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Conclusions
In conclusion, we have demonstrated an environmentally
friendly process: high active and recyclable graphene oxide-
supported palladium nanoparticle-catalyzed reductive Ullmann
reaction of aryl chlorides in ionic liquid–supercritical carbon
dioxide system. The application of cheaper chemicals, such as
aryl chlorides (instead of expensive aryl bromides or iodides),
aluminium (instead of expensive zinc or indium, etc.) and natu-
rally abundant ‘‘greenhouse’’ gas CO2, make this kind of process
quite attractive. The Pd NP catalyst and ionic liquid can be
recycled for at least 5 runs, indicating the economic viability of
this process. The employment of the ionic liquid–supercritical
carbon dioxide system led to immobilization, activation, and
stabilization of the Pd NP catalyst that would be impossible in
classical organic media separately. GO, the novel catalyst
support, was found to replace the traditional active hydrogen
donor readily with much enhanced product separation efficiency.
Carbon dioxide, a naturally abundant, nonflammable, relatively
nontoxic, economical and recyclable ‘‘greenhouse’’ gas, was
found to significantly promote the selectivity of the Pd
NP-catalyzed aluminium-induced reductive Ullmann reaction of
aryl chlorides. Further studies on the phase behaviours of
different ionic liquids in supercritical carbon dioxide for different
coupling reaction are under progress in our laboratory.
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Acknowledgements
We are grateful to the Scientific Foundation of Guangxi Zhuang
Autonomous Region of China (No. 200626152, 200508193,
200925066) for financial support.
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