Received: 6 November 2020 Revised: 28 May 2021 Accepted: 8 June 2021

DOI: 10.1002/er.6986

RESEARCH ARTICLE

Hydrogen adsorption on metal-functionalized benzene and

B-substituted benzene

Priyanka Tavhare1 | Elby Titus2 | Ajay Chaudhari1

1
Department of Physics, The Institute of
Science, Dr. Homi Bhabha State
University, Mumbai, India
2
Department of Mechanical Engineering,
Center for Automation and Technology
(TEMA), University of Averio, Aveiro,
Portugal
Correspondence
Ajay Chaudhari, Department of Physics,
The Institute of Science, Dr. Homi
Bhabha State University, Mumbai-400032,
India.
Email: ajaychau5@yahoo.com
Summary
Hydrogen storage properties of metal doped benzene complexes vary with
positions of boron atom substitution in a benzene ring at MP2/6-311++g(d,p)
level. Two carbon atoms of a benzene (C6H6) ring positioned at 1-2, 1-3 and
1-4 are replaced by two boron atoms and the structures named as BB1-2, BB1-3
and BB1-4, respectively. Further, pristine as well as boron substituted benzene
complexes are decorated with Li, Be,Ti and Ca atoms. C6H6Li, BB1-2Li, BB1-3Li
and BB1-4Li complexes can interact with three, three, two and three H2 mole-
cules, respectively, with 6.64, 6.82, 4.65 and 6.82 wt% H2 uptake capacities.
Only one H2 molecule gets adsorbed on each C6H6Be, BB1-2Be, BB1-3Be and
BB1-4Be complexes with respective H2 uptake capacity of 2.26, 2.32, 2.32
and 2.32 wt%. One additional hydrogen molecule gets adsorbed on
Ti(Ca) decorated boron substituted benzene than C6H6Ti(C6H6Ca) with respec-
tive H2 uptake capacity 7.54(7.98) and 6.02(9.46) wt%. Electron density of
metal atom gets altered significantly after adsorption of H2 molecules. The
averaged H2 adsorption energies with Gibbs free energy correction ΔEG are
found to be negative for all Li- and Ca-doped complexes indicates thermody-
namically unfavorable H2 adsorption where ΔEG values are positive for all Ti-
and Be-doped complexes at room temperature indicating thermodynamically
favorable H2 adsorption. Interaction between H2 molecules and Be- as well as
Ti-doped complexes is found to be stronger than Li- and Ca-doped complexes.
Be-doped complexes considered do not satisfy the target set by DOE regarding
H2 uptake capacity. Boron substitution improves molecular hydrogen uptake
of Benzene-Ti complex by 1.52 wt% and satisfy the target set by DOE. C6H6Li,
BB1-2Li, BB1-3Li and BB1-4Li complexes cannot be used for hydrogen storage
since hydrogen adsorption on these complexes is endothermic. Ti-doped boron
substituted complexes are found to more promising H2 storage material
because of their higher H2 uptake capacity as well as their strong interaction
with adsorbed hydrogen molecules than Li-, Be- and Ca-doped complexes.

KEYWORDS
benzene, boron substitution, H2 adsorption, metal-benzene complex, molecular dynamics
simulations

