Applied Surface Science

Ti-decorated nitrogen-rich BeN4 monolayer for reversible hydrogen storage: DFT

investigations
--Manuscript Draft--

Manuscript Number: APSUSC-D-22-18443

Article Type: Full Length Article

Keywords: Hydrogen Storage; 2D materials; BeN4 monolayer; Desorption temperature; DFT;

Molecular Dynamics

Corresponding Author: Brahmananda Chakraborty, Ph.D.

Bhabha Atomic Research Centre
Mumbai, INDIA

First Author: Ravi Trivedi, PhD

Order of Authors: Ravi Trivedi, PhD

Surinder Kaur, PhD

Nandini Garg, PhD

Brahmananda Chakraborty

Abstract: In the present report, the application of titanium decoration on the nitrogen-rich BeN4
monolayer for hydrogen storage is studied by means of Density Functional Theory
(DFT). BeN4 is made up of five and six-membered rings and has been synthesized
using high-pressure nanofabrication in the recent past. The binding energy of the Ti-
decorated BeN4 monolayer comes out to be -2.04 eV indicating that an energetically
stable complex is formed after metal decoration. The spin-polarized partial density of
states (PDOS) implies that semimetal BeN4 becomes magnetic after Ti decoration.
The charge transfer analysis validates transfer of charge from the Ti metal atom toward
the BeN4 monolayer. The Ti-decorated BeN4 can bind 7H2 molecules via Kubas
interactions with average adsorption energy and desorption temperature of -0.36
eV/H2 and 512 K, correspondingly satisfying DOE’s criteria. The ab initio molecular
dynamics simulations ensure the structural integrity of the BeN4+Ti complex at 300 K.
The high diffusion energy barrier reduces the probability of metal-metal clustering. The
storage capacity of the BeN4+Ti complex comes out to be 14.21 gravimetric wt% of
hydrogen. The present  study signifies that the Ti-decorated nitrogen-rich BeN4
monolayer has the potential to fulfill the requirements to be considered as an energy
storage material.

Suggested Reviewers: Utpal Sarkar, PhD

Professor, Assam University
utpalchemiitkgp@gmail.com
He has lots of experience on nanomaterials by using First Principal Simulation
techniques.

Yoshiyuki Kawazoe, PhD

Professor, Tohoku University New Industry Creation Hatchery Center
kawazoe@e-workshop.co.jp
He is working on hydrogen storage materials He is also the founder of Asian
Consortium on Computational Materials Science (ACCMS), and involving high level
research on computational materials science

Prafulla Jha, PhD

Professor, The Maharaja Sayajirao University of Baroda
prafullaj@yahoo.com
Sound knowledge in this field.

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Declaration

Declaration of interests

☐The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☒The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

Ravi Trivedi reports financial support was provided by Science and Enginerring Research Board, India.
Cover Letter

Dr. Brahmananda Chakraborty

Bhabha Atomic Research Centre
Mumbai 400085, India.
Email- brahma@barc.gov.in
Phone- 91-2225592057
Fax: +91-22-25505150

To,
The Editor in Chief
Applied Surface Science

Dear Sir,
I am enclosing herewith an original research article entitled “Ti-decorated nitrogen-rich
BeN4 monolayer for reversible hydrogen storage: DFT investigations” authored by
Ravi Trivedi, Surinder Kaur, Nandini Garg , Brahmananda Chakraborty for consideration
for publication in “Applied Surface Science”. I confirm that the above submission has
not been published before and is not under consideration for publication elsewhere. The
following are the major highlights of our work:
Hydrogen has the potential to be considered a replacement for conventional fossil fuels,
the onboard storage, and transportation of hydrogen need to be addressed fully. In this
direction, although a wide range of two-dimensional materials has been explored in the
past, but nitrogen-rich nanomaterials got a little less attention. Recently, a new two-
dimensional material i.e. Beryllonitrene was synthesized by applying a high-pressure
fabrication technique which opened a unique category of 2D materials represented as
MN4 [Phys. Rev. Lett. 126 (2021) 175501] and found that BeN4 monolayers have great
potential in energy storage. Keeping this in mind, in the present work we studied the
application of titanium atom (Ti) decoration on the nitrogen-rich BeN 4 monolayer for
reversible hydrogen storage by employing the quantum computational approach using the
Density Functional Theory along with GGA exchange correlation functional. The
titanium decorated BeN4 with a binding energy value of -2.04 eV indicating the energetic
stability and the average adsorption energy of successive addition of H 2 is -0.36 eV
fulfilling DOE-US conditions. The gravimetric hydrogen uptake comes out to be 14.21
wt% for the present system quite higher than the DOE-US requirements as well as
previously studied two-dimensional metal decorated nanomaterials also AIMD
simulations predict the thermal stability of the material.

We feel that this work will significantly advance an area of energy research that pushes
the field in a new direction and/or enables a technology. We strongly believe that this
work will match the strict standards set by “Applied Surface Science” and we look
forward to your decision.

