Materials Science in Semiconductor Processing 167 (2023) 107785

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Probing the catalytic activity of first-row transition metal doped C20

fullerene as remarkable HER electrocatalysts: A DFT study
Sehrish Sarfaraz a, Muhammad Yar a, Ahmed Lakhani b, **, Nadeem S. Sheikh c,
Imene Bayach d, ***, Khurshid Ayub a, *
a
Department of Chemistry, COMSATS University, Abbottabad Campus, KPK, 22060, Pakistan
b
Department of Biomedical and Health Sciences, Calumet College of St. Joseph, 2400, New York Ave, Whiting, IN, 46394, USA
c
Chemical Sciences, Faculty of Science, Universiti Brunei Darussalam, Jalan Tungku Link, Gadong, BE1410, Brunei Darussalam
d
Department of Chemistry, College of Science, King Faisal University, Al-Ahsa, 31982, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: Hydrogen evolution reaction (HER) has captivated the interest of researchers due to ever increasing demand for
C20 fullerene future sources of energy. With the advancement in renewable energy resources, electrocatalytic production of
Transition metal hydrogen has been considered as the most suitable way for hydrogen production for fuel cells and combustion
Gibbs free energy
engines. Herein, we studied HER activity of transition metal doped C20 fullerene (M@C20) by means of
Hydrogen evolution reaction
Electrocatalysts
adsorption energy, Gibbs free energy and electronic density calculations. Ni@C20 and Cu@C20 complexes pro­
vide the best HER activity with Gibbs free energy of − 0.09 eV for each. Furthermore, electronic properties such
as the density of states (DOS) and frontier molecular orbital analyses are performed which indicate that tran­
sition metal doping significantly alters the electronic properties of studied M@C20 complexes. Whereas the
adsorption of hydrogen does not affect the electronic parameters much. The basic understanding of hydrogen
adsorption mechanism together with analyses of electronic parameters is crucial for the synthesis of highly
efficient electrocatalysts for hydrogen energy applications. The critical findings of this study declares that both
Ni@C20 and Cu@C20 complexes can act as promising electrocatalysts for hydrogen evolution reaction with low
overpotential.

1. Introduction development of platinum (Pt) based catalysts is severely limited because

To get relieve from the global environmental pollution and energy
crisis, it is highly demanding to search clean, abundant, and renewable
energy resources [1,2]. Hydrogen, owing to its higher energy density
and zero pollution, has been regarded as an encouraging energy alter­
native to fossil fuels [3]. Hydrogen is a non-polluting, cost-effective, and
the most sustainable energy source [4]. Various methods have been
proposed for hydrogen production, but still the most effective proposed
pathway is the electrochemical water splitting [5]. In hydrogen evolu­
tion reaction, the half-reaction at cathode (H+ + e− → ½ H2) during
water splitting is always in need of a competent electrocatalyst that can
significantly lower its overpotential (ƞ) [6]. In particular, the hydrogen
evolution reaction has gained an outstanding performance by using
metal catalysts of noble metals group [7]. Somehow, the further
of high cost and inadequacy of Pt metals [8–10]. In the past few decades,
considerable attempts have been made to scrutinize other catalysts that
can modify or replace the noble metals for effective hydrogen evolution
process.
To date, a huge number of transition metal doped materials have
been extensively reported for HER to exhibit catalytic activity compa­
rable to that of platinum, such as nitrides [11], sulfides [12], carbides
[13], selenides [14], as well as metal organic complexes [15]. In general,
for HER an efficient electrocatalyst is expected to have abundant cata­
lytic active sites, durability and higher electric conductivity [16]. In this
regard, metal based carbide materials have drawn significant attention
from scientific community due to their high and intriguing catalytic
performance in water electrolysis, which are considered as low-cost
potential replacements for precious metal catalysts [17,18].

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: alakhani@ccsj.edu (A. Lakhani), ibayach@kfu.edu.sa (I. Bayach), Khurshid@cuiatd.edu.pk (K. Ayub).

