TY - JOUR
T1 - Nano-brass colloids
T2 - Synthesis by co-hydrogenolysis of [CpCu(PMe 3)] with [ZnCp*2] and investigation of the oxidation behaviour of α/β-CuZn nanoparticles
AU - Cokoja, Mirza
AU - Parala, Harish
AU - Schröter, Marie Katrin
AU - Birkner, Alexander
AU - Van Den Berg, Maurits W.E.
AU - Klementiev, Konstantin V.
AU - Grünert, Wolfgang
AU - Fischer, Roland A.
PY - 2006
Y1 - 2006
N2 - A novel, non-aqueous organometallic access to colloidal copper and copper/zinc (brass) nanoparticles is described. Hydrogenolysis of the precursor [CpCu(PMe3)] (1) in mesitylene at 150 °C and 3 bar H2 quantitatively gives elemental Cu. Analogously, a solution of [ZnCp*2] (2) reacts with H2 to give elemental Zn in 100% yield. Co-hydrogenolysis of 1 and 2 in exactly equimolar quantities selectively yields the intermetallic phase β-CuZn characterised by powder X-ray diffraction (PXRD). Deep red colloidal solutions of nano-Cu as well as red to violet colloids of nano-brass alloys (α/β-CuZn) are obtained by co-hydrogenolysis of 1 and 2 in the presence of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) as surfactant. All samples of the general formula Cu 1-xZnx (0.09 ≤ x ≤ 0.50) were characterised by means of elemental analysis, PXRD, transmission electron microscopy (TEM, EDX and SAED) and UV-Vis absorption spectroscopy. The presence and alloying of metallic Cu and Zn in the β-CuZn sample as a representative example of the series was confirmed by extended X-ray absorption fine structure spectroscopy (EXAFS). The oxidation behaviour of the nanoparticles was investigated by EXAFS, PXRD and UV-Vis spectroscopy indicating, that CuOx@Cu core-shell type particles were formed for pure copper particles, while in the case of brass particles preferential oxidation of the Zn component takes place, which results in core-shell particles of the type (ZnO)δ@Cu 1-xZnx-δ.
AB - A novel, non-aqueous organometallic access to colloidal copper and copper/zinc (brass) nanoparticles is described. Hydrogenolysis of the precursor [CpCu(PMe3)] (1) in mesitylene at 150 °C and 3 bar H2 quantitatively gives elemental Cu. Analogously, a solution of [ZnCp*2] (2) reacts with H2 to give elemental Zn in 100% yield. Co-hydrogenolysis of 1 and 2 in exactly equimolar quantities selectively yields the intermetallic phase β-CuZn characterised by powder X-ray diffraction (PXRD). Deep red colloidal solutions of nano-Cu as well as red to violet colloids of nano-brass alloys (α/β-CuZn) are obtained by co-hydrogenolysis of 1 and 2 in the presence of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) as surfactant. All samples of the general formula Cu 1-xZnx (0.09 ≤ x ≤ 0.50) were characterised by means of elemental analysis, PXRD, transmission electron microscopy (TEM, EDX and SAED) and UV-Vis absorption spectroscopy. The presence and alloying of metallic Cu and Zn in the β-CuZn sample as a representative example of the series was confirmed by extended X-ray absorption fine structure spectroscopy (EXAFS). The oxidation behaviour of the nanoparticles was investigated by EXAFS, PXRD and UV-Vis spectroscopy indicating, that CuOx@Cu core-shell type particles were formed for pure copper particles, while in the case of brass particles preferential oxidation of the Zn component takes place, which results in core-shell particles of the type (ZnO)δ@Cu 1-xZnx-δ.
UR - http://www.scopus.com/inward/record.url?scp=33745198423&partnerID=8YFLogxK
U2 - 10.1039/b602871c
DO - 10.1039/b602871c
M3 - Article
AN - SCOPUS:33745198423
SN - 0959-9428
VL - 16
SP - 2420
EP - 2428
JO - Journal of Materials Chemistry
JF - Journal of Materials Chemistry
IS - 25
ER -