With best regards

Brahmananda Chakraborty
brahma@barc.gov.in

Date: 05/12/2022
Graphical Abstract (for review) Click here to access/download;Graphical Abstract (for
review);Graphical_Abstract.doc

Graphical Abstract
Highlights (for review)

Highlights
1. Application of titanium atom (Ti) decoration on the nitrogen-rich BeN4
monolayer for hydrogen storage is studied by means of Density Functional
Theory (DFT).
2. The Ti-decorated BeN4 (BeN4+Ti) can bind seven hydrogen molecules via Kubas
interactions with average adsorption energy and desorption temperature of -0.36
eV/H2 and 512 K, correspondingly satisfying DOE’s criteria.
3. The high diffusion energy barrier reduces the probability of metal-metal
clustering formation.
4. The storage capacity of the BeN4+Ti complex comes out to be 14.21 gravimetric
wt% of hydrogen
Manuscript Click here to view linked References

Ti-decorated nitrogen-rich BeN4 monolayer for reversible hydrogen storage: DFT

investigations

Ravi Trivedi1*, Surinder Kaur3, Nandini Garg1,2 , Brahmananda Chakraborty1,2*

1
High Pressure and Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre,
Trombay, Mumbai-400085, India
2
Homi Bhabha National Institute
3
Department of Chemistry, Indian Institute of Ropar, Rupnagar, Punjab - 140001, India
brahma@barc.gov.in

Abstract

The metal-decorated two-dimensional materials have the potential to be considered as

onboard hydrogen storage materials, as they have a high surface area and fast kinetics. Here,
the application of titanium atom (Ti) decoration on the nitrogen-rich BeN4 monolayer for
hydrogen storage is studied by means of Density Functional Theory (DFT). BeN4 is made up
of five and six-membered rings and has been synthesized using high-pressure nanofabrication
in the recent past. The binding energy of the Ti-decorated BeN4 monolayer comes out to be -
2.04 eV indicating that an energetically stable complex is formed after metal decoration. The
spin-polarized partial density of states (PDOS) implies that semimetal BeN4 becomes
magnetic after Ti decoration. The charge transfer analysis validates transfer of charge from
the Ti metal atom toward the BeN4 monolayer. The Ti-decorated BeN4 (BeN4+Ti) can bind
seven hydrogen molecules via Kubas interactions with average adsorption energy and
desorption temperature of -0.36 eV/H2 and 512 K, correspondingly satisfying DOE’s criteria.
The ab initio molecular dynamics (AIMD) simulations ensure the structural integrity of the
BeN4+Ti complex at 300 K. The high diffusion energy barrier reduces the probability of
metal-metal clustering formation. The storage capacity of the BeN4+Ti complex comes out to
be 14.21 gravimetric wt% of hydrogen. The present electronic and molecular level study
signifies that the Ti-decorated nitrogen-rich BeN4 monolayer has the potential to fulfill the
requirements to be considered as an energy storage material.

Keywords: Hydrogen energy, 2D Material, BeN4 monolayer, hydrogen storage, desorption

temperature, molecular dynamics, Density Functional Theory (DFT)
 1. Introduction

The present economy is dependent on conventional fossil fuels which are a non-
renewable source of energy. The fulfillment of exponentially increasing energy demands
using conventional fuels is considered one of the main challenges in front of the world [1]. It
is also known that the combustion of fossil fuels leads to the emission of greenhouse gases
and hence, impacts the climate. In order to fulfill energy needs, scientists are looking for
alternative energy resources. Considering that hydrogen possesses a high energy density i.e.,
142 MJ/Kg, and tends to be used in fuel cell technology [2]. The hydrogen combustion
process result in the formation of water as a by-product suggesting that hydrogen is a
pollution-free source of energy [3-5]. Although hydrogen has the potential to be considered a
replacement for conventional fossil fuels, the onboard storage, and transportation of hydrogen
need to be addressed [6].

Conventional hydrogen storage methods such as liquid and gaseous forms need high pressure
for storage and bulky cylinders for transportation [7]. This indicates that large storage tanks
are required in light-duty vehicles which are not a viable method to use as fuel. However, the
adsorption of hydrogen on solid-state materials could be considered a conceivable storage
method to resolve the storage and transportation issues. For this, the US Department of
Energy (DOE) issued guidelines for the material to be fulfilled to be used for hydrogen
storage. The guidelines suggest that the material should store a minimum of 6.5 wt% of H2
with average adsorption energy varying from 0.2 to 0.7 eV [8, 9]. This results in the
exploration of materials that could fulfill the DOE targets.

In this regard, metal hydrides, fullerenes, metal-alloys, etc. were extensively explored by
different research groups [10-15]. The studies show that hydrogen is chemisorbed on the
surface of metal hydrides which leads to high binding energy values. Mixed metal hydrides
show high hydrogen storage capacities. For instance, LiAlH4 can store 10.5wt% of hydrogen
[16]. Although the hydrogen storage capacity is higher than DOE, a phase transition occurs in
the adsorbents. A large amount of energy is stored in the metal-hydrides because of the strong
binding interactions between hydrogen and metal-hydrides. The stored energy is released
during the desorption cycle and results in a phase transition. This indicates that due to strong
binding interactions between metal hydrides and adsorbed hydrogen molecules, high
desorption temperature limits the use of metal hydrides for energy storage in light-duty
mediums. To amend the energy storage competence of metal hydrides, catalyst participation
was also explored in the past. For instance, reports suggest catalyst (HfCl4) improves the
hydrogen uptake of MgH2. It was found that HfCl4 helped to improve the desorption kinetics
and reduced the desorption temperature [17]. This leads to the exploration of different
catalysts which could help to reduce the hydrogen desorption temperature for metal hydrides.