https://doi.org/10.1016/j.mssp.2023.107785
Received 8 April 2023; Received in revised form 1 August 2023; Accepted 2 August 2023
Available online 8 August 2023
1369-8001/© 2023 Elsevier Ltd. All rights reserved.
S. Sarfaraz et al.
Particularly, Weidman et al. found that the transition metal based
tungsten carbide possesses a catalytic behavior comparable to those of Pt
like catalysts [19]. Similarly, numerous transition metal-based carbides
have been broadly researched as electrocatalysts for hydrogen and ox­
ygen evolution processes [20–22].
In recent times, typical carbon-based single atom catalysts have been
emerged as superior candidates, which can be used as efficient catalysts
for hydrogen evolution process [23–25]. However, the main challenge
in these catalysts is metal aggregation. There are several strategies
which are quite effective to avoid aggregation of metals over designed
surface for single atom catalysis. The most convenient method is the
Stepwise doping strategies which provide better control over the rapid
aggregation of metals [26]. In addition, controlled synthesis conditions
such as reaction time, temperature, pH, and precursor concentration
also play an important role to avoid metal aggregation [27]. Since small
nanocages possess a high surface-to-volume ratio, which helps prevent
dopant aggregations. Similarly, The pyrolysis temperature, percentage
of metal ions, and pyrolysis atmosphere all have significant influence on
the formation of SACs [28]. Certain factors should also be considered
such as pyrolysis temperature, concentration of metal atoms, and proper
pyrolysis environment (NH3 is commonly more helpful) to realize the
single-atom dispersion of targeted metals. In pyrolysis, the metal ag­
gregation between nearby metal atom complexes is expected to be
prevented, resulting to metal atom dispersion [29]. Some prerequisites
should be noteworthy for this strategy: (1) the guests metal atom should
be of particular sizes between pore opening and pore diameter (2)
mononuclear guest metal complexes would be more favorable to control
aggregation of SACs, and (3) the escape or removal of metal species
should be considered in after pyrolysis the support skeletons [30].
Fullerene has gained enormous interest in this field due to their some
outstanding characteristics, which include abundant reserves, low price,
and stability [31]. Recently, density functional theory has been used in
parallel with the experimental strategies by numerous scientists,
because DFT provides the basic understanding of electrocatalysis for
HER [32]. Theoretical studies were performed by Xin Chena et al. on the
mechanism of single walled carbon nanotube (SWCNT) and fullerene
composite as multifunctional metal-free electrocatalyst for hydrogen
evolution, oxygen evolution, and oxygen reduction reactions [24].
Similarly, Pier Paolo et al. [33] conducted electrochemical studies on
carbon nanotube (CNT) electrodes for hydrogen evolution reaction and
reported that CNT surface can easily produce hydrogen. Furthermore,
DFT study was also carried out by Puente et al. [34], where they studied
a novel class of electrocatalysts M3N@C2N fullerenes for HER and
determined that they exhibit an impressive performance for HER.
Moreover, recently Louis et al. presented the catalytic activity of
fullerene-based nanocages with metal doped, encapsulated and
designed materials for hydrogen evolution reaction [31].
Many theoretical simulations as well as experimental studies have
extensively verified that the Gibbs free energy (ΔGH) for hydrogen
adsorption on the surface of electrode is a dominating aspect for the
assessment of HER activity [35,36]. Previous literature have exclusively
shown that Gibbs free energy ΔGH value for HER catalysts on the active
sites is expected to be zero [37–39]. The reason for ΔGH = 0, lies in the
two aspects: the higher negative ΔGH value will make desorption of
hydrogen arduous. Whereas higher positive ΔGH value will result in
weak hydrogen adsorption, which affect electron transfer kinetics. Ac­
cording to Nørskov et al. [40], the absolute Gibbs free energy value
(ΔGH) near zero reveals that adsorbed hydrogen bound neither too
weakly nor too strongly over the catalyst surface, thus, quite favorable in
generating a high performance HER. Therefore, it is very meaningful