Int J Energy Res. 2021;1–17. wileyonlinelibrary.com/journal/er © 2021 John Wiley & Sons Ltd. 1
2 TAVHARE ET AL.
1 | INTRODUCTION
Emission due to burning of fossil fuels is a leading cause
of air pollution in the world. Heavily polluted fossil fuel
technology can be replaced by clean hydrogen fuel cell
technology. But the success of hydrogen economy can be
determined by the development of hydrogen production
and storage techniques. The US Department of Energy
(DOE) has modified hydrogen storage target to 4.5 wt%
by 2020, because the available hydrogen storage systems
fail to reach the DOE's previous target.1 The hydrogen
storage properties of organometallic complexes have pre-
viously been studied extensively.2-14 Maximum 24H2 gets
adsorbed on 6Li/C24 fullerene (12.7 wt%).2 The Li-doped
C70 fullerene is studied by Anafcheh et al.3 Hydrogen
uptake of Li-doped coronene has increased with doping
concentration of Li.4 Guo et al have studied H2 adsorp-
tion on imine-linked covalent organic framework with
the help of first-principles calculations.5 Ionization of Li
atom in Li-doped benzene can introduce a highly local-
ized region of positive charge which enhanced the H2
binding energy.6 Be-doped graphene interacts electrostat-
ically with adsorbed molecular hydrogens.7 More number
of molecular hydrogen gets adsorbed with an increasing
number of Be atoms in Be-doped C2H4 complex.8 Mei
et al have suggested Ti- and Ni-doped SWCNT for hydro-
gen adsorption using density functional theory.9 Xiao-
Dong et al have designed Ti-doped benzene grafted
tetrahydrido-silsequioxane complex for hydrogen stor-
age.10 He et al have found that Sc- and Ti-doped covalent
triazine-based complexes are suitable for H2 storage than
V-, Cr- and Mn-doped covalent triazine-based com-
plexes.11 Niaz et al have obtained interaction between
transition metal (TM) doped multidecker complexes and
H2 molecules.12 Adsorption of H2 molecule on benzene
was studied earlier by Hamel et al.13 Ma et al have found
unusual combination of chemisorption and physisorption
of H2 molecules on TiC6H6 complex.14 Adsorption of H2
molecules on both sides of Ti decorated boron nitride sys-
tem is found to be more favorable than the single-sided
adsorption.15 Phillips et al have fabricated thin films of
C6H6Ti successfully and studied its hydrogen adsorption
properties.16 Thin films of Ti-C2H4 complex were also
fabricated earlier and theoretical calculations on hydro-
gen storage capacity of Ti-C2H4 complex is in excellent
agreement with the experimental determination.17 Simi-
lar ring structures have also been suggested for hydrogen
storage.18,19 The structures suggested are Sc-, Ti- and V-
doped C4H4, C5H5 and C6H6 rings and Ti-doped C8H8
ring. The authors have shown that the number of hydro-
gen molecule adsorption on these structures is according
to the 18-electron rule. There are several theoretical and
experimental investigations in which Ti-Benzene
and other transition metal-Benzene complexes are stud-
ied. Bonding energies between various transition metal
(including Ti) and benzene have been obtained by
Chaquin et al using density functional theory (DFT).20
Thermochemistry of mono- and bis-benzene complexes
of first row transition metal ions from Ti to Cu has been
studied experimentally by Meyer et al and the obtained
bond energies are in agreement with the theoretical pre-
dictions and previous experimental determinations.21
Zheng et al have studied (Ti)n(Benzene)m cluster anion
using mass spectrometry and anion photoelectron spec-
troscopy and determined vertical detachment energies
and adiabatic electron affinities.22 Magnetic moments of
transition metal atoms supported on benzene have been
reported by Pandey et al using DFT.23 Hydrogen mole-
cules get physisorbed over VC6H6 complex with 4.48 wt%
H2 uptake capacity.24 The effect of charge on hydrogen
storage capacity of Sc2-C6H6 complex is also studied by
Guo et al.25
Organometallic complexes can store hydrogen in
molecular form which is essential for reversible hydrogen
storage. But when we go to the larger scale, the
hydrogen uptake capacity of a material gets decreased by
the clustering of metal atoms. Substitutional doping of
heteroatom in the organic substrate can solve the metal
clustering issue. Carbon materials with metal doping and
boron substitution have been suggested for hydrogen
storage.26-34 Li/Be/Sc doped pentalene complexes with
boron substitution have been studied earlier for molecu-
lar hydrogen adsorption.26,27 Scandium-doped boron
substituted porous graphene has shown hydrogen storage
capacity of 9.13 wt%.28 Li-doped B-substituted graphene
has been considered for H2 adsorption.29 Fullerenes with
beryllium doping is found to be feasible for molecular
hydrogen adsorption at room temperature.30 The binding
energy of Be to C60 fullerene is considerably increased
after boron substitution.31 More number of molecular
hydrogen gets adsorbed after B-substitution in transition
metal doped benzene complexes.32 Effect of substitution
of B/N in metal decorated benzene ring on H2 storage
properties was also studied.35-38 The H2 adsorption on
boron and nitrogen substituted benzene doped with
alkali metal/alkaline earth metal ions have also been
studied.34-36
In our previous work,37 we have compared hydrogen
adsorption properties of boron and nitrogen substituted
Ti-doped benzene (BTi). The position of B/N substitution
was 1-4 in a ring. It was found that H2 molecules interact
more strongly with N substituted BTi complex than
boron substituted BTi complex. The boron substituted
BTi complex is an electron deficient structure and accepts
an additional electron which is responsible for the
adsorption of one extra H2 molecule than BTi and
TAVHARE ET AL.
nitrogen substituted BTi complexes. The B substituted Ti-
doped benzene has shown higher H2 uptake capacity
than the N substituted Ti-doped benzene. In our previous
work37 only Ti-doped complexes were considered and
here we have considered Ti-, Be-, Ca- and Li-doped com-
plexes for comparison as well as effect of position of B
atom substitution on their hydrogen adsorption proper-
ties since it was found that position of nitrogen substitu-
tion in BTi complex affects the hydrogen adsorption
properties of a complex. The goal here is to see whether
doping of light metal atom such as Be, Ca and Li instead
of transition metal atom improves the H2 uptake capacity
and hydrogen adsorption properties. It will be interesting
to study whether position of B atom substitution in a ben-
zene ring also affects the H2 adsorption properties of BTi
since it was found earlier that position of N-atom substi-
tution in benzene ring in Ti-doped benzene affects the H2
adsorption, interaction with the substrate, and H2 desorp-
tion temperature.38 The H2 uptake capacity of Ti-doped
benzene is decreased whereas average H2 adsorption
energies are increased after N-substitution. Since lower
hydrogen storage capacity is found after N-substitution in
Ti-benzene, it is interesting to see whether similar effects
can be found after boron substitution also.
The aim of this work is to study and compare the
hydrogen storage properties of Li-, Be-, Ca- and Ti-doped
benzene complexes. The cohesive energy of Ti (4.85 eV/
atom) in bulk is higher than the cohesive energy of Li
(1.63 eV/atom), Ca (1.84 eV/atom) and Be (3.32 eV/
atom) in bulk and its lean toward high possibility of
aggregation of the Ti atoms than Li, Be and Ca atoms.
Clustering of Ti atoms can decrease the hydrogen storage
capacity of Ti-doped benzene complex whereas Li atoms
cannot adsorb H2 molecules at ambient conditions.
Boron substitution in benzene ring can be a solution for
these difficulties. Boron is having low atomic weight than
carbon which is beneficial to increase the hydrogen
uptake capacity of the metal doped organic material. We
have studied the impact of B-substitution on H2 adsorp-
tion properties of Li-/Be-/Ca-/Ti-doped benzene com-
plexes extensively with the help of charge analysis,
structural parameters, H2 adsorption energies, etc. Effect
of position of boron atom substitution in a benzene ring
on hydrogen adsorption properties of Li-/Be-/Ca-/Ti-
doped benzene is also studied.
2 | COMPUTATI ON AL DETAI L S
Electronic structure calculations are performed at
MP2/6-311++g(d,p) level.39 The averaged H2 adsorption
3
energies with zero point energy correction (ΔEZPE) and
averaged H2 adsorption energies with Gibbs free energy
correction (ΔEG) are calculated using total energy of
complexes obtained by Gaussian 09 program.40
The averaged H2 adsorption energies with zero point
energy correction (ΔEZPE) is calculated as:
  
ΔE ZPE ¼ E ZPE ½OM þ ðn*EZPE ½H2 Þ  EZPE OMðH2 Þn =n
ð1Þ
where EZPE[X] is the adsorption energy with zero point
energy correction, OM is the organometallic complex and
n is the number adsorbed H2 molecules.
Similarly, the averaged H2 adsorption energies with
Gibb's free energy correction (ΔEG) is also calculated as:
  