Apart from metal hydrides, high surface area, high porosity, thermal stability, and flexibility
make metal-organic/inorganic (MOFs) frameworks also suitable for hydrogen storage. A
wide range of MOFs were studied in the past by different research groups to explore their
usability in energy storage devices. For example, the hydrogen storage capacity of Al(III)
BUT-22 MOF was investigated by Wang and coworkers [18]. They reported that the
considered MOF can store 11.6 wt% of hydrogen with an operating temperature of 77-160 K.
Kumar and his group studied the hydrogen storage efficiency of Li-decorated metal-inorganic
framework using DFT methods [19]. Although a wide range of MOFs was studied in the past
for their application in energy storage devices, the low adsorption capacity, and complexities
in the fabrication process limit their onboard usage. Considering the limitations of MOFs,
carbon nanomaterials attained research attention.

A range of 0, 1, and 2-dimensional carbon nanomaterials were studied in the past for
utilization in hydrogen uptake [20, 21]. The high porosity, high specific area, rapid
adsorption kinetics, and cost-effectiveness make carbon-containing nanomaterials suitable
candidates for energy storage. For example, the change in the hydrogen storage capacity of
graphene as a function of surface area was explored by Klechikov and coworkers [22]. They
reported an increment in the storage capacity with an increase in the surface area of graphene
nanomaterial at a temperature of 77 K. However, the studies have reported that pristine
carbon-containing materials show poor hydrogen storage performance at high temperatures
[23]. It has been studied in the past that hydrogen storage performance was improved by
varying the electronic properties of carbon nanomaterials [24-27]. The electronic properties
can be tuned by introducing vacancy, doping of heteroatoms, or by a decoration of metal
atoms on the surface of carbon nanomaterials [28, 29]. In this regard, the hydrogen storage
capacity of transition metal decorated carbon nanomaterials was studied in the past using
density functional methods [26]. The effect of Ti-metal atom decoration on the hydrogen
uptake of psi-graphene was researched with computational methods [30]. Authors reported
that Ti-decorated graphene possesses the tendency to adsorb 13.14 wt% of hydrogen with the
binding energies and desorption temperature falling in the range of DOE requirements. The
Sc-decorated holey graphyne shows the capacity to store 9.8 wt% of hydrogen. The Sc-
decorated holey graphyne shows an average hydrogen binding energy value of -0.36 eV with
corresponding desorption temperature of 400 K, fulfilling the DOE requirements [31].
Following this, the role of hybrid carbon heterostructures in hydrogen storage applications
was also studied in the past. Theoretical studies indicated that vacancy-rich graphene
nanosheets can be decorated with pairs of transition metal atoms. For example, Fe- and Ti-
decorated graphene show 5.1 wt% of hydrogen storage and desorption temperature of 400 K
[32].

The H2 storage for hetero atomic two-dimensional materials such as C7N6 were also studied
using computational tools. The reports suggest that C7N6 acts as the superior hydrogen
storage material with a storage capacity of 11.1 wt% [33]. Transition metal atom decorated
graphitic carbon-nitride; g-C3N4 was explored for hydrogen storage applications by Habibi-
Yangjeh and coworkers [34]. The report showed that the Kubas-type interactions facilitate
hydrogen adsorption in such types of nanomaterials. Considering the excellent electronic
properties of the triazene-based g-C3N4 two-dimensional material, the improvement in
hydrogen storage properties of it with transition metal decoration was studied recently by
Brahma and coworkers [35]. The studies showed that the Y-decorated triazene-based g-C3N4
monolayer can absorb up to seven hydrogen molecules resulting in 8.55 wt% of hydrogen.
The role of alkali- and transition-metal atom-doped biphenylene in hydrogen storage was also
considered in the recent past [36, 37]. Brahma and coworkers studied the hydrogen storage
capacity of the Zr-decorated biphenylene monolayer using computational tools [38]. The
study showed that Zr-decorated biphenylene has the tendency to store 9.95 wt% of hydrogen.

Graphene-like materials such as boron nitride were explored for hydrogen storage
applications. The application of Li-decorated boron-nitride nanomaterial for hydrogen storage
devices was studied by Yuan and coworkers using density functional theory [39]. The report
showed that Li-decorated boron-nitride tends to store 10.73 wt% of hydrogen having average
adsorption energy value of -0.26 eV. Likewise, many other nanomaterials such as B40, C24
fullerenes, etc. were also explored for hydrogen storage applications in the past [40-45].
Along with the theoretical studies [46, 47], the hydrogen storage properties of nanomaterials
were also explored by various research groups using experimental techniques. For instance,
with laser ablation technique, the use of metal-doped multi-walled nanotubes for energy
uptake was examined by Mehrabi and coworkers [48]. The superior hydrogen uptake of metal
nanocomposites decorated with two-dimensional nanomaterials was studied by Tarasov [49].