and crucial to investigate ΔGH value on a designed catalyst through
some reliable and accurate DFT calculations.
Despite such extraordinary and remarkable progress in DFT studied,
the electrocatalytic activity on C20 fullerene materials designed with
transition metal dopants for hydrogen evolution reaction has not been
yet elucidated theoretically. Although various experimental and
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Materials Science in Semiconductor Processing 167 (2023) 107785
theoretical investigations have been carried out for hydrogen energy
applications in numerous carbon-based nanostructures [41,42]. How­
ever, so far very less work is reported for C20 fullerene, one of the
world’s smallest caged fullerenes [43]. Hence, it is a better idea to
perform DFT investigation upon C20 fullerene supported with transition
metals to answer few questions like 1) Where do the transition metal
binds in C20 fullerene? 2) How are hydrogen atoms adsorbed on doped
transition metal atom? 3) Is there any structural or electronic changes
occur in the designed catalyst upon adsorption of hydrogen atom? Thus,
in current work, we aim to systematically probe the stability, electronic
properties and geometric parameters at ground state and HER catalytic
activity of the first-row transition metal doped C20 fullerene. The sta­
bility of M@C20 complexes is characterized through interaction energy
analysis. Detailed electronic properties of considered complexes are
investigated through d-band center, work function, density of states
(DOS), frontier molecular orbitals (FMO), natural bond orbital (NBO)
analyses. Furthermore, the catalytic performance of designed M@C20
catalysts is fundamentally evaluated through Gibbs free energy of
hydrogen adsorption, where the value ΔGH near zero corresponds to
superior catalytic activity of that catalyst.
2. Computational details
All the DFT simulations including geometry optimization, frequency
analysis, interaction energies have been carried out using quantum
chemical package Gaussian 09 [44]. The geometry optimization and
vibrational frequency analyses of all complexes are performed using
ωB97XD/6-31G(d,p) level of theory. The ωB97XD is a long-range cor­
rected hybrid functional which accurately accounts for geometry opti­
mizations and for computation of electronic parameters [45].
Additionally, the ωB97XD hybrid functional has also been employed to
estimate the non-covalent interactions and long-range dispersion con­
tributions. The frequency analysis is computed to verify that all the
optimized structures are at true minima on potential energy surface. For
visualization of optimized structures chemcraft and GaussView 5.0
software are utilized [46,47]. B3LYP/6-31G(d,p) level of theory is used
for electronic properties such as natural bond orbital and frontier mo­
lecular orbital analyses due to the well reported accuracy [48,49]. The
Multiwfn code is utilized to generate and total density of states (TDOS)
plots [50].
Interaction energies (Eint) are calculated for M@C20 complexes by
using equation (1):
ΔEint = EM@C20− (EC20+EM) (1)
Where, EM@C20, E20 and EM represent the energy of M@C20 complexes,
energy of pure C20 nanocage and energy of isolated transition metal (M),
respectively. Moreover, adsorption energies (ΔEads) are also calculated
for the adsorption of hydrogen atom over M@C20 complexes. ΔEads is
calculated by using equation (2):
ΔEads = EMH@C20− (EM@C20+1/2EH2) (2)
Where, EMH@C20, EM@C20 and 1/2EH2 indicate the energy of hydrogen
(H) adsorbed M@C20 complexes, the energy of M@C20 SACs and the
energy of isolated hydrogen atom, respectively. The negative adsorption
energy values indicate the release of energy during the adsorption
process, therefore, stabilizing the overall system.
Similarly, the catalytic efficiency of a M@C20 complexes is charac­
terized through Gibbs free energy change (ΔG) [45], calculated as by
using equation (3):
ΔGH = ΔEH + ΔEZPE − TΔSH (3)
Where, ΔEZPE, ΔE, T and ΔS are defined as zero-point energy, electronic
energy, temperature and change in entropy, respectively. For HER, the
best or optimal catalytic performance is presented by ΔGH = 0.
Catalytic activity can also be estimated through the value of over
S. Sarfaraz et al. Materials Science in Semiconductor Processing 167 (2023) 107785

