Uncovering structure-property relationships: from studies of pure and supported metal clusters and colloids to their use in catalysis and sensing. Seminar

Insight into the nature of pure and support-immobilized atomically precise metal clusters and well-defined colloids is of fundamental importance since such metal nanoparticle precursors are useful for the development of better catalysts and sensors.

Our detailed DFT studies of the ligated clusters allowed systematic identification of bands observed in the far-IR spectra (obtained at the Australian Synchrotron)1-3 as well as better understanding of their de-ligation4 and interpretation of the ultra-high resolution electron microscopy images of clusters supported on titania nanosheets.5

Results of recent synchrotron XPS/XAS studies of pure and supported clusters and colloids reveal their unique electronic properties and highlight the importance of support chemistry, which could be tuned by pre-treatments, in controlling aggregation of clusters.6-8

Our catalytic studies highlight the effects of support and gold particle size in electrocatalytic oxidation of glycerol,9-12 initiator- and solvent-free aerobic oxidation of cyclohexene13,14 and effects of the nature of the cluster/colloid precursors and activation treatments in the aerobic oxidation of benzyl alcohol.15 We have also demonstrated that green catalytic process of aerobic oxidation of amines to nitriles can be driven by the visible light using hydrous ruthenium oxide nanoparticles on TiO2.16

The Au-WO3-based composites fabricated using clusters (Au9) and colloids (Au101) demonstrate excellent performance as optical and conductometric sensors for hydrogen, providing evidence that ultra-small clusters outperform large NPs.17,18 We have also demonstrated sensing (including size effect) of important toxins and viruses at nanomolar concentrations by the surface-modified Au colloids.19,20

 

Acknowledgements

This talk will covers results of a number of multidisciplinary studies, which would be impossible without contributions by colleagues and their teams from University of Canterbury, University of Adelaide, Flinders University, NIMS, RMIT and University of Otago. Individual contributors are listed in the references below.

 

References

(1) Alvino, J. F.; Bennett, T.; Anderson, D.; Donoeva, B.; Ovoshchnikov, D.; Adnan, R. H.; Appadoo, D.; Golovko, V.; Andersson, G.; Metha, G. F. Far-infrared absorption spectra of synthetically-prepared, ligated metal clusters with Au-6, Au-8, Au-9 and Au6Pd metal cores. RSC Advances 2013, 3, 22140-22149.

(2) Bennett, T.; Adnan, R. H.; Alvino, J. F.; Golovko, V.; Andersson, G. G.; Metha, G. F. Identification of the Vibrational Modes in the Far-Infrared Spectra of Ruthenium Carbonyl Clusters and the Effect of Gold Substitution. Inorganic Chemistry 2014, 53, 4340-4349.

(3) Bennett, T.; Falcinella, A. J.; White, R. J.; Adnan, R. H.; Golovko, V.; Andersson, G. G.; Metha, G. F. The effect of counter ions on the far-infrared spectra of tris(triphenylphosphinegold) oxonium dimer salts. RSC Advances 2015, 5, 74499-74505.

(4) Reuben White, T. B., Vladimir Golovko, Gunther G. Andersson, and Gregory F. Metha. A Systematic Density Functional Theory Study of the Complete De–ligation of Ru3(CO)12. ChemistrySelect 2016, 3, 1-7.

(5) Al Qahtani, H. S.; Kimoto, K.; Bennett, T.; Alvino, J. F.; Andersson, G. G.; Metha, G. F.; Golovko, V. B.; Sasaki, T.; Nakayama, T. Atomically resolved structure of ligand-protected Au9 clusters on TiO2 nanosheets using aberration-corrected STEM. The Journal of Chemical Physics 2016, 144, 114703.

(6) Anderson, D. P.; Alvino, J. F.; Gentleman, A.; Al Qahtani, H.; Thomsen, L.; Polson, M. I. J.; Metha, G. F.; Golovko, V. B.; Andersson, G. G. Chemically-synthesised, atomically-precise gold clusters deposited and activated on titania. Physical Chemistry Chemical Physics 2013, 15, 3917-3929.

