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Microwave-assisted synthesis of ultra small bare gold clusters supported over Al2O3 and TiO2 as catalysts in reduction of 4-nitrophenol to 4-aminophenol

Research Authors
Mostafa Farrag
Research Abstract

In this work I present a novel method to prepare ultra small bare gold clusters (Aun) loaded over different
supports. Size selected gold clusters protected by glutathione ligand (Au25(SG)18) was prepared and
deposited over aluminium dioxide (Al2O3 Puralox SCCa-190HPV) and anatase titanium dioxide (TiO2) by
impregnation method with doping percentage 0.5 and 1 wt %. Then the doped catalysts were irradiated
1 h by microwave synthesis labstation at 80 C and 500 W to remove the glutathione ligands (GSH) and
leave the bare gold clusters (Au25) supported over alumina and titania as a strategy for enhancing their
catalytic activity and selectivity. The high resolution transmission electron microscope analysis
confirmed the particle size of protected (1 wt % Au25(SG)18/Al2O3) and bare (1 wt % Au25/Al2O3) gold
clusters over alumina have the same size distribution (~1 nm). The TEM images of doped gold clusters
over TiO2 before and after microwave treatment are clearer than alumina. This means the gold clusters
over alumina and titania did not suffer from any agglomeration by microwave treatment. From nitrogen
sorption isotherms at 196 C for the protected and bare gold clusters over supports showed two
different loop types of isotherms H3 and H1, respectively. Their specific surface area SBET, pore volume
and average pore diameter were calculated. The pore size distribution of supported gold clusters before
and after microwave treatment was measured. These results confirmed the ligands were removed from
the supported gold clusters by microwave treatment. The pores in alumina and titania which were
blocked by the protected clusters have become available. Reduction of 4-nitrophenol (4-NP) into 4-
aminophenol (4-AP) in presence of NaBH4 was used as a test reaction to compare the catalytic activity
of supported bare and protected gold clusters over alumina. The results showed that the 1 wt % Au25/
Al2O3 catalyst exhibited the best catalytic performance in the reduction of 4-NP into 4-AP and revealed
100% conversion following 90 s stirring at room temperature. The extreme catalytic activity of the ultra
small gold clusters attributed to their electronic properties and geometrical configuration.

Research Department
Research Journal
Microporous and Mesoporous Materials
Research Publisher
Elsevier
Research Rank
1
Research Vol
Vol. 232
Research Website
http://www.sciencedirect.com/science/article/pii/S1387181116302347
Research Year
2016
Research Pages
pp. 248-255