Although a wide range of two-dimensional materials has been explored in the past, nitrogen-
rich nanomaterials got a little less attention. Recently, a new two-dimensional material i.e.
Beryllonitrene was synthesized by applying a high-pressure fabrication technique which
opened a unique category of 2D materials represented as MN4 [50]. The thermal and
mechanical stability of MN4 nanomaterials where M is taken as Be, Mg, Ir, Rh, Ni, Cu, Au,
Pd, and Pt was studied by Zhuang and coworkers [51]. The studies showed that MN4
materials have the potential to act as an anode in Li, Na, and Ca-ion batteries. The studies
have shown that the BeN4 monolayers have great potential in nanoelectronics, energy storage,
and conversion devices. Considering this, the structural, electronic, and hydrogen adsorption
properties of Ti-decorated BeN4 have been investigated in this work using computational
methods. Past studies reported that metal atoms with d-electrons can improve the hydrogen
binding energies and impact the hydrogen storage capacity which inspired us to examine the
effect of Ti atom decoration on the hydrogen storage properties of BeN4 monolayer.
The present study shows that Ti-decorated BeN4 monolayer can bind with hydrogen
molecules. The hydrogen storage capacity of Ti-decorated BeN4 comes out to be 14.21wt%
of hydrogen which indicates that nitrogen-rich monolayers can act as superior hydrogen
storage candidates. The change in the electronic and magnetic behavior of Ti-decorated BeN4
monolayers is discussed with the help of density of states (PDOS). The change in the charge
density of BeN4 after Ti metal atom decoration is studied in terms of charge transfer analysis.
The thermal stability of Ti-decorated BeN4 at elevated temperatures, a crucial parameter to
investigate the practical suitability of the material in onboard energy storage, was also studied
using ab-initio molecular dynamics simulations (AIMD). As long range interactions may
impact the binding of hydrogen molecules, we have tried to understand the role of long-range
van der walls interactions on the binding of hydrogen. This aspect has not been considered in
many of the previous studies [17-18]. The computational methods used to study the above-
mentioned properties are mentioned in section 2 followed by results and discussion in section
3. The conclusion and future directions are mentioned in section 3.

2. Computational Methodology

In this work, density functional theory (DFT) calculations were carried out with the aid of
Vienna ab initio simulation package (VASP) code [52-55]. During computations, projector-
augmented wave (PAW) pseudopotentials were implemented for inner-shell electrons. The
generalized gradient approximation (GGA) was used to include exchange-correlation
functional [56]. The long-range interactions play a role in hydrogen storage material studies.
In this study, to embrace the long-range interactions, the Grimme-DFT-D3 exchange-
correlation function was integrated [57, 58].
A unit cell of BeN4 monolayers is used to mimic the real system. The interactions between
the neighboring layers were ignored by introducing the vacuum of 30 Å in the z-direction.
The plane wave cut-off energy was taken to be 500 eV in the studies. To get the minimum
energy and the most stable geometry of the monolayer, the energy convergence limit, and
ionic force limit were taken to be 10-5 eV and 0.01eV/Å, separately. The -centered
Monkhorst-Pack K-point mesh of 7x7x1 in the first Brillouin zone was considered in the
computations [59]. The Ab initio Molecular Dynamics (AIMD) simulations were executed
using an NVT ensemble. The total simulation time was taken to be 10 ps with a time step of
1fs in the Nośe Hover thermostat.
The Ti-decorated BeN4 monolayers are denoted as BeN4+Ti throughout the manuscript. The
systems formed after the adsorption of hydrogen molecules on BeN4+Ti are symbolized as
BeN4+Ti+nH2 (n=number of hydrogen molecules).
The electronic properties of the BeN4+Ti and BeN4+Ti+nH2 systems were studied as the
density of states (DOS) and partial density of states (PDOS) plots. To understand the type of
interactions between hydrogen molecules and nanosheets, Kubas interaction and the
qualitative and quantitative charge transfer properties were analyzed as charge density plots
and Bader charge analysis, respectively.

3. Results and Discussion:

3.1 Structural properties of BeN4 and Ti-decorated BeN4 (BeN4+Ti) monolayers:

The optimized geometry of the pure BeN4 monolayer is presented in Figure 1(a). It
shows that BeN4 monolayer is formed of five and six-member rings. Each nitrogen atom is
bonded with two nitrogen and one beryllium atom whereas each beryllium atom is bonded
with four neighboring nitrogen atoms. Although two-dimensional materials possess a high
surface area, they show poor performance as hydrogen storage devices due to their weaker
interactions with the hydrogen molecules [29-31]. Considering this, metal-decorated
nanomaterials were explored in the past for hydrogen storage as mentioned above. In the
present work, the effect of Ti-atom decoration for the hydrogen uptake properties of BeN4
monolayer was investigated. To get the most stable adsorption site for Ti on the BeN4
monolayer, Ti was placed at various possible sites such as above the Be atom, in the center of
six-and five-membered rings, above Be-N and N-N bonds. The relaxed geometries of the
various possible sites where Ti metal atom can be decorated on the BeN4 layer are shown in
Figure 1(b-f).
To get the minimum energy metal decorated complex, binding energies were computed using
the following equation:

𝐸𝐵𝐸 = 𝐸𝐵𝑒𝑁4+𝑇𝑖 − 𝐸𝐵𝑒𝑁4 − 𝐸𝑇𝑖 [1]

where 𝐸𝐵𝑒𝑁4+𝑇𝑖 implies the energy of Ti-decorated BeN4 monolayer. 𝐸𝐵𝑒𝑁4 and 𝐸𝑇𝑖 imply the
energies of pure BeN4 and isolated Ti atom, individually. The negative 𝐸𝐵𝐸 indicates the
energetic stability of the complex. The 𝐸𝐵𝐸 values for the Ti-decorated BeN4 complexes were
calculated using the above-mentioned equation and are tabulated in Table 1. The 𝐸𝐵𝐸 values
are negative for all the 𝐸𝐵𝑒𝑁4+𝑇𝑖 complexes indicating that Ti metal atom decoration is an
energetically viable process [27].
The binding is stronger for the decoration of the Ti metal atom above the six-membered ring
of the BeN4 monolayer and hence, is considered for further studies in this work. For this
complex, the Ti metal atom adsorbs at 2.13 Å above the centre of the six-membered ring.
The binding between the Ti metal atom and the BeN4 monolayer will tune the electronic
properties of the latter. Considering this, the change in the electronic properties of the BeN4
monolayer was investigated from density of states (DOS) analysis.
 3.2 Analysis of Density of states