Fig. 1. Optimized (a) top and (b) sideview of pure C20 fullerene at ωB97XD/6-31G(d,p) level of theory.

potential. Lower overpotential value implies better catalytic perfor­ reaction). It means transition metals are preferably adsorbed over car­
mance, and vice versa. Overpotential can be calculated by using Gibbs bon atoms of C20 fullerene, which is probably due to the electronegative
free energy as given below: nature of C atoms, compared to transition metal. Therefore, C20
fullerene provides access to the electropositive studied transition metals
− |ΔG|
Ƞ= (4) to bind conjugatively over the C20 surface. This illustrates the phe­
e
nomenon of charge transfer from the metal atom to C20 fullerene, which
is validated by the amount of charge transferred from the adsorbate (M)
3. Results and discussion
to the adsorbent (C20), reported well in literature [31]. For all designed
M@C20 complexes, the bond distance between each M—C bond is
3.1. Structural analysis and interaction energy
calculated in the range of 1.79 Å to 2.09 Å, with corresponding NBO
charge transfer in the range of 0.577 |e| to 1.044 |e| (see Table 1). The
For a deep insight of the catalytic performance of M@C20 complexes
electropositive nature of metal atoms reveals that the charge transfer
as SACs and their improved reactivity for HER, a detailed DFT study has
should take place from metal atoms to C20 fullerene in the designed
been carried out here. The titled fullerene of interest; C20 nanocage
complexes, which is further validated from NBO analysis. The Maximum
consists of twelve fused five membered rings with an average C–C bond
NBO value is calculated in case of Sc@C20 complex (1.044 |e|) followed
length (b5,5 bond) of 1.44 Å, which is consistent with reported literature
by Ti@C20 complex (0.942 |e|), whereas the least charge transfer is
[51]. Both top and side view of computed topology of C20 nanocage is
calculated for Zn@C20 complex (0.577 |e|). It is observed that the value
given in Fig. 1. The C20 nanocage is doped with first row transition
of NBO charges decrease across the first-row transition metals from Sc to
metals (Sc to Zn) exohedrally. To get the most stable possible spin state,
Zn linearly with the increase in atomic number. The least NBO charge
DFT spin polarized simulations are performed with the lowest four
transfer in case of Zn@C20 complex is also due to the completely filled
possible spin states for all considered transition metals. The relative
d-orbital of Zn metal.
energies of considered spin states of transition metal doped C20 fullerene
Moreover, stability of designed transition metal supported on C20
(in au) are presented in Table S1 (Supplementary Information). Namely,
complexes is evaluated via interaction energy analysis (Table 1). The
doublet, quartet, sextet, and octet spin states are optimized for Sc@C20,
interaction energy results indicate that the doping of transition metals
V@C20, Mn@C20, Co@C20 and Cu@C20 complexes. Among these com­
over C20 fullerene is an exothermic and a facile process for all ten metal
plexes the most stable spin state is doublet for Sc & Cu, quartet for V &
atoms. The highest interaction energy value is calculated for Ni@C20
Co and sextet for Mn, respectively. Whereas for Ti@C20, Cr@C20,
complex, thus, revealing the higher thermodynamic stability of this SAC.
Fe@C20, Ni@C20 and Zn@C20 complexes, singlet, triplet, quintet, and
The highest interaction energy of Ni@C20 complex is in good agreement
septet spin states are optimized. In this case, the most stable spin states
with the shortest M—C bond distance (see Table 1). All the designed
are triplet (Ti), quintet (Cr & Fe) and singlet (Ni & Zn). However, all the
complexes exhibit higher Eint values in the range of − 2.92 to − 6.17 eV,
designed M@C20 complexes are stabilized at zero charge. The least en­
which further unveil the strong chemisorption of M atom over C20
ergy spin states are reflected as the most stable one and are utilized in
fullerene. Overall, no structural deformation after optimization is
current study for afterward discussion.
observed in any M@C20 complex (see Fig. 2). Moreover, the lowest
Transition metals are doped at two different positions over C20
interaction energy is observed in case of V@C20 complex which is nicely
nanocage i.e., at the interface of b5,5 and at the middle top of pentagon
correlated with the high interaction distance of 1.97 Å. In all designed
rings. In all doped complexes, transition metals occupy the position at
M@C20 complexes, the post optimization M—C bond distances show
the top of b5,5 interface between two carbon atoms as most stable one,
almost good agreement with their corresponding interaction energy
except Zn which occupies the position at the top of carbon atom. The
values.
stable geometry of the most stable configuration of all studied systems
are considered for their HER performance as SACs. The optimized
structures of single metal atom doped C20 complexes (endohedral) with 3.2. Electronic properties of TM@C20 complexes
metal atom labelling and M—C bond lengths are presented in Fig. 2.
Whereas the interaction energies for the adsorption of single transition 3.2.1. FMO analysis
metal (M) atom and C20 fullerene are given in Table 1. To better understand the influence of the catalytic activity of M@C20
The interaction energy results in Table 1 clearly depicted that Eint complexes, electronic properties such as frontier molecular orbitals
values for all designed M@C20 complexes are negative (feasible (FMOs), work function (ɸ), total density of states (TDOS) and partial
density of states (PDOS) of all the designed complexes are studied. FMO

3
S. Sarfaraz et al.
Fig. 2. Optimized structures of transition metal doped C20 complexes (Sc to Zn) at ωB97XD/6-31G(d,p) level of theory; where grey color is for carbon atoms (bond
distances are mentioned in Å).
analysis helps to comprehend the electronic effect of transition metal
supported C20 complexes. The calculated energies of HOMO, LUMO and
their corresponding energy gap are given in Table 1. The HOMO and
LUMO isodensities are presented in Fig. 3.
The HOMO and LUMO energy values of C20 fullerene are nearly
equal to − 5.06 eV and − 3.06 eV, respectively, whereas the corre­
sponding energy gap is 2.00 eV. Upon interaction of transition metal
with C20 fullerene, the energy gap reduces significantly in case of
Cr@C20, Fe@C20, Ni@C20 and Zn@C20 complexes, whereas in all other
studied complexes the energy gap is slightly increased compared to pure
C20 fullerene (see Table 1). It is further observed that HOMO energy
value slightly increases in all designed complexes except Mn@C20
complex, where HOMO energy (− 5.13 eV) is slightly lower compared to
HOMO (− 5.06 eV) of C20 cage. This slightly decrease in HOMO energy
level of Mn@C20 complex most probably resulted due to stability of
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Materials Science in Semiconductor Processing 167 (2023) 107785
valence d-orbitals. Similarly, the increased LUMO energy values reveal
the enhanced electron accepting ability of studied M@C20 systems.
However, the highest decrease in energy gap is calculated for Ni@C20
complex, which is nicely correlated with the highest interaction energy
of this complex. Thus, FMO results are consistent with the results of
interaction energy analysis. Moreover, in case of pure C20 fullerene, the
HOMO and LUMO densities are uniformly distributed over whole
nanocage (see Fig. 3). Upon doping with transition metal atom, the
HOMO and LUMO densities involve metal atom too, representing the
involvement of metal atom in charge transfer. Both C20 nanocage and
doped atoms are metallic in nature, thus, electronic density remains
uniformly distributed on surface and dopants due to their same elec­
tronic nature. However, in case of Cu@C20 and Zn@C20 complexes,
LUMO orbital is only concentrated over C20 nanocage.
Total density of states (TDOS) as well as partial density of states
S. Sarfaraz et al. Materials Science in Semiconductor Processing 167 (2023) 107785