ΔEG ¼ E G ½OM þ ðn*E G ½H2 Þ – E G OMðH2 Þn =n ð2Þ
where EG[X] is the adsorption energy with Gibb's free
energy correction (thermal correction).
The H2 uptake capacity of a complex is calculated as:
H2 uptake capacity ðwt%Þ ¼f2n*Ar ½H=ð2n*Ar ½H þ Ar ½ComplexÞg
*100%
ð3Þ
where n is the number of adsorbed H2 molecules and Ar
[X] is atomic weight of X.
The boron substitution energy for benzene complex
with ZPE correction is calculated as:
E Sub ¼ E ZPE ½C6 H6  þ 2*E ZPE ½B – E ZPE ½BB1n  – 2*E ZPE ½C
ð4Þ
where EZPE[X] is the energy of X with zero point energy
correction and n is the position of second substituted
boron atom in benzene.
The van't Hoff equation has been used to calculate H2
desorption temperature for all the complexes.41,42
GaussSum has been used to obtain partial density of
states (PDOS).43 Atom centered density matrix propaga-
tion (ADMP) molecular dynamics (MD) simulations are
also performed for all the complexes at 300 K.44 Opti-
mized structure of respective complex is taken as an ini-
tial geometry for the ADMP simulation and time step is
set at 0.2 fs. The 300 K temperature is maintained with
the help of velocity scaling method throughout molecular
dynamics simulations.
4 TAVHARE ET AL.

3 | R ES U L T S A N D D I S C U S S I O N capacity of C6H6Li, BB1-2Li, BB1-3Li and BB1-4Li

complexes is found to be 6.64, 6.82, 4.65 and 6.82 wt%,
As shown in Figure 1, two carbon atoms at 1-2, 1-3, and respectively. Substitution of boron atoms does not have
1-4 position in benzene ring are replaced by two B atoms large effect on its capacity for storing hydrogen for
and the structures are named as BB1-2, BB1-3 and BB1-4, C6H6Be. B-substitution does not affect the number of
respectively. The energy required to substitute two boron adsorbed molecular hydrogens on Be doped benzene
atoms at 1-2, 1-3, and 1-4 position of benzene is found to complex. All Be-doped complexes can adsorb single H2
be 9.58, 10.42 and 8.80 eV, respectively. Negative molecule and not capable of satisfying the target set by
values of boron substitution energies indicate that the DOE regarding H2 uptake capacity. The H2 uptake capac-
substitution of boron atoms in benzene is an endothermic ity of C6H6Be, BB1-2Be, BB1-3Be and BB1-4Be complexes is
process. The aim behind the substitution of boron for car- found to be 2.26, 2.32, 2.32 and 2.32 wt%, respectively.
bon is not only to improve the H2 uptake capacity but Number of molecular hydrogen adsorbed on C6H6Ti is
also to increase binding of metal atom with benzene. The four thereby showing with 6.02 wt% storage capacity.
B atom is lighter 1.1997 u than C atom that helps to Due to boron substitution, one additional H2 molecule
lower the weight of a substrate and ultimately the hydro- gets adsorbed on Ti-doped benzene complex irrespective
gen storage capacity. Additional molecular hydrogens of position of boron atom substitution. B-substitution
may get adsorbed on organometallic structures after sub- improves molecular hydrogen uptake of C6H6Ti complex
stitution of an electron deficient boron atom. Figure 2 by 1.52 wt%. BB1-2Ti, BB1-3Ti and BB1-4Ti complexes
shows the electronic states for C6H6, BB1-2, BB1-3 and adsorb five molecular hydrogens each with 7.54 wt%
BB1-4 complexes. Electronic states in lower unoccupied uptake.
molecular orbitals (LUMO) region are found to be more
dense for all boron substituted benzene complexes than
that of C6H6. It indicates that the boron atom is an elec-
tron withdrawing substituent which makes benzene ring
electron deficient.
Substitution of boron atom in organic substrates is
not enough to improve hydrogen uptake capacity.45
Therefore, pristine and boron substituted benzene is dec-
orated with lithium (Li), beryllium (Be), calcium
(Ca) and titanium (Ti) and their interaction with H2 mol-
ecules is studied extensively. Maximum H2 adsorbed Li-,
Be-, Ti- and Ca-doped complexes are shown in Figures 3
to 6, respectively. From Figure 3, three molecular hydro-
gens interact with each complex containing Li even after
boron substitution except BB1-3Li complex on which only
two H2 molecules get adsorbed. Position of boron atom
in benzene ring affects number of molecular hydrogen F I G U R E 2 Energy states for benzene and B-substituted
adsorption on complexes doped with Li. The H2 uptake benzene [Colour figure can be viewed at wileyonlinelibrary.com]

F I G U R E 1 Geometry of optimized structures of (A) C6H6, (B) BB1-2, (C) BB1-3 and (D) BB1-4 complexes [Colour figure can be viewed at
wileyonlinelibrary.com]
TAVHARE ET AL. 5

F I G U R E 3 Geometry of
optimized Structures of
(A) C6H6Li(H2)3, (B) BB1-2Li
(H2)3, (C) BB1-3Li(H2)2 and
(D) BB1-4Li(H2)3 complexes
[Colour figure can be viewed at
wileyonlinelibrary.com]