(7) Anderson, D. P.; Adnan, R. H.; Alvino, J. F.; Shipper, O.; Donoeva, B.; Ruzicka, J.-Y.; Al Qahtani, H.; Harris, H. H.; Cowie, B.; Aitken, J. B.; Golovko, V. B.; Metha, G. F.; Andersson, G. G. Chemically synthesised atomically precise gold clusters deposited and activated on titania. Part II. Physical Chemistry Chemical Physics 2013, 15, 14806-14813.

(8) Ruzicka, J.-Y.; Abu Bakar, F.; Hoeck, C.; Adnan, R.; McNicoll, C.; Kemmitt, T.; Cowie, B. C.; Metha, G. F.; Andersson, G. G.; Golovko, V. B. Toward Control of Gold Cluster Aggregation on TiO2 via Surface Treatments. The Journal of Physical Chemistry C 2015, 119, 24465-24474.

(9) Padayachee, D.; Golovko, V.; Marshall, A. T. The effect of MnO2 loading on the glycerol electrooxidation activity of Au/MnO2/C catalysts. Electrochimica Acta 2013, 98, 208-217.

(10) Padayachee, D.; Golovko, V.; Ingham, B.; Marshall, A. T. Influence of particle size on the electrocatalytic oxidation of glycerol over carbon-supported gold nanoparticles. Electrochimica Acta 2014, 120, 398-407.

(11) Marshall, A. T.; Golovko, V.; Padayachee, D. Influence of gold nanoparticle loading in Au/C on the activity towards electrocatalytic glycerol oxidation. Electrochimica Acta 2015, 153, 370-378.

(12) Steven, J. T.; Golovko, V. B.; Johannessen, B.; Marshall, A. T. Electrochemical stability of carbon-supported gold nanoparticles in acidic electrolyte during cyclic voltammetry. Electrochimica Acta 2016, 187, 593-604.

(13) Donoeva, B. G.; Ovoshchnikov, D. S.; Golovko, V. B. Establishing a Au Nanoparticle Size Effect in the Oxidation of Cyclohexene Using Gradually Changing Au Catalysts. ACS Catalysis 2013, 3, 2986-2991.

(14) Ovoshchnikov, D. S.; Donoeva, B. G.; Williamson, B. E.; Golovko, V. B. Tuning the selectivity of a supported gold catalyst in solvent- and radical initiator-free aerobic oxidation of cyclohexene. Catalysis Science & Technology 2014, 4, 752-757.

(15) Adnan, R. H.; Andersson, G. G.; Polson, M. I. J.; Metha, G. F.; Golovko, V. B. Factors influencing the catalytic oxidation of benzyl alcohol using supported phosphine-capped gold nanoparticles. Catalysis Science & Technology 2015, 5, 1323-1333.

(16) Ovoshchnikov, D. S.; Donoeva, B. G.; Golovko, V. B. Visible-Light-Driven Aerobic Oxidation of Amines to Nitriles over Hydrous Ruthenium Oxide Supported on TiO2. ACS Catalysis 2015, 5, 34-38 (Cover).

(17) Ahmad, M. Z.; Sadek, A. Z.; Yaacob, M. H.; Anderson, D. P.; Matthews, G.; Golovko, V. B.; Wlodarski, W. Optical characterisation of nanostructured Au/WO3 thin films for sensing hydrogen at low concentrations. Sensors and Actuators B-Chemical 2013, 179, 125-130.

(18) Ahmad, M. Z.; Golovko, V. B.; Adnan, R. H.; Abu Bakar, F.; Ruzicka, J.-Y.; Anderson, D. P.; Andersson, G. G.; Wlodarski, W. Hydrogen sensing using gold nanoclusters supported on tungsten trioxide thin films. International Journal of Hydrogen Energy 2013, 38, 12865-12877.

(19) Poonthiyil, V.; Nagesh, P. T.; Husain, M.; Golovko, V. B.; Fairbanks, A. J. Gold Nanoparticles Decorated with Sialic Acid Terminated Bi-antennary N-Glycans for the Detection of Influenza Virus at Nanomolar Concentrations. ChemistryOpen 2015, 4, 708-716 (Cover).

(20) Poonthiyil, V.; Golovko, V. B.; Fairbanks, A. J. Size-optimized galactose-capped gold nanoparticles for the colorimetric detection of heat-labile enterotoxin at nanomolar concentrations. Organic & Biomolecular Chemistry 2015, 13, 5215-5223.