Table 1 investigating the catalytic efficiency of designed materials. The d-band

Summary of interaction energies (Eint), energies of HOMO, LUMO and their (Ɛd) values of Fe@C20, Ni@C20 and Cu@C20 complexes are calculated as
energy gap (Egap), NBO charges on metal atom (QM), work function (ɸ) and d- − 4.30 eV, − 4.07 eV and − 4.92 eV, respectively, which suggest that the
band center value of all M@C20 complexes (all energy values are in eV). Ɛd values in these complexes are close to Fermi level (see Table 1).
M@C20 Eint HOMO LUMO Egap QM | ɸ Ed-band Whereas, for Mn@C20 complex, the Ɛd value is nearly approaching to
(eV) (eV) (eV) (eV) e| (eV) (eV) Fermi level (− 3.85 eV). While rest of the designed M@C20 complexes
Sc@C20 − 3.11 − 4.56 − 2.32 2.24 1.044 3.44 1.67 have Ɛd values shifted away Fermi level. However, for Ni@C20 and
Ti@C20 − 3.20 − 4.67 − 2.40 2.27 0.942 3.53 0.86 Cu@C20 complex, lower Gibbs free energy value (0.09 eV) and shift in Ɛd
V@C20 − 2.92 − 4.71 − 2.55 2.15 0.833 3.63 − 0.23 closer to fermi level facilitated adsorption and desorption of H over these
Cr@C20 − 3.42 4.59 2.67 1.92 0.858 3.63 − 1.53
surfaces and hence result in higher HER performance.
− −
Mn@C20 − 5.39 − 5.13 − 2.89 2.24 0.850 4.01 − 3.85
Fe@C20 − 6.15 − 4.83 − 3.01 1.82 0.898 3.92 − 4.30
Co@C20 − 5.39 − 4.89 − 2.88 2.01 0.858 3.88 − 1.80
Ni@C20 − 6.17 − 4.74 − 3.13 1.61 0.813 3.93 − 4.07 3.3. HER modeling on designed single atom catalysts (SACs)
Cu@C20 − 4.87 − 4.83 − 2.67 2.15 0.748 3.75 − 4.92
Zn@C20 − 4.89 4.85 2.95 1.90 0.577 3.90 − 7.06
− −
Gibbs free energy change (ΔGH) for the HER i.e., 2H+ + 2e− → H2 is
C20 – − 5.06 − 3.06 2.00 – 4.06 –
considered as zero under specified conditions [55]. For hydrogen evo­
lution reaction, large positive Gibbs free energy value (ΔGH > 0) is not a
provide valuable information regarding exact HOMO and LUMO energy kinetically favorable electrocatalyst. On the other hand, the large
levels changes before and after adsorption of TMs atoms over C20 cage. negative value (ΔGH < 0) suggests that the adsorbed H atom will not be
PDOS spectra also give the information that which fragment is respon­ easily released from that electrocatalyst. Hence, both high positive and
sible for overall change in HOMO-LUMO energy gaps of complexes. negative Gibbs free energy (ΔGH) values make HER process difficult.
PDOS and TDOS spectra of all considered M@C20 complexes are Therefore, an effective electrocatalyst must possess optimal ΔGH value
computed by using the Multiwfn package [50]. In Fig. 4, we present the (close to zero) for HER. In this section, we discuss the key parameters
TDOS and PDOS spectra calculated for all studied M@C20 complexes and that are most relevant to the activity of M@C20 complexes in HER free
observe the following general trends; a) the changes in peak intensity of energy (ΔGH) and overpotential (ƞ). The calculated values of all these
TDOS spectra for all complexes are observed with variance in adsorbed parameters are reported in Table 2. Similarly, we have also designed
metal, b) TDOS spectra is sum of energy levels of fragment and C20 structures with M-C19 formula and have calculated HER activity with
cages. Another important parameter related to the electronic charac­ the best hydrogen evolution performance (Ni–C19 and Cu–C19) reported
teristics is the partial density of states (PDOS), which better helps to in Table S3 and Fig. S1 (supporting information). The M—H bond dis­
evaluate the contributions of the individual component towards the tances for after the adsorption of hydrogen over designed M@C20
TDOS and HOMO-LUMO energy gap. C20 nanocage contributes to both complexes are in the range of 1.52 Å to 1.88 Å. A general trend of
HOMO and LUMO energy levels, consistent with the isodensities pre­ decrease in M—H bond length is observed with increase in atomic
sented in Fig. 3. However, PDOS spectra reveal that adsorption peaks of number transition metal atom from Sc to Zn (see Fig. 5).
adsorbed TMs are higher in energy compared to energy level of C20 To evaluate the catalytic activity of M@C20 systems for HER, we