F I G U R E 4 Geometry of
optimized Structures of
(A) C6H6Be(H2)1, (B) BB1-2Be
(H2)1, (C) BB1-3Be(H2)1 and
(D) BB1-4Be(H2)1 complexes
[Colour figure can be viewed at
wileyonlinelibrary.com]
6 TAVHARE ET AL.
Calcium-doped complexes show higher H2 uptake
capacity46-48 and also H2 molecules get adsorbed with
higher adsorption energies on substrates than Be.49
Therefore, we have studied the interaction of H2 mole-
cules with Ca-doped benzene complexes and obtained
results are compared with Be as well as Li- and Ti-doped
complexes. Five H2 molecules get adsorbed on C6H6Ca
complex whereas six H2 molecules on each BB1-2Ca,
BB1-3Ca and BB1-4Ca complex as shown in Figure 6. The
H2 uptake capacity of C6H6Ca complex is found to be
7.98 wt% and it increases to 9.46 wt% for each Ca-doped
boron substituted complex. The H2 uptake capacity of
Ca-doped complexes is higher than Li-, Be- and Ti-doped
complexes.
Binding energy (BE) of Li, Be, Ca and Ti atom to
C6H6 is lower than their respective cohesive energy in
bulk and found to be 0.26, 2.58, 0.38 and 2.76 eV, respec-
tively, and it gets significantly enhanced after boron sub-
stitution. The binding energy of Li, Be, Ca and Ti atom to
the boron substituted substrates before H2 adsorption has
increased in the range of 2.48 to 3.75, 1.73 to 3.90, 2.97 to
3.32 and 2.87 to 4.73 eV, respectively, than that with
F I G U R E 5 Geometry of
optimized structures of
(A) C6H6Ti(H2)4, (B) BB1-2Ti
(H2)5, (C) BB1-3Ti(H2)5 and
(D) BB1-4Ti(H2)5 complexes
[Colour figure can be viewed at
wileyonlinelibrary.com]
C6H6. The Li, Be, Ca and Ti atom bind strongly to the
BB1-3 substrate than the remaining boron substituted
substrates. There is no large change in metal binding
energy to the substrate before and after adsorption of H2
molecules for the Li-, Be- and Ca-doped complexes. How-
ever, a significant decrease in metal BE with substrate for
Ti-doped complexes after adsorption of molecular hydro-
gens is observed than that for before H2 adsorption.
Natural bond orbitals (NBO) charges for all the com-
plexes before and after adsorption of H2 molecules are
given in Table 1. The charge on Li atom in C6H6Li,
BB1-2Li, BB1-3Li and BB1-4Li complexes before H2 adsorp-
tion is found to be 0.79, 0.77, 0.82 and 0.84 e, respec-
tively. Though charge on Li atom is nearly equal in
BB1-3Li and BB1-4Li complexes, Li atom has donated
more charge to the substrate in BB1-4Li(3H2) complex as
compare to BB1-3Li(2H2) complex and therefore adsorbed
one additional H2 molecule. The charge on Be atom
before H2 molecule adsorption is almost equal in all Be-
doped complexes that results in only one H2 molecule
adsorption on each Be-doped complex. The Be atom of
BB1-4Be(1H2) complex transfers charge to the boron atom
TAVHARE ET AL.
F I G U R E 6 Geometry of
optimized Structures of
(A) C6H6Ca(H2)5, (B) BB1-2Ca
(H2)6, (C) BB1-3Ca(H2)6 and
(D) BB1-4Ca(H2)6 complexes
[Colour figure can be viewed at
wileyonlinelibrary.com]
of a substrate. It is more positively charged in BB1-4Be
(1H2) complex as compared to BB1-2Be(1H2) and BB1-3Be
(1H2) complexes. The charge on Ti atom remarkably
changed after molecular hydrogen adsorption as compare
to Li-, Be- and Ca-doped complexes. The charge on Ti
atom in all Ti-doped complexes becomes more negative
after H2 adsorption. The charge on Ti atom is found to be
0.91 e in C6H6Ti complex and becomes 1.29 and 1.45 e
in BB1-3Ti and BB1-4Ti complexes respectively but
remains almost same in BB1-2Ti complex. It indicates that
position of substituted boron atoms affects the charge of
Ti atom. In all H2 adsorbed complexes, metal atom
donates charge to the adsorbed H2 molecules as well as
the substrate. Higher charge on adsorbed molecular
hydrogens is found in complexes doped with beryllium
than lithium though Be-doped complexes adsorbed less
H2 molecules than Li-doped complexes. It indicates that,
no significant charge gets transferred from Li to the
adsorbed H2 molecules. This results in weaker interaction
of molecular hydrogens with the substrate. NBO charge
on adsorbed hydrogen molecules in C6H6Ti(4H2)
7
complex is found be 0.97 e and it increases after boron
substitution which results in one additional H2 molecule
adsorption.
Contribution of different orbitals of Li, Be, Ti and Ca
atom to the total density of states of corresponding com-
plex is computed and plotted in Figures 7 to 10, respec-
tively. In all Li-doped complexes, electron density of Li
atom has increased after H2 molecule adsorption except
in BB1-4Li(3H2). Electron density of Be atom is nearly
equal before and after molecular hydrogen adsorption in
complexes doped with beryllium. It may be due to
adsorption of only one hydrogen molecule on each of
these complexes. Ti-doped complexes interact with more
number of H2 molecules than Li- and Be-doped com-
plexes results in higher electron density of Ti atom after
adsorption of maximum H2 molecules than Li and Be
atom. Figures 11 to 14 show highest occupied molecular
orbitals (HOMO) and lowest unoccupied molecular
orbitals (LUMO) of Li-, Be-, Ti- and Ca-doped complexes,
respectively. The shape of the frontier molecular orbitals
of Li-, Be-, Ti- and Ca-doped complexes gets
8 TAVHARE ET AL.

T A B L E 1 NBO charge on C6H6M,

Complex C B M H2
BB1-2M, BB1-3M and BN1-4M complexes
C6H6Li(H2)3 1.86(1.98) — 0.51(0.79) 0.16 (where M = Li, Be and Ti) after
BB1-2Li(H2)3 1.51(1.57) 0.25(0.21) 0.51(0.77) 0.17 adsorption of H2 molecules
BB1-3Li(H2)2 2.13(2.21) 0.86(0.83) 0.60(0.82) 0.12
BB1-4Li(H2)3 2.01(2.12) 0.75(0.76) 0.52(0.77) 0.16
C6H6Be(H2)1 1.95(2.17) — 0.54(0.93) 0.20
BB1-2Be(H2)1 1.56(1.69) 0.06(0.02) 0.52(0.93) 0.24
BB1-3Be(H2)1 2.24(2.40) 0.73(0.68) 0.54(0.96) 0.25
BB1-4Be(H2)1 1.91(2.07) 0.48(0.37) 0.44(0.93) 0.25
C6H6Ti(H2)4 1.27(2.18) — 1.00(0.91) 0.97
BB1-2Ti(H2)5 1.36(1.82) 0.19(0.17) 0.98(0.90) 1.50
BB1-3Ti(H2)5 2.11(2.79) 0.79(0.71) 0.74(1.29) 1.44
BB1-4Ti(H2)5 1.93(2.73) 0.72(0.59) 0.87(1.45) 1.47
C6H6Ca(H2)5 2.05(1.85) — 1.09(0.59) 0.28
BB1-2Ca(H2)6 1.93(2.00) 0.17(0.20) 1.26(1.60) 0.17
BB1-3Ca(H2)6 2.71(2.82) 0.61(0.57) 1.27(1.67) 0.26
BB1-4Ca(H2)6 2.29(2.39) 0.23(0.14) 1.23(1.66) 0.25

