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Citation: Li Guang-Jin, Guo Xie-Xian, Fujimoto Toshiyuki, Ichikawa Masaru. Mechanismic Study of the Synthesis of Intrazeolite Pt Carbonyl Clusters[J]. Acta Physico-Chimica Sinica, ;1994, 10(08): 710-715. doi: 10.3866/PKU.WHXB19940808 shu

Mechanismic Study of the Synthesis of Intrazeolite Pt Carbonyl Clusters

1.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chenese Academy of Sciences, Dalian 116023

Received Date: 3 April 1993
Available Online: 15 August 1994

The mechanism of the synthesis of platinum carbonyl clusters [Pt_3(CO)_6]~(2-)_n(n=3,4) in cages of NaY was studied by IR, EXAFS ~(13)CO exchange reaction and No interaction. The results suggest that oaldized Pt species in NaY cages reacts with CO at 300-373 K to form PtO(CO) (σ_(CO)=2110 cm~(-1)) which aggregates into "Pt_3(CO)_6"(σ_(CO)=2112, 1896 and 1841 cm~(-1)) and eventually converts into dark-green carbonyl cluster [Pt_(12)(CO)_(24)]~(2-). The carbonyl "Pt_3(CO)_6" can exchange with ~(13)CO very quickly at 298 K but the exchange reaction between ~(13)CO and intrazeolite Pt carbonyl clusters [Pt_3(CO)_6]~(2-)_n (n=3,4) proceeds slowly even at enhanced temperature such as 343 K. It is interesting to find that NO breaks successively the intra and inter-tri nal Pt-Pt bonds of the Pt_(12) carbonyl clusters (even at 298 K) and the "Pt_3(C)_6" formed is further reacted to give PtO(CO) with the formation of N_2O and CO_2 in the gas phase. Pt_(12)(CO)_(24)]~(2-) can be reversibly regenerated from the Pt subcarbonyls such as PtO(CO) and "Pt_3(CO)_6" inside NaY by reacting wich CO at 300—353 K.
- Zeolites,
- Pt,
- Carbonyl clusters,
- 13CO exchange,
- EXAFS
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