Effective enhancement on methanol adsorption in Cu-BTC by combination of lithium-doping and nitrogen-doping functionalization
Grand canonical Monte Carlo method (GCMC) simulation combined with density functional theory calculation was used to investigate the adsorption in Cu-BTC, with nitrogen- and lithium-doping functionalization in order to understand the underlying performance of MOFs in methanol adsorption. A new N-doping structure, 3N–CuBTC, was theoretically constructed by replacing the carbon atoms with hydrogen connection in the organic linkers by nitrogen atoms. 3N–CuBTC shows higher methanol capacity in the measured pressure range due to the increased dispersive interactions caused by the lone electron pair of nitrogen atoms. Another Li-doping structure, 3Li–3N–CuBTC, was fabricated by doping Li atoms on the base of 3N–CuBTC. 3Li–3N–CuBTC demonstrated higher methanol capacity due to the stronger interaction between the induced Li atoms and methanol molecules. Furthermore, these two results can be attributed to the new adsorption sites created by N- and Li-doping, as revealed by the more exothermic binding energies on N-sites (− 49.37 kJ mol−1) and Li-sites (− 122.28 kJ mol−1) than Cu-sites (− 40.62 kJ mol−1). According to the simulation results, it can be concluded that both functionalized Cu-BTCs are capable of enhancing the methanol adsorption capacity of the framework at pressure from 0 to 14 kPa at 298 K.
We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21436005 and 21576094), the National High Technology Research and Development Program of China (No. 2013AA065005), SRFDP (No. 20130172110012).
- 26.Jeremias F, Fröhlich D, Janiak C, Henninger SK (2014) Water and methanol adsorption on MOFs for fast cycling heat transformation processes, new. J Chem 38:1846–1852Google Scholar
- 30.Sachdeva S, Venkatesh MR, Mansouri BE, Wei J, Bossche A, Kapteijn F, Zhang GQ, Gascon J, Smet LCPM, Sudholter EJR (2017) Sensitive and reversible detection of methanol and water vapor by in situ electrochemically grown CuBTC MOFs on interdigitated electrodes. Small 13:1064150–1064155Google Scholar
- 35.Yu C, Bourrelly S, Martineau C, Saidi F, Bloch E, Lavrard H, Taulelle F, Horcajada P, Serre C, Llewellyn PL, Magnier E, Devic T (2015) Functionalization of Zr-Based MOFs with alkyl and perfluoroalkyl groups: the effect on the water sorption behavior. Dalton Trans 44:19687–19692CrossRefGoogle Scholar
- 36.Huang HL, Zhang WJ, Yang F, Wang B, Yang QY, Xie YB, Zhong CL, Li JR (2016) Enhancing CO2 adsorption and separation ability of Zr(IV)-based metal–organic frameworks through ligand functionalization under the guidance of the quantitative structure–property relationship. Model Chem Eng J 289:247–253CrossRefGoogle Scholar
- 37.Debatin F, Thomas A, Kelling A, Hedin N, Bacsik Z, Senkovska I, Kaskel S, Junginger M, Müller H, Schilde U, Jäger C, Friedrich A, Holdt HJ (2010) In situ synthesis of an imidazolate-4-amide-5-imidate ligand and formation of a microporous zinc–organic framework with H2 and CO2-storage ability. Angew Chem Int Ed 49:1258–1262CrossRefGoogle Scholar
- 44.Dassault Systèmes BIOVIA (2017) Materials Studio 2017. Dassault Systèmes, San DiegoGoogle Scholar
- 46.Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE (2009) Gaussian 09, revision A. 02, vol 19. Gaussian, Inc, Wallingford, pp 227–238Google Scholar