Note: NBO charges in C6H6M, BB1-2M, BB1-3M, and BN1-4M complexes (where M = Li, Be, Ti and Ca) before
adsorption of H2 molecules are given in parenthesis.

F I G U R E 8 PDOS plots for Be atom in (A) C6H6Be(H2)1,

F I G U R E 7 PDOS plots for Li atom in (A) C6H6Li(H2)3,
(B) BB1-2Be(H2)1, (C) BB1-3Be(H2)1 and (D) BB1-4Be(H2)1
(B) BB1-2Li(H2)3, (C) BB1-3Li(H2)2 and (D) BB1-4Li(H2)3 complexes.
complexes. Blue dashed line indicates Fermi level which is set
Blue dashed line indicates Fermi level which is set to zero [Colour
to zero [Colour figure can be viewed at wileyonlinelibrary.com]
figure can be viewed at wileyonlinelibrary.com]
TAVHARE ET AL.
F I G U R E 9 PDOS plots for Ti metal atom in (A) C6H6Ti(H2)4,
(B) BB1-2Ti(H2)5, (C) BB1-3Ti(H2)5 and (D) BB1-4Ti(H2)5 complexes.
Blue dashed line indicates Fermi level which is set to zero [Colour
figure can be viewed at wileyonlinelibrary.com]
altered after adsorption of H2 molecules. The shape of
the LUMO is changed significantly after H2 adsorption
than HOMO for all complexes. The shape of HOMO and
LUMO of Li-doped complexes changes a little as compare
to Be- and Ti-doped complexes after adsorption of H2
molecules.
Bond lengths in Li-/Be-/Ti-/Ca-doped complexes
before and after adsorption of molecular hydrogens are
given in supplementary data as Table S1. The C─C, C─B
and B─B bond lengths in all complexes remain unaf-
fected after maximum H2 adsorption. The C─C bond
length is found to be shorter than the C─B and B─B
bond lengths in all the complexes. The C─M bond length
in all complexes is shorter than the B─M bond length.
The Li─H2 bond length is found to be 2.23, 2.35, 2.16 and
2.34 Å in C6H6Li(3H2), BB1-2Li(3H2), BB1-3Li(2H2)
and BB1-4Li(3H2) complexes, respectively. It indicates
that hydrogen molecules in BB1-3Li(2H2) are adsorbed at
shorter distances than that in remaining three Li-doped
complexes. The Be-H2 distance is nearly equal in all Be-
doped complexes. Elongated Ti─H2 bond in Ti-doped
complexes after boron substitution indicates weak inter-
action between B-substituted Ti-doped substrates and
hydrogen molecules than that for C6H6Ti substrate. The
9
F I G U R E 1 0 PDOS plots for Ca atom in (A) C6H6Ca(H2)5,
(B) BB1-2Ca(H2)6, (C) BB1-3Ca(H2)6 and (D) BB1-4Ca(H2)6
complexes. Blue dashed line indicates Fermi level which is set
to zero [Colour figure can be viewed at wileyonlinelibrary.com]
H2 molecules are adsorbed at longer distances in all Ca-
doped complexes than Li-, Be- and Ti-doped complexes.
The H─H bond length in isolated H2 molecule is found
to be 0.74 Å and it remains unaffected after adsorption
on Li- and Ca-doped complexes whereas it increases little
in Be-doped complexes. The H─H bond is significantly
elongated in complexes containing Ti in which maximum
number of hydrogen molecules are adsorbed. This elon-
gation of H─H bond is in association with Kubas type
interaction between the substrate and the molecules.
ΔEZPE and ΔEG values at ambient conditions are
given in Table 2. ΔEZPE values are found to be more posi-
tive for BB1-2Li(2H2) complex than remaining Li-doped
complexes. The ΔEG values obtained for substrates doped
with Be and Ti are more positive than that with Li. It
indicates that H2 molecules adsorbed weakly on latter
than the former. ΔEG values are negative for the com-
plexes containing Li indicate that their formation is not
favorable at given thermodynamic conditions. The ΔEG
value for C6H6Be(1H2), BB1-2Be(1H2), BB1-3Be(1H2) and
BB1-4Be(1H2) complexes is found to be 0.06, 0.08, 0.10
and 0.19 eV, respectively, and these values show thermo-
dynamically more favorable H2 adsorption than that on
Be-doped borane and carborane complexes.50 For the
10 TAVHARE ET AL.

F I G U R E 1 1 Molecular orbitals of
Li-doped complexes [Colour figure can
be viewed at wileyonlinelibrary.com]

F I G U R E 1 2 Molecular orbitals of
Be-doped complexes [Colour figure can
be viewed at wileyonlinelibrary.com]

F I G U R E 1 3 Molecular orbitals of
Ti-doped complexes [Colour figure can
be viewed at wileyonlinelibrary.com]
TAVHARE ET AL. 11

FIGURE 14 Molecular orbitals of Ca-doped complexes [Colour figure can be viewed at wileyonlinelibrary.com]

