Silver

Zero-Valent Reaction:

Synthesis Setup:

Chemicals:

Silver nitrate; 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazocyclotetradecane, acetone

Procedure:

Silver disproportionates in the presence of a tetraazocyclic amine (L above). The tetraazocyclic amine will complex the silver 2+ that is formed keeping it locked away from the layered material.

There is no need to prepare the glassware. Setup the reflux setup as shown. There is no need to use an air-free setup. Heat a solution of 0.01 g silver nitrate (AgNO₃) and 0.1g 5,5,7,12,12,14-hexamethyl-1,4,8,11- tetraazocyclotetradecane in 5 mL acetone in the round-bottom flask to just below reflux (48°C). Once heated, drop in the 2D material, free or suspended on a substrate, into the round bottom flask. Keep heating just below reflux for 4 hours. After 4 hours, remove the substrate or 2D crystal from solution and rinse with acetone or ethanol several times. Rinsing with heated acetone will help remove any other salt impurities that may end up on the substrate.

How much can be intercalated into Bi₂Se₃ nanoribbons:

AgNO₃	Tetroazocyclicamine	acetone	time	~ intercalated in Bi₂Se₃
0.01 g	0.1 g	5 mL	4 hours	50-60 atm % ± 5%

Relevant Publications:

K.J. Koski, C.D. Wessells, B.W. Reed, J.J. Cha, D. Kong, and Y.Cui, Chemical intercalation of zero-valent metals into 2D layered Bi₂Se₃ Nanoribbons. J. Am. Chem. Soc. 134, 13773 (2012).

M. Wang, D. Williams, G. Lahti, S. Teshima, D. Dominguez-Aguilar, K. J. Koski, Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides. 2D Materials, 5, 045005 (2018)

Supported by NSF DMR-1658019