The total DOS plots for BeN4 and BeN4 + Ti monolayers are shown in Figure 2. In the
case of the pristine BeN4 monolayer, the valence band and conduction band are separated by
a very little gap which is close to zero. This indicates that the pure BeN4 monolayer is
similar to semi-metallic two-dimensional material. Further, the spin-up and spin-down states
are identical suggesting non-magnetic signature of the material in its pure form. However,
with the decoration of the Ti metal atom, the density of states appeared at the fermi region,
suggesting the introduction of metallic behaviour in the material with metal decoration
(Figure 2(b)). In addition to this, the material becomes magnetic after Ti metal atom
decoration as the spin-up and spin-down states do not remain symmetric anymore similar to
our previous report [60-61]. This indicates that Ti metal atom decoration tunes the electronic
and magnetic properties of the BeN4 monolayer which may affect the role of this nitrogen-
rich two-dimensional material in hydrogen storage applications.
The partial density of states (PDOS) of BeN4 and BeN4+Ti is also investigated as given in
Figure 3(a-c). The PDOS of N-2p orbitals is enhanced with the Ti-metal atom decoration as
displayed in Figure 3(b) compared to pristine BeN4 indicating that metal is transferring
charge toward the monolayer. The comparison of PDOS of Be-2s orbitals of BeN4 and
BeN4+Ti monolayers indicate that Ti decoration leads to the enhancement of Be-2s orbitals
near the Fermi region as shown in figure 3(a). The significant appearance of Be-2s states is
because of charge transfer from Ti towards BeN4. The PDOS of Ti-3d orbitals of Ti and
BeN4+Ti monolayers are also investigated and analyzed. The significant density of states
appeared at the Fermi region in the case of isolated Ti as shown in Figure 3(c). With the
decoration of Ti on the surface of the BeN4 monolayer, the Ti-3d density of states
significantly reduced around the Fermi region Figure 3(c) indicating that metal act as a
charge donor and is responsible for tuning the electronic properties of the monolayer.

3.3 Bader Charge analysis

The Bader charge analysis helped to investigate the quantitative charge transfer between
BeN4 monolayer and Ti metal atom [62]. The analysis indicates a transfer of 1.18e charge
from the Ti metal atom towards the BeN4 monolayer showing that the former acts as an
electron donor. This transfer of charge from the Ti metal atom towards the BeN4 is
accountable for stronger interactions. The spatial distribution of charge can be visualized
from the charge density difference plot presented in Figure 4..
The binding energy values and charge transfer studies show that BeN4+Ti is a stable complex
with tuned electronic and magnetic properties, which may improve the hydrogen uptake
tendency of the monolayer. Contemplating this, successive adsorption of hydrogen molecules
on BeN4+Ti was studied in this work as discussed below.

3.4 Adsorption of hydrogen molecules on BeN4+Ti monolayer

In order to determine the application of BeN4+Ti in hydrogen storage applications, the

successive hydrogen molecules were adsorbed on the surface of metal-decorated two-
dimensional material. The first hydrogen molecule was kept at ~2 Å above the BeN4+Ti
monolayer. The minimum distance of the hydrogen molecule was reduced to 1.97 Å after
relaxation. The optimized geometries of the hydrogen-adsorbed complexes (BeN4+Ti+nH2)
are shown in Figure 5. In BeN4+Ti+nH2, n represents the number of hydrogen molecules. In
this case, stable geometries were obtained for the adsorption of maximum seven hydrogen
molecules. The stability of the BeN4+Ti+nH2 (n=1-7) complexes were expressed as
adsorption energy using the following equation:

𝐸𝑎𝑑𝑠 = 𝐸𝐵𝑒𝑁4+𝑇𝑖+𝑛𝐻2 − 𝐸𝐵𝑒𝑁4+𝑇𝑖 − 𝑛𝐸𝐻2 [2]

where the 𝐸𝐵𝑒𝑁4+𝑇𝑖+𝑛𝐻2is the minimum energy of the hydrogen adsorption on Ti-decorated
BeN4 complex. The n=1, 3, 5, and 7 denotes the number of hydrogen molecules. The term
𝐸𝐵𝑒𝑁4+𝑇𝑖 is the minimum energy of Ti-decorated BeN4. The last term,𝐸𝐻2 , indicates the
energy of isolated H2 molecules. The adsorption energy values for BeN4+Ti+nH2 (n=1-7)
complexes computed using the above-mentioned equations are provided in Table 2. The Van
der Waals interactions play a key part in understanding the hydrogen storage of two-
dimensional materials as mentioned in the introduction. That is why the adsorption energy
values with and without Van der Waals interactions are given in Table 2. The E ads value for
first hydrogen molecule comes out to be -0.58 eV, which lays in the range of DOE criteria.
This suggests that further adsorption of the hydrogen molecules can be considered. The
hydrogen adsorption energy value is slightly higher than the weak van der Waals interactions
suggesting that the hydrogen binds to the BeN4+Ti complex via Kubas interactions. Further,
it has been observed that seven hydrogen molecules can bind on BeN4+Ti nanomaterial
without distorting the structure of the adsorbent. The average adsorption energy values per H2
molecule without and with vdW interactions for complexes are -0.29 eV and -0.36 eV,
respectively.
3.4 Analysis of partial density of states