T A B L E 2 ΔEZPE and ΔEG values in eV at ambient conditions substitution has enhanced the interaction between com-
for C6H6M, BB1-2M, BB1-3M, and BN1-4M complexes (where M = plexes doped with Be and hydrogen molecule, but the
Li, Be, Ti and Ca) after H2 adsorption opposite is true for the Ti-doped complexes. ΔEG values
show that H2 adsorption is thermodynamically favorable
Energy (eV)
at ambient condition only for BB1-2Be, BB1-3Be, BB1-4Be,
Complex ΔEG ΔEZPE C6H6Ti and BB1-4Ti complexes. For the remaining com-
C6H6Li(H2)3 0.24 0.01 plexes it is unfavorable at ambient conditions. The H2
BB1-2Li(H2)3 0.24 0.03 adsorption energy with Gibb's free energy correction is
BB1-3Li(H2)2 0.20 0.03 found to be negative for all Ca-doped complexes. It indi-
cates that formation of Ca-doped complexes is energeti-
BB1-4Li(H2)3 0.20 0.01
cally not favorable at ambient conditions. ΔEZPE values
C6H6Be(H2)1 0.06 0.24
are positive for all complexes except BB1-2Li(H2)3 and
BB1-2Be(H2)1 0.08 0.37 C6H6Ca(H2)5 complexes and it is due to the weak interac-
BB1-3Be(H2)1 0.10 0.39 tions of H2 molecules with these complexes than
BB1-4Be(H2)1 0.19 0.48 remaining complexes.
C6H6Ti(H2)4 0.17 0.47 Pressure and temperature range for thermodynami-
cally favorable hydrogen adsorption can be decided by
BB1-2Ti(H2)5 0.01 0.29
calculating ΔEG values at different temperature and pres-
BB1-3Ti(H2)5 0.01 0.28
sure. The difference in ΔEG values with respect to tem-
BB1-4Ti(H2)5 0.07 0.37 perature and pressure can be seen in Figures 15 and 16,
C6H6Ca(H2)5 0.33 0.06 respectively. From Figure 15A, ΔEG values are found to
BB1-2Ca(H2)6 0.25 0.01 be negative for BB1-2Li(3H2) complex at entire tempera-
BB1-3Ca(H2)6 0.24 0.02 ture range considered here, whereas for remaining Li-
BB1-4Ca(H2)6 0.24 0.03 doped complexes it found to be positive below 10 K. ΔEG
values for the C6H6Be(1H2) complex become positive
below 250 K whereas it is positive for all boron
substituted Be doped complexes at all temperatures con-
C6H6Ti(4H2), BB1-2Ti(5H2), BB1-3Ti(5H2) and BB1-4Ti sidered here. ΔEG values are more positive for BB1-4Be
(5H2) complexes, ΔEG value is found to be 0.17, 0.01, (1H2) complex among all the complexes containing Be
0.01 and 0.07 eV, respectively. It indicates that boron for entire temperature and pressure range considered
12
F I G U R E 1 5 Temperature dependent Gibbs free energy
corrected H2 adsorption energies for (A) Li-doped, (B) Be-doped,
(C) Ti-doped and (D) Ca-doped C6H6, BB1-2, BB1-3 and BB1-4
complexes after H2 adsorption [Colour figure can be viewed at
wileyonlinelibrary.com]
here. It indicates stronger interaction of adsorbed mole-
cules with BB1-4Be substrate than the remaining Be-
doped substrates. Unlike Be-doped complexes, ΔEG
values for Ti-doped complexes are found to be positive
for C6H6Ti(4H2) complex for the entire range of tempera-
ture considered here. ΔEG values become positive below
350 K for BB1-4Ti complex and below 300 K for BB1-2Ti
and BB1-3Ti complexes. The negative ΔEG values at dif-
ferent pressure for all Li doped complexes shows that the
formation of all these complexes is an endothermic pro-
cess at 298.15 K and entire pressure range considered
here. ΔEG value for C6H6Be(1H2) complex is negative at
1 atm pressure and becomes positive at higher pressure,
whereas for all Be-doped boron substituted complexes at
entire pressure range ΔEG is positive. It indicates thermo-
dynamically favorable hydrogen adsorption at high pres-
sure than 1 atm and room temperature on complexes
doped with Be. The ΔEG values for all Ti-doped com-
plexes become more positive at higher pressure, indicat-
ing thermodynamically more favorable H2 adsorption
at higher pressure. Figures 15 and 16 show that the
adsorption of H2 molecules on C6H6Ca complex is
TAVHARE ET AL.
F I G U R E 1 6 Pressure dependent Gibbs free energy corrected
H2 adsorption energies for (A) Li-doped (B) Be-doped, (C) Ti-doped
and (D) Ca-doped C6H6, BB1-2, BB1-3 and BB1-4 complexes after H2
adsorption [Colour figure can be viewed at wileyonlinelibrary.com]
thermodynamically unfavorable at all temperature and
pressure range considered here whereas it is possible for
BB1-3Ca and BB1-4Ca complexes below 50 K and 1 atm.
Pressure. Though H2 uptake capacity of Ca-doped com-
plexes is high, the interaction of H2 molecules with these
complexes is found to be weak which results in negative
values of Gibb's free energy corrected H2 adsorption
energy.
The interaction energies between two molecules in a
same H2 adsorbed complexes are calculated and given in
Table 3. Interaction between adsorbed H2 molecules and
metal doped complexes are found to be attractive for all
Li-, Be-, Ti- and Ca-doped complexes. Interaction ener-
gies between H2 molecules and metal doped complexes
are found to be higher for Be and Ti containing com-
plexes than Li- and Ca-doped complexes. In Li-doped
complexes, the interaction energy of BB1-3Li substrate
with adsorbed molecules is more attractive than
remaining Li-doped complexes. Interaction energies for
C6H6Be complex and H2 molecules becomes more attrac-
tive after boron substitution. The interaction energy for
the hydrogen molecules adsorbed at shorter distances
from the metal doped complexes is more attractive. Inter-
action between most of the H2 molecules is found to be
weaker and repulsive in all the complexes. Interaction
 TAVHARE ET AL.