peaks. This shows that, d-orbitals of adsorbed TMs generated new en­ have utilized the Sabatier principle [56]. To investigate the HER activity
ergy level, which are higher in energy compared to p-orbitals of C-atoms of the studied systems, the interaction existing between H atom and
of C20 cage. These results of TDOS and PDOS also verify the increase or M@C20 complexes are studied via computing the optimized structures of
decrease in HOMO-LUMO energy gaps before and after adsorption of the H adsorbed M@C20. The reduction of water molecule occurs at
transition metals. cathode, which combined with electrolyte, acts as an electrocatalyst for
HER in the acidic media. The HER process can either be proceeded
3.2.2. Work function through Volmer-Tafel or Volmer-Heyrovsky mechanisms [45]. In stan­
The work function (ɸ) is also considered as a key property of a ma­ dard conditions, hydrogen evolution reaction is proceeded through the
terial related to the electronic structure, and can be mathematically hydrogen reduction on the surface of electrocatalyst i.e., Volmer step.
defined in Eq. (5) [45,52]: The reaction for this step can be presented as:
IP + EA H+ + e− + M ⇄ MH
ɸ= (5)
2
Where, MH presents H atom adsorbed over catalyst surface and M is the
The values of work function for nanostructures for example the ones metal center. The Volmer step is associated through reactant (H+ + e− ),
under studied here, broadly reveal the amount of energy requires to an intermediate state (H*) and the product 1/2H2 (g). By applying
remove or eject an electron from that system. From ɸ values in Table 1, theoretical model [57], the chemical potential of pair (H+ + e− ) is equal
we conclude that the ɸ values do not show prominent variations in most to the half of H2 molecule (1/2H2). The higher negative ΔGH value will
of studied systems (3.44–4.01 eV). In general, the work function values make desorption of hydrogen arduous. Whereas higher positive ΔGH
in all studied M@C20 complexes show a decrease as compared to pure value will result in weak hydrogen adsorption, which affect electron
C20 fullerene (4.06 eV). The decrease in work function values reveals transfer kinetics. Therefore, the ideal ΔGH value for an efficient elec­
that the catalytic properties of C20 fullerene are improved upon doping trocatalyst should be zero or close to zero for HER. To examine the HER
of transition metals. performance of the studied systems, ΔGH is calculated from the Eads
values of hydrogen on the M@C20 complexes using Eq. (3) for all the ten
3.2.3. d-band center configurations, and the free energy values are listed in Table 2. Based on
The d-band center (Ɛd) is an important descriptor to correlate the free energy calculations ΔGH values for Ni@C20 and Cu@C20 complexes
catalytic ability various transition metal doped surface [53,54]. Tran­ are nearly equal to ideal i.e., − 0.09 eV for each. Moreover, reasonable
sition metals involve active d-orbital, which significantly contribute to catalytic activity is displayed by Sc@C20, Ti@C20, Fe@C20 and Co@C20
changing the electronic properties of system. Hence, d-band center (Ɛd) complexes with ΔGH values in the range of − 0.26 eV–0.60 eV. However,
is also computed to further investigate the catalytic activity of designed based on Gibbs free energy results, we conclude that the best catalytic
M@C20 complexes (see Table 1). In general, there is no direct relation­ performance for HER is presented by Ni@C20 and Cu@C20 complexes
ship between decrease in Gibbs free energy and shift in d-band center to out of ten studied SACs owing to their low ΔGH values. The ΔGH values
fermi level. However, both factors play an important role in are further reinforced in Fig. 6, where free energy is presented as a

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S. Sarfaraz et al. Materials Science in Semiconductor Processing 167 (2023) 107785

Fig. 3. HOMO-LUMO orbital densities all designed M@C20 configurations computed at B3LYP/6-31G(d,p).

