Abstract
The structure of nanoparticles typically differs from its bulk counterpart. Predominantly, the structures of gold nanoparticles have been under exceedingly intense discussion since the discovery of their high catalytic activity. We found an increasing bond length contraction with decreasing particle size for citrate-stabilized gold nanoparticles in aqueous solution as determined by in situ extended X-ray absorption fine structure (EXAFS) spectroscopy. Particle sizes and size distributions were determined by small-angle X-ray scattering. The analysis of the obtained EXAFS spectra employing ab initio calculations reveals that the Au–Au bond length undergoes a contraction of 2 pm for nanoparticles with a radius of 2.9 nm. NIST reference material RM 8011 gold nanoparticles with a radius of 4.4 nm exhibit a smaller contraction of approximately 1 pm. Finally, gold atoms in RM 8013 particles with a radius of 25.7 nm show distances of 288 pm—identical to the distance in gold foil—and exhibits bulk-like properties. The observed bond length contraction of gold nanoparticles in solution is significantly smaller than previously reported for gold nanoparticle deposited on surfaces, which is up to 15 pm. This indicates that the bond length contraction effect of “free” and “surface-immobilized” nanoparticles differ fundamentally. Such difference could be essential for the understanding of nanoparticle-supported catalysis.
Similar content being viewed by others
References
Burda C, Chen XB, Narayanan R, El-Sayed MA (2005) Chem Rev 105:1025
Das SK, Das AR, Guha AK (2009) Langmuir 25:8192
Han J, Liu Y, Guo R (2009) Adv Funct Mater 19:1112
Algar WR, Massey M, Krull UJ (2009) Trac-Trends Anal Chem 28:292
Daniel MC, Astruc D (2004) Chem Rev 104:293
Haruta M, Kobayashi T, Sano H, Yamada N (1987) Chemistry Letters 2:405
Hashmi ASK, Hutchings GJ (2006) Angew Chem Int Ed 45:7896
Jia CJ, Liu Y, Bongard H, Schuth F (2010) J Am Chem Soc 132:1520
Billinge SJL, Levin I (2007) Science 316:561
Jadzinsky PD, Calero G, Ackerson CJ, Bushnell DA, Kornberg RD (2007) Science 318:430
Zhou XC, Xu WL, Liu GK, Panda D, Chen P (2010) Journal of the American Chemical Society 132:138
Miller JT, Kropf AJ, Zha Y, Regalbuto JR, Delannoy L, Louis C, Bus E, van Bokhoven JA (2006) J Catal 240:222
Beale AM, Weckhuysen BM (2010) Phys Chem Chem Phys 12:5562
Reifsnyder SN, Lamb HH (1999) J Phys Chem B 103:321
Schmid G, Meyer-Zaika W, Pugin R, Sawitowski T, Majoral JP, Caminade AM, Turrin CO (2000) Chem Eur J 6:1693
Zhang P, Sham TK (2002) Appl Phys Lett 81:736
Balerna A, Bernieri E, Picozzi P, Reale A, Santucci S, Burattini E, Mobilio S (1985) Surf Sci 156:206
Harada M, Saijo K, Sakamoto N (2009) Colloids Surf A Physicochem Eng Asp 349:176
Frens G (1973) Nature-Physical Science 241:20
Stribeck N (2006) X-ray scattering of soft matter. Springer, Berlin
Bienert R, Emmerling F, Thunemann AF (2009) Anal Bioanal Chem 395:1651
Newville M (2001) J Synchrotron Radiat 8:322
Paris O, Li CH, Siegel S, Weseloh G, Emmerling F, Riesemeier H, Erko A, Fratzl P (2007) J Appl Crystallogr 40:S466
Nelder JA, Mead R (1965) Comput J 7:308
Ravel B, Newville M (2005) J Synchrotron Radiat 12:537
Ankudinov AL, Nesvizhskii AI, Rehr JJ (2003) Phys Rev B 67:115120
Kline SR (2006) J Appl Crystallogr 39:895
Polte J, Ahner TT, Delissen F, Sokolov S, Emmerling F, Thunemann AF, Kraehnert R (2010) J Am Chem Soc 132:1296
Cleveland CL, Landman U, Schaaff TG, Shafigullin MN, Stephens PW, Whetten RL (1997) Phys Rev Lett 79:1873
Uppenbrink J, Wales DJ (1992) J Chem Phys 96:8520
Acknowledgments
The authors are grateful for access to the facilities of BESSY. This research was supported by BAM. We thank U. Reinholz and M. Radtke for help with EXAFS experiments.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Szczerba, W., Riesemeier, H. & Thünemann, A.F. Bond length contraction in gold nanoparticles. Anal Bioanal Chem 398, 1967–1972 (2010). https://doi.org/10.1007/s00216-010-4200-z
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-010-4200-z