TABLE 3 Interaction energies for C6H6M, BB1-2M, BB1-3M, and BN1-4M complexes (where M = Li, Be, Ti and Ca) after H2 adsorption at MP2/6-311++g(d,p) level of theory

Interaction energy (kcal/mol)

Li Be Ti Ca

Interaction energy term C6H6 BB1-2 BB1-3 BB1-4 C6H6 BB1-2 BB1-3 BB1-4 C6H6 BB1-2 BB1-3 BB1-4 C 6H 6 BB1-2 BB1-3 BB1-4
OM-1H2 1.22 0.90 2.18 1.78 9.65 12.04 12.26 15.00 14.25 21.93 16.80 22.57 6.13 1.09 2.14 3.06
OM-2H2 1.22 0.34 2.18 1.86 — — — — 22.88 13.78 4.03 17.15 10.03 1.31 1.52 3.06
OM-3H2 1.96 2.32 — 1.78 — — — — 26.95 2.44 19.92 17.15 5.04 0.58 2.32 2.50
OM-4H2 — — — — — — — — 14.22 25.21 19.94 22.58 6.12 1.30 1.88 3.65
OM-5H2 — — — — — — — — — 18.00 16.81 3.68 5.06 3.64 2.66 2.50
OM-6H2 — — — — — — — — — — — — — 0.58 2.68 2.12
1H2-2H2 0.24 0.19 0.23 0.17 — — — — 1.19 1.32 1.71 2.12 0.01 0.08 0.34 0.51
1H2-3H2 0.13 0.18 — 0.19 — — — — 5.89 2.32 0.01 2.12 0.16 0.12 0.01 0.01
1H2-4H2 — — — — — — — — 0.02 0.02 2.33 0.01 0.23 0.08 0.09 0.01
1H2-5H2 — — — — — — — — — 1.55 2.43 1.49 0.01 0.15 0.01 0.24
1H2-6H2 — — — — — — — — — — — — — 0.12 0.36 0.12
2H2-3H2 0.13 0.14 — 0.19 — — — — 1.74 2.12 1.99 0.01 0.37 0.27 0.33 0.24
2H2-4H2 — — — — — — — — 1.19 3.27 1.99 2.13 0.001 0.004 0.1 0.01
2H2-5H2 — — — — — — — — — 0.01 1.71 2.62 0.37 0.24 0.01 0.01
2H2-6H2 — — — — — — — — — — — — — 0.01 0.01 0.12
3H2-4H2 — — — — — — — — 5.89 1.19 2.56 2.13 0.01 0.01 0.11 0.39
3H2-5H2 — — — — — — — — — 4.14 2.33 2.61 0.08 0.01 0.33 0.01
3H2-6H2 — — — — — — — — — — — — — 0.49 0.01 0.08
4H2-5H2 — — — — — — — — — 2.32 0.01 1.48 0.16 0.24 0.08 0.39
4H2-6H2 — — — — — — — — — — — — — 0.27 0.12 0.16
5H2-6H2 — — — — — — — — — — — — — 0.01 0.22 0.08

Note: OM is the organometallic complex and iH is the ith hydrogen molecule in a complex.
13
14 TAVHARE ET AL.

