Electronic band structures of pristine and chemically modified cellulose allomorphs

Divya Srivastava; Mikhail S Kuklin; Jouni Ahopelto; Antti J Karttunen

doi:10.1016/j.carbpol.2020.116440

Electronic band structures of pristine and chemically modified cellulose allomorphs

Carbohydr Polym. 2020 Sep 1:243:116440. doi: 10.1016/j.carbpol.2020.116440. Epub 2020 May 18.

Authors

Divya Srivastava¹, Mikhail S Kuklin¹, Jouni Ahopelto², Antti J Karttunen³

Affiliations

¹ Department of Chemistry and Materials Science, Aalto University, P.O. Box 16100, FI-00076, Aalto, Finland.
² VTT Technical Research Centre of Finland Ltd, P.O. Box 1000, FI-02044, VTT, Espoo, Finland.
³ Department of Chemistry and Materials Science, Aalto University, P.O. Box 16100, FI-00076, Aalto, Finland. Electronic address: antti.j.karttunen@iki.fi.

PMID: 32532390
DOI: 10.1016/j.carbpol.2020.116440

Abstract

We have investigated the structural properties, vibrational spectra, and electronic band structures of crystalline cellulose allomorphs and chemically modified cellulose with quantum chemical methods. The electronic band gaps of cellulose allomorphs I_α, I_β, II, and III₁ lie in the range of 5.0 to 5.6 eV. We show that extra states can be created in the band gap of cellulose by chemical modification. Experimentally feasible amidation of cellulose I_β with aniline or 4,4' diaminoazobenzene creates narrow bands in the cellulose band gap, reducing the difference between the occupied and empty states to 4.0 or 1.8 eV, respectively. The predicted states 4,4'diaminoazobenzene-modified cellulose I_β fall in the visible spectrum, suggesting uses in optical applications.

Keywords: Band structure; Cellulose; Density functional calculations; Density of states; Electronic properties; Quantum chemistry.

MeSH terms

Cellulose / analogs & derivatives*
Cellulose / chemistry*
Molecular Structure

Substances

Cellulose