6
S. Sarfaraz et al.
Fig. 3. (continued).
function of reaction coordinates.
Catalytic activity can also be estimated through overpotential i.e.,
lower overpotential implies better catalytic performance, and vice versa.
Therefore, overpotentials is also calculated for all ten designed M@C20
complexes using Eq. (4) and values are also listed in Table 2. Physically,
overpotential (ƞ) is defined as the extra amount potential necessarily
required to drive the water splitting reaction through electrochemical
process. From the computed overpotential values reported in Table 2, it
is obvious that for all the studied H-adsorbed M@C20 systems, the values
are lying in the range of 0.09 V–3.23 V. However, the lowest over­
potential value of 0.09 V is observed in case of both Ni@C20 and Cu@C20
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Materials Science in Semiconductor Processing 167 (2023) 107785
catalysts, making them best electrocatalysts for hydrogen evolution
process. Thus, we further conclude that Ni and Cu doping over C20
fullerene considerably reduces the overpotential and mark them as
highly efficient and superior HER catalysts. The overpotential calculated
for Ni@C20 and Cu@C20 catalysts (0.09 V) is also comparable with the
already reported hydrogen descriptor for noble metal platinum (0.03 V)
[58]. In literature, better catalytic behavior of Ni and Cu catalysts has
been extensively reported for hydrogenation reactions [59–61].
Furthermore, the obtained results are also nicely correlated with refer­
ence [40], which presents the experimental and theoretical comparison
overpotential and free energy of noble metals and some transition
S. Sarfaraz et al. Materials Science in Semiconductor Processing 167 (2023) 107785

Fig. 4. TDOS and PDOS plots studied M@C20 complexes computed at B3LYP/6-31G(d,p).

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S. Sarfaraz et al. Materials Science in Semiconductor Processing 167 (2023) 107785

Fig. 4. (continued).

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S. Sarfaraz et al. Materials Science in Semiconductor Processing 167 (2023) 107785

Fig. 4. (continued).

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S. Sarfaraz et al. Materials Science in Semiconductor Processing 167 (2023) 107785

Table 2 metals for HER.

Summary of computed change in Gibbs free energy, overpotential, energies of
HOMO-LUMO and their corresponding energy gap (Egap) of considered HM@C20 3.4. Electronic properties of hydrogen adsorbed M@C20 complexes
electrocatalysts (all the reported values are in eV).
HM@C20 ΔGH = ΔEads + ΔEZPE - TΔSH ƞ HOMO LUMO Egap To elucidate the variations in electronic parameters of studied
HSc@C20 − 0.42 0.42 − 4.87 − 2.98 1.89 complexes after the hydrogen adsorption FMO and DOS analyses also
HTi@C20 − 0.26 0.26 − 5.09 − 2.84 2.26 computed. The calculated HOMO-LUMO energy values and their cor­
HV@C20 1.08 1.08 − 5.24 − 3.21 2.03 responding energy gap (Egap) of hydrogen adsorbed M@C20 complexes
HCr@C20 1.22 1.22 5.39 3.18 2.22
are listed in Table 2. The HOMO and LUMO orbital densities of HM@C20
− −
HMn@C20 3.23 3.23 − 5.25 − 3.10 2.15
HFe@C20 − 0.20 0.20 − 6.68 − 3.55 3.14 complexes are presented in Fig. 7. To further evaluate the electronic
HCo@C20 0.60 0.60 − 4.95 − 2.68 2.27 characteristics of hydrogen adsorbed MH@C20 complexes TDOS and
HNi@C20 − 0.09 0.09 − 5.37 − 3.44 1.92 PDOS plots are also generated and are presented in Fig. S2 (supporting
HCu@C20 − 0.09 0.09 5.50 3.57 1.94
− −
information). Upon hydrogen adsorption over considered M@C20 cata­
HZn@C20 − 1.08 1.08 − 4.79 − 2.85 1.94
lysts, there is not much perturbation in electronic properties. FMO and

Fig. 5. Optimized structures of hydrogen adsorbed M@C20 complexes (Sc to Zn) at ωB97XD/6-31G(d,p) level of theory.