The effect of hydrogen adsorption on the electronic properties is computed in terms of

partial density of states (PDOS) plots. The spin-polarized PDOS plots of BeN4+Ti and
BeN4+Ti+H2 complexes are provided in Figure 7. Figure 7(a) shows that an intense density
of states near Fermi region for Ti-3d orbitals reduces with the binding of H2 Figure 7(b). This
reduction in Ti-3d PDOS below the Fermi region with hydrogen adsorption indicates charge
transfer from Ti towards H-atom. In order to verify it, the PDOS plots of the H-1s orbital of
isolated hydrogen and BeN4+Ti+H2 are also shown in Figure 7(c) and Figure 7(d),
respectively. In the case of the H2, the density of states for the H-1s orbital is not visible in
the Fermi region. However, the enhancement of the density of states for the H-1s orbital in
BeN4+Ti+H2complex is observed signifying the transfer of charge from Ti toward the H2.
The increase in the density of states for the H-1s orbital is responsible for the increase in the
H-H bond length and supports the involvement of the Kubas interactions in the present
system.
The PDOS of Ti-3d orbitals for BeN4+Ti+nH2 (n=1-7) complexes are plotted and shown in
Figure 8. The reduction in the PDOS of Ti-3d orbitals at the Fermi level is observed in the
case of BeN4+Ti+2H2 as compared to the BeN4+Ti+H2 complex. The reduction in PDOS of
Ti-3d orbitals is observed around the Fermi region for the successive adsorption of hydrogen
molecules signifying the charge transfer from Ti towards H2 molecules. A change in PDOS at
the Fermi region suggests the interactions between the monolayer and the hydrogen
molecules.
3.5 Diffusion energy barrier

A titanium atom binds to BeN4 nanomaterial with a binding energy value of -2.04 eV.
The cohesive energy value of titanium is -4.85 eV [63], lower than the binding energy value
directing the probability of metal clustering which may control the hydrogen storage
tendency of BeN4+Ti nanomaterial. So to investigate the clustering chances, we need to
compute the diffusion energy barrier which would be helpful to assess the practical use of
BeN4+Ti monolayer for hydrogen storage. The diffusion energy barrier was computed for the
translation of the Ti atom from the most stable site to the equivalent site. The diffusion
energy barrier was plotted with respect to the movement of the Ti from the most stable
position to the equivalent position as shown in Figure 9. The diffusion energy comes out to
be 2.93 eV, which may prevent the metal-metal clustering by not allowing Ti atom to move.
This suggests that BeN4+Ti are a viable material for hydrogen storage applications.

3.6 Reversible hydrogen storage

It is known that nanomaterials possessing reversible hydrogen storage capability can be

used for practical applications. The adsorption energy of hydrogen molecules to the BeN4+Ti
monolayer should be strong enough so that it cannot desorbs with thermal fluctuations. At the
same time, it should not be adsorbed with very strong interactions with the BeN4+Ti
monolayer which could hinder its utilization as a fuel. In simpler ways, the hydrogen
molecules should neither bind very strongly nor very weakly to the BeN4+Ti monolayer.
The reversible use of hydrogen molecules can be determined by computing the desorption
temperature. In this work, the desorption temperature (Td) was computed using van’t Hoff
equation [64]:
𝐸𝑎𝑑𝑠 ∆𝑆 −1
𝑇𝑑 = [ ] ( 𝑅 − 𝑙𝑛𝑃) [3]
𝐾𝑏

The term Eads symbolizes adsorption energy values for BeN4+Ti+nH2 complexes. The
notation S indicates the difference in entropy for the conversion of H2 from its gas phase to
the liquid phase. The R is to represent the universal gas constant value. The P represents the
atmospheric pressure. With the help of this equation, desorption temperature was computed
for the BeN4+Ti+nH2 complexes. The average desorption temperature value for the
BeN4+Ti+nH2is tabulated in Table 2. The tabulated values indicate that the average
desorption temperature with GGA and GGA+vdW functionals come out to be 437 K and 512
K, respectively which comes out to be higher than the room temperature. This suggests that
adsorbed H2 cannot leave the monolayer with thermal fluctuations indicating the reversibility
of the hydrogen molecules. This also hints that the material is suitable for its practical
application for H2 storage.

The diffusion energy barrier and desorption temperature parameters help to understand that
the BeN4+Ti nanomaterial is suitable for its practical use in hydrogen storage devices.
Considering this, further, the gravimetric uptake of hydrogen is also computed for this
material which is discussed explicitly below.

3.7 Gravimetric hydrogen wt%

To determine the gravimetric hydrogen wt% of BeN4+Ti monolayer, Ti metal atoms were
loaded on both the surface of the considered nanomaterial as illustrated in figure 6. The
loading of 7 Ti atoms on each of upper and lower surface in the supercell results in the
storage of 14.21 wt% of H2 (Table 2). The achieved gravimetric hydrogen wt% higher than
the DOE-US requirements and some other previous investigations [30, 47, 65, 66, and 67]
hence, makes the considered nanomaterial suitable for hydrogen storage devices.
Further, the adsorption energy value, desorption temperature, and gravimetric hydrogen wt%
of the present material are also compared with the previously studied materials to understand
their feasibility. The Eads value, desorption temperature, and gravimetric hydrogen wt% of
studied material, and literature values are tabulated in Table 3. It is evident from the table that
the considered material shows quite higher gravimetric hydrogen wt% as compared to
literature results and hence, is a superior H2 storage candidate.