energies obtained for H2 molecules are more repulsive in

Ti-doped substrates than the Li-doped substrates.
The temperature required to desorb hydrogen mole-
cules from complexes are calculated by van't Hoff equa-
tion. The hydrogen desorption temperature for all
complexes doped with Li and Ca is found to be below
40 K which indicates weaker interaction of H2 molecules
with Li- and Ca-doped complexes. The H2 desorption
temperature for C6H6Be(1H2) complex is found to be
308 K and it has increased by 167, 192 and 308 K for
BB1-2Be(1H2), BB1-3Be(1H2) and BB1-4Be(1H2) complexes,
respectively. The H2 molecules can be desorbed at
603, 372, 359 and 475 K from C6H6Ti(4H2), BB1-2Ti(5H2),
BB1-3Ti(5H2) and BB1-4Ti(5H2) complexes, respectively.
The energy difference between the highest occupied
molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) is also obtained. The larger
HOMO-LUMO (H-L) gap always refers to higher kinetic
stability and lower chemical reactivity. The HOMO-
LUMO gap for C6H6Li complex is found to be 4.46 eV
and it is increased by 2.92, 3.78 and 2.75 eV for BB1-2Li,
BB1-3Li and BB1-4Li complex, respectively. The HOMO- F I G U R E 1 7 Trajectories of time evolution of distance of H2
LUMO gap for all Li-doped complexes slightly decreases molecules from respective Li atom in (A) C6H6Li(H2)3, (B) BB1-2Li
with successive adsorption of H2 molecules. The HOMO- (H2)3, (C) BB1-3Li(H2)2, (D) BB1-4Li(H2)3 complexes [Colour figure
can be viewed at wileyonlinelibrary.com]
LUMO gap for C6H6Be, BB1-2Be, BB1-3Be and BB1-4Be
complexes before H2 adsorption is found to be 6.47, 7.73,
8.71 and 7.77 eV, respectively, whereas it little decreases
for all Be-doped complexes after H2 adsorption. The
HOMO-LUMO gap for BB1-2Ti, BB1-3Ti and BB1-4Ti and
C6H6Ti complexes is found to be 6.75, 7.14, 6.42
and 5.24 eV, respectively. The HOMO-LUMO gap for
C6H6Ti and BB1-3Ti complexes increases to 7.14 and
8.73 eV, respectively, after adsorption of first H2 mole-
cules and again decrease to 5.47 and 8.04 eV, respectively,
when second H2 molecule gets adsorbed. It is due to the
fact that the first hydrogen molecule gets dissociated and
adsorbed in atomic form on C6H6Ti and BB1-3Ti com-
plexes. The HOMO-LUMO gap for C6H6Ca, BB1-2Ca,
BB1-3Ca and BB1-4Ca complexes is found to be 4.41(4.31),
5.31(5.96), 6.16(6.93) and 5.03(5.87) eV, respectively,
before(after) adsorption of H2 molecules. In Li-, Be- and
Ti-doped complexes, metal doped BB1-3 complex is found
to be more stable with higher HOMO-LUMO gap than
the remaining complexes.
Atom centered density matrix propagation molecular
dynamics (ADMP-MD) simulations are performed for all F I G U R E 1 8 Trajectories of time evolution of distance of H2
these complexes at 300 K using MP2/6-311++g(d,p) level molecules from respective Be atom in (A) C6H6Be(H2)1, (B) BB1-2Be
of theory. ADMP-MD simulation is initialized by using (H2)1, (C) BB1-3Be(H2)1, (D) BB1-4Be(H2)1 complexes [Colour figure
optimized structure of respective complex. Figure 17A can be viewed at wileyonlinelibrary.com]
shows that not a single H2 molecule remain adsorbed on
C6H6Li complex at 300 K during the simulations and flies H2 molecule each, whereas both H2 molecules fly away
away immediately. In Li-doped boron substituted com- from BB1-3Li complex. As shown in Figure 18, the only
plexes, BB1-2Li and BB1-4Li complexes can hold only one H2 molecule remain adsorbed on all the Be-doped
TAVHARE ET AL.
F I G U R E 1 9 Trajectories of time evolution of distance of H2
molecules from respective Ti metal atom in (A) C6H6Ti(H2)4,
(B) BB1-2Ti(H2)5, (C) BB1-3Ti(H2)5, (D) BB1-4Ti(H2)5 complexes
[Colour figure can be viewed at wileyonlinelibrary.com]
complexes and oscillates between 1.5 and 2.2 Å.
Figure 19 shows the trajectories of adsorbed H2 mole-
cules from Ti atom of respective complexes. Three, three,
two and four hydrogen molecules remain adsorbed on
C6H6Ti, BB1-2Ti, BB1-3Ti and BB1-4Ti complexes, respec-
tively, at 300 K during ADMP-MD simulations. The H2
uptake capacity of C6H6Ti, BB1-2Ti, BB1-3Ti and BB1-4Ti
complexes obtained from electronic structure calculations
is decreased by 1.44, 2.87, 4.38 and 1.41 wt% during
ADMP-MD simulations. Figure 20 shows that during the
ADMP simulations, not a single H2 molecule remains
adsorbed on any of the Ca-doped complexes at 300 K and
flies away instantly, with the exception of the BB1-4Ca
complex. On the BB1-4Ca complex, only one H2 molecule
remains adsorbed.
MD simulations performed at temperature T = 300 K
supports the DFT results in the sense that when the ΔEG
value is close to zero at T, most of the adsorbed H2 mole-
cules in an initial geometry of MD simulation remain
adsorbed during the simulations. If the simulations are
performed at 300 K where ΔEG value is away from zero
(negative), some or all of the adsorbed H2 molecules in
an initial geometry of MD simulation fly away during the
simulations.
15
F I G U R E 2 0 Trajectories of time evolution of distance of H2
molecules from respective Ti metal atom in (A) C6H6Ca(H2)5,
(B) BB1-2Ca(H2)6, (C) BB1-3Ca(H2)6, (D) BB1-4Ca(H2)6 complexes
[Colour figure can be viewed at wileyonlinelibrary.com]
C6H6Li, BB1-2Li, BB1-3Li and BB1-4Li complexes
cannot be used for hydrogen storage since hydrogen
adsorption on these complexes is endothermic as can be
seen from the negative ΔEG values. The H2 adsorption on
these complexes is thermodynamically unfavorable, that
is, endothermic and these complexes are not suitable for
storing hydrogen at ambient conditions. The interaction
between H2 molecules and C6H6Li, BB1-2Li, BB1-3Li and
BB1-4Li complexes is very weak. Ti-doped boron
substituted complexes are found to more promising H2
storage material because of their higher H2 uptake capac-
ity as well as their strong interaction with adsorbed
hydrogen molecules than Li-, Be- and Ca-doped
complexes.
4 | CONCLUSIONS
The hydrogen storage capacity of benzene doped with Li,
Be, Ca and Ti is found to be 6.64, 2.26, 7.98 and 6.02 wt%,
respectively, and it gets enhanced after boron substitution
for all complexes except BB1-3Li complex. In Li-doped
boron substituted complexes, charge transfer between Li
atom and substrate varies with the position of boron
16
atom and it affects the H2 uptake capacity of these com-
plexes. Adsorption of H2 molecules on Li-, Be- and Ti-
doped complexes is also confirmed from PDOS calcula-
tions. The H2 uptake capacity obtained from electronic
structure calculations for all Li- and Ti-doped complexes is
decreased during the ADMP-MD simulations, but it
remains the same for Be-doped complexes. Ti-doped com-
plexes interact with more number of H2 molecules than Li-
and Be-doped complexes results in higher electron density
of Ti atom after adsorption of maximum H2 molecules than
Li and Be atom. Hydrogen storage capacity of Li-doped sub-
strates is satisfying the target of DOE but their interaction
with H2 molecules is very weak even at lower temperature.
Though, Be-doped complexes can adsorb hydrogen mole-
cules at ambient conditions with thermodynamically favor-
able adsorption, their H2 uptake capacity does not satisfy
the DOE target. The H2 adsorption on all Li- and Ca-doped
complexes is thermodynamically unfavorable whereas it is
thermodynamically favorable on Ti- and Be-doped com-
plexes at room temperature. Though more number of H2
molecules get adsorbed on Ca-doped boron substituted ben-
zene, H2 adsorption on these complexes is thermodynami-
cally unfavorable. In conclusion, Ti-doped boron
substituted complexes are found to more promising H2 stor-
age material because of their higher H2 uptake capacity as
well as their strong interaction with adsorbed hydrogen
molecules than Li-, Be- and Ca-doped complexes.
A C K N O WL E D G E M E N T
P.T. is thankful to DST, New Delhi, for financial support
in terms of Women's Scientist Fellowship (SR/WOS-A/
PM-33/2017).
CONFLICT OF INTEREST
The authors declare that there are no conflicts of
interest regarding the publication of this paper.
DATA AVAILABILITY STATEMENT
Data available on request from the authors.
ORCID
Ajay Chaudhari https://orcid.org/0000-0002-4110-4493
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SU PP O R TI N G I N F O RMA TI O N
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.
How to cite this article: Tavhare P, Titus E,
Chaudhari A. Hydrogen adsorption on metal-
functionalized benzene and B-substituted benzene.
Int J Energy Res. 2021;1–17. https://doi.org/10.
1002/er.6986