Nanomaterials have a high surface-to-mass ratio and their surface properties significantly affect their features and application potential. Phosphorene, a single layer of black phosphorus (BP), was the first homoatomic two-dimensional material to be prepared after the discovery of graphene. The structure of phosphorene resembles the honeycomb arrangement of graphene, but its layers are buckled and highly anisotropic. We studied how this difference affects the surface properties of BP, namely the free surface energy and adsorption affinity of various organic molecules. Using inverse gas chromatography, we measured the total surface free energy of BP powder to be 90 mJ m-2 and showed that it was dominantly determined by dispersion forces, but, unlike on graphene, with a notable contribution from specific acid-base interactions. We further measured adsorption enthalpies of volatile organic compounds on BP and rationalized them using density functional theory calculations. Polar molecules showed an increased affinity due to a significant contribution of dipole-dipole interactions to the molecule-surface bonding, because the buckled surface of BP causes higher diffusion barriers than those on graphene, hinders molecular in-plane motion and supports mutual orientation of molecular dipoles over longer distances, in contrast to graphene.

Regional Centre of Advanced Technologies and Materials Department of Physical Chemistry Faculty of Science Palacký University Olomouc tř 17 listopadu 12 77 146 Olomouc Czech Republic

Zobrazit více v PubMed

Xia F., Wang H., Jia Y. Nat. Commun. 2014;5:4458. PubMed

Qiao J., Kong X., Hu Z.-X., Yang F., Ji W. Nat. Commun. 2014;5:4475. PubMed PMC

Wang X., Jones A. M., Seyler K. L., Tran V., Jia Y., Zhao H., Wang H., Yang L., Xu X., Xia F. Nat. Nanotechnol. 2015;10:517. PubMed

Liu H., Du Y., Deng Y., Ye P. D. Chem. Soc. Rev. 2015;44:2732. PubMed

Sofer Z., Sedmidubský D., Huber Š., Luxa J., Bouša D., Boothroyd C., Pumera M. Angew. Chem. 2016;128:3443. PubMed

Liu H., Neal A. T., Zhu Z., Luo Z., Xu X., Tománek D., Ye P. D. ACS Nano. 2014;8:4033. PubMed

Vogt P., De Padova P., Quaresima C., Avila J., Frantzeskakis E., Asensio M. C., Resta A., Ealet B., Le Lay G. Phys. Rev. Lett. 2012;108:155501. PubMed

Bianco E., Butler S., Jiang S., Restrepo O. D., Windl W., Goldberger J. E. ACS Nano. 2013;7:4414. PubMed

Gusmão R., Sofer Z., Pumera M. Angew. Chem., Int. Ed. 2017;56:8052. PubMed

Bridgman P. W. J. Am. Chem. Soc. 1914;36:1344.

Das S., Zhang W., Demarteau M., Hoffmann A., Dubey M., Roelofs A. Nano Lett. 2014;14:5733. PubMed

Li D., Del Rio Castillo A. E., Jussila H., Ye G., Ren Z., Bai J., Chen X., Lipsanen H., Sun Z., Bonaccorso F. Appl. Mater. Today. 2016;4:17.

Tran V., Soklaski R., Liang Y., Yang L. Phys. Rev. B. 2014;89:235319.

Li L., Yu Y., Ye G. J., Ge Q., Ou X., Wu H., Feng D., Chen X. H., Zhang Y. Nat. Nanotechnol. 2014;9:372. PubMed

Takao Y., Morita A. Physica B+C. 1981;105:93.

Sofer Z., Luxa J., Bouša D., Sedmidubský D., Lazar P., Hartman T., Hardtdegen H., Pumera M. Angew. Chem., Int. Ed. 2017;56:9891. PubMed

Engel M., Steiner M., Avouris P. Nano Lett. 2014;14:6414. PubMed

Du Y., Liu H., Deng Y., Ye P. D. ACS Nano. 2014;8:10035. PubMed

Kang K., Xie S., Huang L., Han Y., Huang P. Y., Mak K. F., Kim C.-J., Muller D., Park J. Nature. 2015;520:656. PubMed

Lewis E. A., Brent J. R., Derby B., Haigh S. J., Lewis D. J. Chem. Commun. 2017;53:1445. PubMed

Huang Y., Qiao J., He K., Bliznakov S., Sutter E., Chen X., Luo D., Meng F., Su D., Decker J., Ji W., Ruoff R. S., Sutter P. Chem. Mater. 2016;28:8330.