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S. Sarfaraz et al.
Fig. 6. Free energy diagram presenting Gibbs free energy (eV) for adsorption of hydrogen over M@C20 catalysts for HER.
DOS analyses show almost similar results for HM@C20 complexes as
those for M@C20 complexes. In all MH@C20 complexes, the highest
decrease in energy gap with respect to C20 fullerene is calculated for
HSc@C20 (1.89 eV) complex followed by NiH@C20 (1.92 eV), CuH@C20
(1.94 eV) and HZn@C20 (1.94 eV) complexes. Whereas for all other
studied M@C20 complexes, an increase in HOMO-LUMO energy gap is
observed. However, the energy gap results of HM@C20 complexes are
almost comparable to M@C20 complexes and very slight changes in peak
intensities are observed in DOS spectrum.
Hydrogen adsorption over M@C20 complexes do not change the
distribution of HOMO-LUMO orbital densities significantly (see Fig. 7).
HOMO orbital densities are mainly appeared over M@C20 complexes
excluding the hydrogen atom except HNi@C20 complex, where HOMO
density appears over entire system. Similarly, the LUMO density appears
over hydrogen atom too in case of HSc@C20, HNi@C20 and HCu@C20
complexes, while in rest of studied complexes LUMO density is only
distributed over metal atom and C20 nanocage. The calculated d-band
center of Ni@C20 and Cu@C20 catalysts are nearly close to Fermi level
(see Table 1 and Fig. S2). Thus, making Ni@C20 and Cu@C20 catalysts
most suitable for adsorption and desorption of hydrogen atom, which in
turn result in better HER activity. This d-orbital shifting is more pro­
nounced in case of Ni@C20 and Cu@C20 complexes as compared to other
M@C20 complexes. These results are not only consistent with other
electronic parameters but also show good correlation with adsorption
energy (Eint) and Gibbs free energy results. Therefore, Ni@C20 and
Cu@C20 complexes are the excellent candidates for the hydrogen
adsorption and facilitate hydrogen evolution process efficiently.
HER catalytic activities of Ni@C20 and Cu@C20 catalysts computa­
tionally obtained in this work are compared with those of the reported
state-of-the-art electrocatalysts (Table 3) from the literature by
comparing the ΔGH values. The ΔGH value of Pt(111) is − 0.09 eV which
is used as a benchmark in various computational based HER studies. The
obtained ΔGH value for Ni@C20 and Cu@C20 catalysts in this work (0.09
eV), agrees well with the benchmark Pt(111) surface and other previous
works.
The absolute Gibbs free energy value (0.09 eV) of Ni@C20 and
Cu@C20 is comparable with Pt (ΔGH = − 0.09 eV) [62]. Remarkably, the
designed Ni@C20 and Cu@C20 catalysts are expected to show almost
comparable HER catalytic activity than previously reported noble metal
based catalysts (Ru2@C2N, Pt–TaC(111) and Pt–W2S(0001)). Similarly,
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Materials Science in Semiconductor Processing 167 (2023) 107785
if we compare our results with other transition metal-based catalysts, the
designed Ni@C20 and Cu@C20 catalysts show much better catalytic
performance for HER (see Table 3).
4. Conclusions
In summary, first-row transition metal (M) doped C20 fullerenes are
investigated using density functional theory simulations for HER activ­
ity. The structural and electronic properties as well as hydrogen evolu­
tion reaction catalytic performances are studied for ten designed M@C20
complexes. The doping of transition metal atom significantly changes
the electronic parameters of M@C20 complexes. Our simulated results
suggest that Ni@C20 complex, with the lowest HOMO-LUMO energy gap
of 1.61 eV compared to rest of the studied complexes, has the best cat­
alytic performance towards HER. In pursuit of the most effective HER
electrocatalyst among the studied complexes, adsorption energy and
free energy are calculated. Gibbs free energy of Ni@C20 and Cu@C20
complexes (0.09 eV) is also more favorable and closer to optimal value
(ΔGH ≈ 0). For an ideal electrocatalyst catalyst for HER activity, the
value of overpotential (ƞ) should be zero, and our overpotential values
are in the range of 0.09–3.23 eV, fairly close to zero. The studied elec­
tronic parameters as well as d-band center value also justify the best
catalytic performance of Ni@C20 and Cu@C20 complexes for HER.
Hence, based on the presented results, we really hope that experimen­
talists will get proper guidance for designing efficient fullerene based
electrocatalysts for hydrogen evolution reaction.
CRediT authorship contribution statement
Sehrish Sarfaraz: Writing – original draft, Software, Methodology,
Investigation, Data curation, Conceptualization. Muhammad Yar:
Validation, Methodology, Investigation, Formal analysis. Ahmed
Lakhani: Validation, Software, Resources. Nadeem S. Sheikh: Inves­
tigation, Formal analysis, Data curation. Imene Bayach: Validation,
Funding acquisition, Formal analysis. Khurshid Ayub: Writing – review
& editing, Supervision, Project administration.
Declaration of competing interest
The authors declare that they have no known competing financial
S. Sarfaraz et al. Materials Science in Semiconductor Processing 167 (2023) 107785

Fig. 7. HOMO-LUMO orbital densities all hydrogen adsorbed M@C20 configurations computed at B3LYP/6-31G(d,p).

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