Kolb, Metal deposition on n-
electrocatalyst preparation: in situ characterization of the underpotential deposition
Si(111):H electrodes, Electrochim. Acta 45 (2000) 4599–4605.
of Cu on supported Au nanoparticles, J. Am. Chem. Soc. 133 (2011) 19448–19458.
[4] M.B. Quiroga Arganaraz, C.I. Vázquez, G.I. Lacconi, Copper electrodeposition onto hy-
[30] B.J. Plowman, R.G. Compton, Inhibition of Cu underpotential deposition on Au nano-
drogenated Si(111) surfaces: influence of thiourea, J. Electroanal. Chem. 639 (2010)
particles: the role of the citrate capping agent and nanoparticle size, Chem. Electro.
95–101.
Chem. 1 (2014) 1009–1011.
[5] C. Ji, G. Oskam, P.C. Searson, Electrodeposition of copper on silicon from sulfate so-
[31] O.A. Oviedo, L. Reinaudi, S.G. García, E.P.M. Leiva, in: F. Scholz (Ed.), Underpotential
lution, J. Electrochem. Soc. 148 (2001) C746–C752.
Deposition: From Fundamentals and Theory to Applications at the Nanoscale.
[6] A. Reitzle, F.U. Renner, T.L. Lee, J. Zegenhagen, D.M. Kolb, Electrochemical growth of
Monographs in Electrochemistry, Springer, 2015 (Chapter 5).
copper on well-defined n-Si(111):H surfaces, Surf. Sci. 576 (2005) 19–28.
[32] D.M. Kolb, Structure studies of metal electrodes by in-situ scanning tunneling mi-
[7] S. Jakob, W. Schindler, Impact of electric fields on the Co electrodeposition onto n-
croscopy, Electrochim. Acta 45 (2000) 2387–2402.
Si(111):H surfaces, Surf. Sci. 631 (2015) 178–184.
[33] J. Turkevich, P.C. Stevenson, J. Hillier, A study of the nucleation and growth processes
[8] K.H. Kima, J.D. Lee, J.J. Lee, B.Y. Ahna, H.S. Kim, Y.W. Shin, Growth of α-Fe films on n-
in the synthesis of colloidal gold, Discuss. Faraday Soc. 11 (1951) 55–75.
Si(111) substrate by pulsed electrodeposition in a non-aqueous solution, Thin Solid
[34] G. Frens, Controlled nucleation for the regulation of the particle size in monodis-
Films 483 (2005) 74–78.
perse gold suspensions, Nature (London), Phys. Sci. 241 (1973) 20–22.
[9] M. Kolíbal, M. Konecny, F. Ligmajer, D. Skoda, T. Vystavel, J. Zlámal, P. Varga, T.
[35] A.J. Bard, L.R. Faulkner, Electrochemical Methods Fundamentals and Applications,
Sikola, Guided assembly of gold colloidal nanoparticles on silicon substrates
John Wiley & Sons, Inc., 2000 (Chapter 14).
prepatterned by charged particle beams, ACS Nano 6 (2012) 10098–10106.
[36] R.G. Barradas, D. Porter, Studies in electrocrystallization: part IV. Experimental in-
[10] Y. Yamanoi, T. Yonezawa, N. Shirahata, H. Nishihara, Immobilization of gold nano-
vestigation of two-dimensional nucleation-growth processes in terms of surface
particles onto silicon surfaces by Si-C covalent bonds, Langmuir 20 (2004)
coverage derived from transient measurements, J. Electroanal. Chem. 110 (1980)
1054–1056.
159–180.
[11] K. Aisha Yaacob, G.W. Gyn, Formation of gold nanoparticles film on silicon wafer by
[37] M. Noel, K.I. Vasu, Cyclic voltammetry and the frontiers of electrochemicstry, Forma-
self-assembled method, Adv. Mater. Res. 795 (2013) 726–731.
tion and Dissolution of Monolayes, Oxford & IBH publishing Co. Pvt. Ltd., New Delhi,
[12] F. Li, I. Ciani, P. Bertoncello, P.R. Unwin, J.J. Zhao, C.R. Bradbury, D.J. Fermin, Scanning
1990 (Chapter 7).
electrochemical microscopy of redox-mediated hydrogen evolution catalyzed by
[38] V. Bostanov, W. Obretenov, G. Staikov, E. Budevski, Monolayer formation by instan-
two-dimensional assemblies of palladium nanoparticles, J. Phys. Chem. C 112
taneous two-dimensional nucleation in the case of electrolytic crystal growth, J.
(2008) 9686–9694.
Electroanal. Chem. 146 (1983) 303–312.
[13] M. Carrara, J.J. Kakkassery, J.P. Abid, D.J. Fermin, Modulation of the work function in
[39] A. Milchev, I. Krastev, Two-dimensional progressive and instantaneous nucleation
layer-by-layer assembly of metal nanoparticles and poly-L-lysine on modified Au
with overlap: the case of multi-step electrochemical reactions, Electrochim. Acta
surfaces, Chem. Phys. Chem. 5 (2004) 571–575.
56 (2011) 2399–2403.
[14] J.J. Kakkassery, J.P. Abid, M. Carrara, D.J. Fermin, Electrochemical and optical proper-
[40] M. Palomar-Pardavé, M. Miranda-Hernández, I. González, N. Batina, Detailed charac-
ties of two dimensional electrostatic assembly of Au nanocrystals, Faraday Discuss.
terization of potentiostatic current transients with 2D–2D and 2D–3D nucleation
125 (2004) 157–169.
transitions, Surf. Sci. 399 (1998) 80–95.
[15] J. Aldana-González, M. Palomar-Pardavé, S. Corona-Avendaño, M.G. Montes de Oca,
[41] B.R. Scharifker, J. Mostany, Three-dimensional nucleation with diffusion controlled
M.T. Ramírez-Silva, M. Romero-Romo, Gold nanoparticles modified-ITO electrode
growth. Part I: number density of active sites and nucleation rates per site, J.
for the selective electrochemical quantification of dopamine in the presence of
Electroanal. Chem. 177 (1984) 13–23.
uric and ascorbic acids, J. Electroanal. Chem. 706 (2013) 69–75.
[16] J. Aldana-González, J. Olvera-García, M.G. Montes de Oca, M. Romero-Romo, M.T.
Ramírez-Silva, M. Palomar-Pardavé, Electrochemical quantification of the electro-