Vol.:(0123456789) 1 3
Adsorption
https://doi.org/10.1007/s10450-018-9963-0
H
2
S adsorption and dissociation on Rh(110) surface: a first-principles
study
Tariq Usman
1
· Ming‑qiu Tan
1
Received: 15 March 2018 / Revised: 17 July 2018 / Accepted: 20 July 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018
Abstract
First-principle study based on density functional theory are used to scrutinize the mechanism of H
2
S adsorption and disso-
ciation over Rh(110) surface. For adsorption mechanisms, we probe the most favorite sites of H
2
S monomers over Rh(110)
surface. It is determined that H
2
S vigorously adsorbed over high symmetry adsorption sites with preferred long-bridge (LB)
site having adsorption energy − 1.00 eV, with no more than 0.50 eV, binding energy. Also we found that HS chemisorption is
higher as compared to H
2
S on Rh(110) surface having − 3.76 eV adsorption energy, where atomic S and H binding at hollow
and short-bridge site is more stronger. The energy barriers to split the bond of S–H in first and second H
2
S dehydrogenation
are 0.18–0.36 and 0.30 eV. To further investigate, electronic density of state are employed to illustrate the interaction of
adsorbed H
2
S with the surface of Rh(110), which is able to account for energy divergences of all species adsorbed on Rh(110)
surface. Hence, our calculated results confirm that H
2
S dissociation over Rh(110) surface is exothermic as well as an easy
process, however kinetically and thermodynamically the existence of atomic S avoid the breaking of H–S bond procedure.
Keywords Rh(110) surface · H
2
S · First-principle study · Adsorption · Dissociation
1 Introduction
Study of gas interaction with metal surfaces has revived
great interests in fundamental and surface science. Particu-
larly, a further best approach can furnish to propose cor-
rosion resistant structural’s metal. In these gases hydrogen
sulphide is the most notorious and violent gas and its mol-
ecules are pertinent for various causes. Initially hydrogen
sulphide is taken as a molecular scheme model to investigate
the phenomenon of corrosion owing to sulfur compounds.
In addition, H
2
S is a proverbial infectivity in syn-gas and
fossil-fuels that have vastly toxic impacts on metals and met-
als based catalyst uses for various reactions to deactivate
their catalyzing influence in petrochemical industries. The
H
2
S dissociation barriers are usually small due to weak H–S
bond particularly on transition metals (Hedge and White
1986; Blyth et al. 2003), primarily to rapid deposition of
sulfur and consequent sulfide formation. Also adsorbed sul-
fur is familiar owing to works like toxin, which decreases
decomposition of H
2
on metal surfaces (Wilke and Scheffler
1995), and a stern obstacle on transition metals to hydro-
gen desorption (Johnson and Madix 1981). At last one can
deduce that, the interaction of hydrogen atoms of H
2
S with
solid, embrittling metals such as Ni and Fe (Rice and Wang
1989; Srikrishnam and Liu 1975; Briant and Sieradzki
1989).
Rhodium is a multipurpose catalyst for diverse sorts of
reactions, during various spots its bustle go beyond like
platinum (Yates et al. 1979). The rhodium that profession-
ally catalyzed the reactions are hydrogenation of olefins
(Beeck 1950), deuterium swap by hydrocarbons (Anderson
and Kemball 1954), NH3 (Kemball 1952), hydrogenation
of benzene (12), Ketone and nitrogen oxide attenuation (12,
Shelef 1975), fabrication of nitric acid (14), and hydrogen
oxidation (12). In addition it can add CO into hydrocarbons,
as well as create methane and additional hydrocarbon such
as of CO and H
2
(Mills and Steffgen 1974). Platinum is dif-
ferent as rhodium because rhodium can eagerly smash C–O
bonds and also H–H, C–H and C–C bonds. Furthermore, it
has an affluent organometallic chemistry and in group type
is utilized in solution as a homogeneous catalyst (Castner
et al. 1978).
* Ming-qiu Tan
mqtan@zju.edu.cn
1
Department of Physics, Zhejiang University,
Hangzhou 310027, People’s Republic of China