3.8 Ab-initio molecular dynamics simulations (AIMD)

To determine the thermal stability of the considered material, AIMD simulations were
computed in both NVE and NVT ensemble. First, the temperature of the system was
increased in NVE ensemble slowly till it reaches 300 K. Then the system was equilibrated in
NVT ensemble at 300 K. We have used Nosé-Hoover thermostat for temperature control. The
total simulation time was kept as 3 ps with a time step of 1 fs. The variation in distance
between Ti and Be atoms were plotted in Figure 10 to investigate the stability of the BeN4+Ti
monolayer at 300 K. The thermal fluctuation of Ti-Be bond length was plotted with time in
Figure 11 (a) indicating that the fluctuation is not much (only 7 %). The BeN4+Ti monolayer
structure is also shown in Figure 11 indicating that the material remains thermally stable at
room temperature.
Further, we have also checked the possibility of metal-metal clustering at 300 K with the help
of AIMD simulations. We have loaded 2 Ti atoms and performed AIMD at 300 K. The
distance between titanium atoms with respect to time is plotted in Figure 11(a). It can be
inferred that the metals are not coming closer and fluctuation in Ti-Ti distance is very less
(6%). Also, the structure remains stable at 300 K as displayed in Figure 11(b). Thus, the
AIMD simulations help to indicate that the material remains thermally stable and hence, is a
suitable material for hydrogen uptake.

3.9 Conclusion

Herein, the application of titanium-decorated nitrogen-rich BeN4 monolayer is explored

using first-principles calculations. The titanium binds to the BeN4 with a binding energy
value of -2.04 eV indicating the energetic stability of the titanium-decorated BeN4. The stable
BeN4+Ti complex is formed because of charge transfer from titanium metal atom towards
BeN4. The average adsorption energy of successive addition of H2 is -0.36 eV fulfilling DOE-
US conditions. The average desorption temperature for the BeN4+Ti+nH2 complexes is
computed to be 512 K suggesting that the material can be used for reversible hydrogen
storage. The van der Waals interactions play a significant role in this work. The hydrogen
molecules bind to the BeN4+Ti complex via Kubas interactions. The high diffusion energy
barrier rules out the probability of Ti-Ti cluster formation which could destabilize the
complex. The gravimetric hydrogen uptake comes out to be 14.21 wt% for the present
system, quite higher than the DOE-US requirements as well as previously studied two-
dimensional metal decorated nanomaterials. The AIMD simulations predict the thermal
stability of the material. The present study implies that the hydrogen storage capacity of
nitrogen-rich BeN4 can be tuned with the help of Ti metal decoration and hence, can act as a
superior hydrogen storage material.

Statement & Declaration

Funding –

This work was supported by SERB files no. PDF/2021/003221. Ravi Trivedi has received
research support from Science and Engineering Research Board, New Delhi.
Competing Interests:

Conflict of interest: The authors declare that they do not have any conflict of interest

Data availability statement –

The data that support this study are available upon reasonable request.

Acknowledgements

RKT thanks to SERB for providing funding. Authors acknowledge the super-
computing facility of BARC.
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Table 1. Binding Energy (BE), and average Be-Ti bond length for the Ti-decoration at
different sites.

System BE (eV) Be-Ti bond length (Å)

BeN4
BeN4Ti [Ti on Be] -2.03 2.24
BeN4Ti [Ti on Hexa] -2.04 2.13
BeN4Ti [Ti on N] -1.84 2.45
BeN4Ti [Ti on Penta] -1.84 2.47
BeN4Ti [Ti at Be-N] -2.03 3.01
BeN4Ti [Ti at N-N] -1.85 3.30

Table 2. Bond length (Ti-H), adsorption energies, and magnetic moment for BeN4, BeN4+Ti,
and BeN4+Ti+nH2 (n=1-7) complexes using GGA and GGA+Van der Waals interactions,
respectively.
Adsorption Magnetic
Bond length Energy (eV) Moment
Composition
Ti-H (Å) (µB)
GGA GGA+VdW
BeN4 0
BeN4+Ti -2.04 0.99
BeN4+Ti+1H2 1.97 -0.50 -0.58 1
BeN4+Ti+3H2 1.88 -0.33 -0.41 0
BeN4+Ti+5H2 2.43 -0.19 -0.26 0
BeN4+Ti+7H2 2.72 -0.12 -0.21 0
Average
binding energy -0.29 -0.36
per H2
Average
desorption 437 K 512 K
temperature
Gravimetric
14.21%
wt%
Table 3. The adsorbed H2, average adsorption energy (eV), average desorption temperature
(K), and gravimetric uptake of H2 for the BeN4+Ti system and the previously studied metal-
decorated 2D nanomaterials.

