ORIGINAL PAPER Adsorption of light mercaptans over metal (Co, Cu, Fe, Ni) doped hexagonal boron nitride nanosheets: a first-principles study Zahra Moghadaszadeh 1 & Mohammad Reza Toosi 1 & Mohammad Reza Zardoost 1 Received: 27 December 2018 /Accepted: 4 April 2019 # Springer-Verlag GmbH Germany, part of Springer Nature 2019 Abstract Light mercaptans (R–SH, R = C 1 –C 4 ) as volatile malodorous and toxic compounds were theoretically adsorbed on metal (Co, Cu, Fe, Ni) doped hexagonal boron nitride (h-BN) nanosheets to obtain the adsorption energies of the mercaptans and electronic structures of the sheets before and after adsorption using the density functional theory method. The results indicate that doping B/ N vacancy h-BN sheets with the metals decreased E g compared to the pristine h-BN. Adsorption energies showed strong chemisorption of light mercaptans over metal doped h-BN. It is found that by increasing the alkyl chain in mercaptan the adsorption energy increases. Charge analysis and study of the correlation between variation of charge in the sulfur atom and the adsorption energy of mercaptan are presented. Keywords Adsorption . Light mercaptans . Hexagonal boron nitride . 2D materials Introduction Light mercaptans, such as methyl mercaptan (MM) and ethyl mercaptan (EM), are known as volatile sulfur compounds (VSCs) with high volatility, toxicity, and extremely low odor threshold [1]. Generally, they can be found in natural gas resources and as a byproduct of metabolism of natural com- pounds, such as asparagus, radishes, and organic matter in marshes. Light mercaptans as malodorous compounds have a strongly disagreeable odor and corrosion effects on iron alloys that can damage natural gas pipelines and different units of gas/oil refineries. In addition, they cause poisoning effects in catalysts used in various units of gas/oil refineries, such as steam reforming, Fischer–Tropsch, and methanol plants resulting in loss of activity [2]. Emission of mercaptans also leads to irritation in the eyes and nose and harmful effects for the nervous system at high concentrations. Several methods have been developed for the removal of mercaptans, such as catalytic oxidation [3], photocatalytic decomposition [4], and adsorptive removal by natural or synthetic adsorbents [5–8]. Two dimensional (2D) layered materials as new adsor- bents of gaseous molecules have recently drawn interest for theoretical and experimental applications of nano and optoelectronic devices. Among them, van der Waals solids, such as graphene, hexagonal BN (h-BN), and black phosphorene, have been applied to develop several quan- tum advanced devices [9]. Hexagonal-boron nitride is a 2D layered compound consisting of alternating boron and ni- trogen atoms in a honeycomb arrangement and sp 2 -bonded two-dimensional sheets. The layers of h-BN are held to- gether by weak van der Waals forces, similar to graphite. h- BN has recently gained attention because of its outstanding physical and chemical properties, such as high melting point, low density, high mechanical strength, oxidation re- sistance, and attractive thermal and electrical properties [10]. The pristine h-BN nanosheet is inherently an insula- tor according to its wide band gap energy (E g ), which is not suitable for electronic applications. However, some ad- vanced methods of h-BN synthesis have been presented for gas sensing applications [11–13]. Moreover, addition of impurities or making defects by a consequence of elec- tron irradiation or aggressive annealing treatments in dif- ferent reactive-ion-gaseous etching environments can pro- duce extremely fascinating properties in h-BN. Because of the different electronegativity of B and N, doping h-BN with transition metals can improve the sensitivity or ad- sorption of gases by changing the nature of the chemical bond of the h-BN surface after doping. Several theoretical * Mohammad Reza Toosi mrtoosi@gmail.com * Mohammad Reza Zardoost m1605chemist@yahoo.com 1 Department of Chemistry, Qaemshahr branch, Islamic Azad University, Qaemshahr, Iran Journal of Molecular Modeling (2019) 25:138 https://doi.org/10.1007/s00894-019-4030-7