Mayorga-Martinez C. C., Sofer Z., Pumera M. Angew. Chem., Int. Ed. 2015;54:14317. PubMed

Cui S., Pu H., Wells S. A., Wen Z., Mao S., Chang J., Hersam M. C., Chen J. Nat. Commun. 2015;6:8632. PubMed PMC

Ho R., Heng J. Y. Y. KONA Powder Part. J. 2013;30:164.

Mohammadi-Jam S., Waters K. E. Adv. Colloid Interface Sci. 2014;212:21. PubMed

Lapčík L., Otyepka M., Otyepková E., Lapčíková B., Gabriel R., Gavenda A., Prudilová B. Curr. Opin. Colloid Interface Sci. 2016;24:64.

Blöchl P. E. Phys. Rev. B. 1994;50:17953. PubMed

Kresse G., Joubert D. Phys. Rev. B. 1999;59:1758.

Klimeš J., Bowler D. R., Michaelides A. Phys. Rev. B. 2011;83:195131.

Lazar P., Karlický F., Jurečka P., Kocman M., Otyepková E., Šafářová K., Otyepka M. J. Am. Chem. Soc. 2013;135:6372. PubMed

Brown A., Rundqvist S. Acta Crystallogr. 1965;19:684.

Lazar P., Martincová J., Otyepka M. Phys. Rev. B. 2015;92:224104.

Van Der Spoel D., Lindahl E., Hess B., Groenhof G., Mark A. E., Berendsen H. J. C. J. Comput. Chem. 2005;26:1701. PubMed

Jorgensen W. L., Tirado-Rives J. Proc. Natl. Acad. Sci. U. S. A. 2005;102:6665. PubMed PMC

van der Spoel D., Maaren V. P. J., Caleman C. Bioinformatics. 2012;28:752. PubMed

Sresht V., Pádua A. A. H., Blankschtein D. ACS Nano. 2015;9:8255. PubMed

Cheng A., Steele W. A. J. Chem. Phys. 1990;92:3867.

Shi B., Wang Y., Jia L. J. Chromatogr., A. 2011;1218:860. PubMed

Van Oss C. J., Good R. J., Chaudhury M. K. Langmuir. 1988;4:884.

Volpe C. D., Siboni S. J. Colloid Interface Sci. 1997;195:121. PubMed

Das S. C., Larson I., Morton D. A. V., Stewart P. J. Langmuir. 2011;27:521. PubMed

Karlický F., Otyepková E., Banáš P., Lazar P., Kocman M., Otyepka M. J. Phys. Chem. C. 2015;119:20535.

Ferguson A., Harvey A., Godwin I. J., Bergin S. D., Coleman J. N. 2D Mater. 2017;4:015040.

Lazar P., Otyepková E., Karlický F., Čépe K., Otyepka M. Carbon. 2015;94:804.

Otyepková E., Lazar P., Luxa J., Berka K., Čépe K., Sofer Z., Pumera M., Otyepka M. Nanoscale. 2017;9:19236. PubMed PMC

Lazar P., Otyepková E., Banáš P., Fargašová A., Šafářová K., Lapčík L., Pechoušek J., Zbořil R., Otyepka M. Carbon. 2014;73:448.

Otyepková E., Lazar P., Čépe K., Tomanec O., Otyepka M. Appl. Mater. Today. 2016;5:142.

Karlický F., Otyepková E., Lo R., Pitoňák M., Jurečka P., Pykal M., Hobza P., Otyepka M. J. Chem. Theory Comput. 2017;13:1328. PubMed PMC

Ferguson A., Caffrey I. T., Backes C., Coleman J. N., Bergin S. D. Chem. Mater. 2016;28:6355.

Shulenburger L., Baczewski A. D., Zhu Z., Guan J., Tománek D. Nano Lett. 2015;15:8170. PubMed

Hedgeland H., Fouquet P., Jardine A. P., Alexandrowicz G., Allison W., Ellis J. Nat. Phys. 2009;5:561.

Cabaleiro-Lago E. M., Hermida-Ramon J. M., Pena-Gallego A., Martinez-Nunez E., Fernandez-Ramos A. J. Mol. Struct.: THEOCHEM. 2000;498:21.

Kokalj A. Phys. Rev. B. 2011;84:045418.

Acetonitrile-assisted exfoliation of layered grey and black arsenic: contrasting properties