Average
Average
Adsorbed H2 desorption Gravimetric
Two-dimensional materials adsorption
molecules temperature hydrogen wt%
energy (eV)
(K)
BeN4+Ti (present work) 7 -0.36 512 14.21
Graphene + Ti [44] 8 -0.415 511.50 7.8
Psi-Graphene + Ti [30] 9 -0.30 387 13.41
B@r57haeckelite + Li [47] 12 -0.16 -- 10.0
Holey graphyne + Sc [31] 5 -0.36 464 9.8
Graphyne + Sc [65] 4 -0.60 -- 9.8
Holey graphyne + Li [66] 4 -0.22 282 12.8
C2N+Ti [67] 10 -0.28 358.10 6.81
Bi+Zr [38] 9 -0.35 405.08 9.95
Figure 1: Ground state structures scheme of (a) 2D materials BeN4 and (b-f) BeN4 doped
with Ti with all the respective sites [Ti atom with different position (b) Ti above Be (c) Ti
above Hexa position (d) Ti above penta position (e) Ti above Be-N bridge (f) Ti above N-N
bridge. Atoms Be, Ti, and N are represented by Blue, Red, and green colors respectively.
 Total Density of States(States/eV)
30 TDOS(BeN )
4
20
10
0
-10
-20
EF
-30
30
TDOS(BeN4+Ti)
Charge states enhancements
20
10
0
-10
-20 EF
-30
-5 -4 -3 -2 -1 0 1 2 3 4 5

E-EFin(eV)
Figure 2:Total DOS of (a) BeN4 and (b) BeN4 doped with Ti. Fermi level is represented by
the vertical line.
 Partial Density of States(States/eV)
0.15 (a) Be 2s orbital(BeN4)
0.10
0.05
0.00
-0.05
-0.10 EF
-0.15
0.03
Be 2s orbital(BeN4+Ti)
0.02 Charge states enhance

0.01
0.00
-0.01
-0.02 EF

-0.03
-5 -4 -3 -2 -1 0 1 2 3 4 5

E-EFin(eV)
Figure 3a: Comparison between PDOS of Be-2s orbital in BeN4 and BeN4+Ti Fermi level is
shown by vertical line.
 Partial Density of States(States/eV)
0.4 (b) N 2p orbtial(BeN4)

0.2

0.0

-0.2
EF
-0.4
0.6
N 2p orbital (BeN4+Ti)
0.4 Charge states enhance

0.2
0.0
-0.2
-0.4 EF

-0.6
-5 -4 -3 -2 -1 0 1 2 3 4 5

E-EFin(eV)
Figure 3b: Comparison between PDOS of N-2p orbital in BeN4 and BeN4+Ti Fermi level is
shown by vertical line.
 Partial Density of States(States/eV)
36 (C) Ti 3d orbital (Isolated Ti)

24
12
0
-12
EF
-24
20
Ti 3d orbital (BeN4+Ti)
Charge states loosing
10

-10
EF
-20
-5 -4 -3 -2 -1 0 1 2 3 4 5

E-EFin(eV)
Figure 3C: Comparison between PDOS of Ti-3d orbital in between isolated Ti and BeN4+Ti
Fermi level is shown by vertical line.

Figure 4. Iso-surface plot for charge density of BeN4+Ti for iso value of 0.1e; blue indicate
charge gain and red is showing charge loss region respectively
Figure 5. DFT optimized structures of (a) BeN4+Ti+1H2, (b) BeN4+Ti +3H2, (c) BeN4+Ti
+5H2 and (d) BeN4+Ti +7H2. Be, N, Ti and H are represented by blue, green, red, and cyan
colors respectively. The average bond distance between Ti and H is also mentioned.

Figure 6. DFT optimized structures of structural figure for computing wt% (by loading
possible number of metal atoms) (a) upper view (b) side view [Be, N, and Ti are represented
by blue, green, red balls]
Figure 7: PDOS of (a) 3d-orbital of Ti in BeN4+Ti (top panel) and BeN4+Ti+1H2 (bottom
panel) and (b) H -1s orbital in isolated H2 (top panel) and BeN4+Ti+1H2 (bottom panel).
Fermi level is shown by the vertical line.
 Partial Density of States(States/eV) 10 Ti 3d orbtial(BeN4+Ti+1H2)

5
0
-5 EF

-10
10 Ti 3d orbital(BeN4+Ti+3H2)
5
0
EF
-5
-10
10 Ti 3d Orbital(BeN4+Ti+5H2)
5
0
-5 EF
-10
10
Ti 3d Orbital(BeN +Ti+7H )
5 4 2

0
-5 EF
-10
-5 -4 -3 -2 -1 0 1 2 3 4 5

E-EF(eV)

Figure 8. PDOS of (a) 3d-orbital of Ti in BeN4+Ti system with attachment of (1) 1H2 (top
panel), (2) 3H2 (panel 2nd from top), (3) 5H2 (panel 3rd from top) and (4) 7H2 (bottom panel).
Fermi level is shown by dotted line.
 3.5
Diffusion energy Barrier = 2.93 eV
3.0

2.5
E-Ein(eV)

2.0

1.5 FP
IP

1.0

0.5

0.0

-1 0 1 2 3 4 5 6 7

Displacement (Å)
Figure 9. The diffusion energy barrier with respect to the displacement of the Ti metal atom
from the most stable position to the equivalent position.

Figure 10. Variation of Ti-Be bond length of Ti decorated BeN4 with time step at 300 K
simulated through molecular dynamics (a) Indicating bond length fluctuation (b)
corresponding structure
Figure 11. Molecular dynamics snapshot of Ti decorated BeN4 at 300 K to avoid cluster-
cluster overlapping (a) Indicating bond length fluctuation (b) corresponding structure