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We show that an extended two-dimensional(2D)nanospace forms between graphene sheets and solid surfaces,where guest atoms or molecules can be accommodated at the interfaces and chemical reactions may be performedtherein.It has been demonstrated that O,Pb,Ni,and Si atoms can diffuse underneath graphene at elevatedtemperatures,decoupling the graphene layers from the Ru(0001)substrate.Even at room temperature,theintercalation of CO molecules at graphene/Pt(111)interfaces was also observed.The 2D nanospace presents as anextended confined environment,which exhibits nano-confinement effect on the chemical reactions on the solidsurface.In-situ low energy electron microscopy(LEEM)/photoemission electron microscopy(PEEM),ambientpressure X-ray photoelectron spectroscopy(AP-XPS),polarization-modulation infrared reflection absorptionspectroscopy(PM-IRAS),and density functional theory(DFT)calculations reveal the nano-confinement effectfrom the graphene cover,which destablizes adsorption of CO on Pt(111)surfaces and promotes the catalytic COoxidation confined under graphene cover.CO intercalation and CO oxidation under BN cover has also beenexplored and a similar confinement of the BN cover on surface chemistry was observed.