Bismuth


Zero-Valent Reaction:

Bi

Synthesis Setup:

Reflux

Chemicals:

Bismuth chloride, Stannous chloride, acetone


Procedure:

Stannous Chloride (Sn(II) Cl2) is an excellent reducing agent and can be used to reduce many of the metal chlorides to a zero-valent species. The electrochemical redox potential favors oxidation of the tin halide and reduction of the metal halide. Bismuth, with an oxidation state of 2+ or 3+ can be reduced all the way to Bi(0).

Redox Potentials: SnCl2 → SnCl4   -0.1375
  Bi3+ + 2e- → Bi   0.308
    Total: 0.1705

There is no need to prepare the glassware before intercalation. Setup the reflux setup as shown. There is also no need to use an air-free setup. Prepare a stock solution of stannous chloride from 0.01 – 0.02 g of SnCl2 in 5 mL.

Heat a solution of 0.016 g bismuth(III) chloride in 5 mL acetone in the round-bottom flask to just below reflux (48°C). Once heated, drop the 2D material, free or suspended on a substrate, into the round bottom flask. Dropwise, add in the solution of tin(II) chloride very slowly over the course of 3 hours. Keep heating during this time at just below reflux. After 3 hours, and complete injection of the stannous chloride solution, wait an additional 30 – 45 mins with heating. After, remove the substrate or 2D crystal from solution and rinse with acetone or ethanol several times. Rinsing with heated acetone (~45°C) will help remove any other salt impurities that may end up on the substrate.


How much can be intercalated into Bi2Se3 nanoribbons:

Bi(III)Cl3 SnCl2 acetone time ~ intercalated in Bi2Se3
0.016 g 0.1 g 5 mL 3.75 hours ?? 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