Accepted Manuscript

Computational Design of Boron Doped Lithium (BLin) Cluster-Based Catalyst

for N2 Fixation

Mohd Riyaz, Neetu Goel

PII: S2210-271X(18)30092-6
DOI: https://doi.org/10.1016/j.comptc.2018.03.010
Reference: COMPTC 2744

To appear in: Computational & Theoretical Chemistry

Received Date: 21 February 2018

Revised Date: 13 March 2018
Accepted Date: 14 March 2018

Please cite this article as: M. Riyaz, N. Goel, Computational Design of Boron Doped Lithium (BLin) Cluster-Based
Catalyst for N2 Fixation, Computational & Theoretical Chemistry (2018), doi: https://doi.org/10.1016/j.comptc.
2018.03.010

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 Computational Design of Boron Doped Lithium (BLin) Cluster-Based
Catalyst for N2 Fixation

Mohd Riyaza and Neetu Goela,*

a
Theoretical & Computational Chemistry Group, Department of Chemistry and Centre of
Advanced Studies in Chemistry, Panjab University, Chandigarh, 160014, India

ABSTRACT
The activation of dinitrogen bond and its conversion to ammonia under ambient condition is one
of the most attracted issues in chemistry. Based on first principle investigations, we propose a
boron doped lithium (BLin, n=5-7) cluster based catalysts for N2 fixation. Our calculations
predict BLi6 to be a suitable catalyst for conversion of N2 to ammonia with a limiting potential of
19.13kcal/mol. Two mechanistic routes i.e. distal and enzymatic pathways have been
investigated in detail to understand the feasibility of the reaction. The possibility of grafting the
cluster on the support surface such as graphene and boron nitride sheet has also been explored.
The study concludes that like the isolated cluster, the supported BLi6 cluster is a promising
catalyst for N2 activation.
Graphical abstract
Highlights:

 Activation of dinitrogen bond and its conversion to ammonia under ambient condition.
 Boron doped lithium (BLin, n=5-7) cluster based catalysts for N2 fixation.
 BLi6 found to be suitable catalyst for conversion of N2 to ammonia.
 Grafting of the cluster catalyst on graphene and BN-sheet has been explored
1. Introduction
Dinitrogen (N2) is one of the most inert chemical elements owing to its extremely strong triple
bond. Nearly 78% of atmospheric volume is N2, but its conversion to ammonia (NH3) or nitrides
(nitrogen fixation) is necessary for its direct utilization by living organisms [1,2]. The Haber-
Bosch process, that uses Fe catalyst, is the most common industrial method to convert N2 to NH3
and the reaction proceeds in extreme reaction conditions and needs tremendous amount of
energy [3-5]. However nature accomplishes this task using nitrogenase enzymes that activate
dinitrogen under ambient conditions at transition metal (Fe/Mo, V)-sulfide cluster sites [6].
Understanding the mechanism of nitrogen fixation by these enzymes is crucial to design efficient
catalyst for conversion of N2 to active forms of nitrogen.
Numerous strategies for N2 fixation have been explored in the past and it is one of the
trending topics of discussion in synthetic as well as theoretical chemistry. Since the discovery of
dinitrogen complex in 1965, a number of dinitrogen complexes with transition metal exhibiting
different binding orientation of N2 (end-on, side-on and bridging) have been reported [7,8].
Owing to these efforts, numerous metal and metal oxides based catalysts have been explored
which include homogenous catalysis [9, 10], photochemical [11,12], electrochemical [13-14] and
heterogeneous based thermo-catalytic processes [15]. The Fe and Mo-based complex are widely
explored catalyst to activate N2 due to its presence in active sites of natural nitrogenase enzymes
[8,16-19]. These Fe and Mo complexes with suitable ligands mostly pincer ligands of PPP- and
PNP-pincer type [Example of PNP= 2,6-bis(di-tert-butylphosphinomethyl)pyridine) and
PPP=bis(di-tert-butylphosphinoethyl)phenylphosphine] show promising catalytic activity for N 2
fixation.
Cluster mediated catalytical processes are of particular interest now a days [20-22], as
they individually can act as active sites and one can tune their activity and selectivity as a
function of size of the cluster. Particularly, the clusters of Li have received special attention for
their applications in various fields like electronics, hydrogen storage and electroncatalytic
processes. Lithium monoxide (LinO) and Lithium carbide (LinC) are the two most famous
heterogeneous Li cluster that are well established theoretically as well as experimentally [23-26].
Recently lithium-boron cluster system has been studied extensively to explore its possible use in
lithium batteries, hydrogen storage and catalytical applications [27-34]. Ma et al. [33] have
investigated the activation of CO2 with BLin (n=2-6) clusters for C-H carboxylation of benzene
and found that BLi5 and BLi6 easily activate CO2 and their structure remains intact during the
reaction. Previously Roy et al. [35] discussed the detailed mechanism for insertion of N2 into
model Li-cluster that clearly showed the manner in which N2 can be activated and the N≡N bond
gets elongated by electron transfer. It has been proposed that while homoatomic Li cluster cannot
act as catalysts for the N≡N bond dissociation, incorporation of some other element in the cluster
looks promising strategy to design nitrogen fixing catalyst. In view of the fact that BLin exhibits
super-alkali atom characteristics, with the likelihood of charge transfer from BLin to the π*
orbital of N2, present work proposes boron-lithium cluster (BLin , n=5-7) as efficient catalyst for
N2 fixation.
In a number of recent studies, supported catalysts, in which the catalytically active site is
anchored to nanosurfaces like graphene and boron nitride sheet (BN-sheet), emerge as a new
dimension in heterogeneous catalysis [36-39]. For instance Zhao et al. [36] have reported
promising catalytic activity of Mo-embedded BN-sheet for N2 fixation and thoroughly discussed
its reaction mechanism using density functional theory (DFT) computations. Using DFT
computations Schenk et al. [40] have investigated Schrock Mechanism of Dinitrogen reduction
mediated by molybdenum complex with HIPTN3N ligand (HIPT= hexaisopropyl-terphenyl) and
deduced the thermodynamically most feasible pathway. Recent advances in using a more
systematic scientific approach for catalyst design and developing novel functional materials
through molecular aggregation have generated interest among researchers to scrutinize the
processes at atomic level. Impressive advances in large scale DFT computations have facilitated
not only the design of new and efficient catalysts but also help in deeper understanding of
reaction mechanism. In the search for a versatile and efficient synthetic method for the catalytic
formation of ammonia from molecular dinitrogen under ambient reaction conditions for
constructing a “post-Haber−Bosch process” we propose BLin cluster as a mediator for the
conversion of N2 to NH3 using first principle DFT calculations that also help us to elucidate the
reaction mechanism in detail. While the reaction route has been traced in gas phase, anchoring of
cluster to the graphene and BN-sheet has also been studied with the view to deposit the catalytic
cluster on a nanosurface.
2. Computational details
All the calculations have been performed with spin-polarized DFT computations using Gaussian
09 (A.1) [41] package. For geometry optimization and frequency calculation, DFT based B3LYP
[42-44] hybrid functional was adopted in conjugation with 6-31G+(d) (split-valance basis set
with diffuse and polarization functions). The reliability of employed level of theory for lithium-
boron cluster system has been established in previous studies [30, 32]. A mixed basis set of 6-
31G+(d) + LanL2DZ coupled with same hybrid functional was used to optimize the metallocene
containing Co transition metal. Long range van der Waals interactions have been incorporated by
employing the empirical correction in the Grimme scheme [45-46]. Natural bond orbital (NBO)
[47] charge analysis was performed to compute the charge transfer during the course of reaction.
There are six net coupled proton and electron transfer steps involved in the catalytic cycle
for conversion of N2 to two molecules of NH3 (N2 + 6H+ + 6e- → 2NH3). The energies of
electron and proton (E(e ) , E(H+) were calculated using the model of Lutidinium ([2,6LutH]+) as
a proton source and a metallocene [CoCp*2] as an electron source [40]. The E(H+) = (ELutH+
ELut) and E(e ) values obtained in the present work are -273.24kcal/mol and -103.49kcal/mol
respectively, these are concordant with the previously reported values [38-40]. The adiabatic and
vertical ionization energies (AIE, VIE) of the LiBn clusters are also in agreement with the
literature values (Table 1).
[X] +LutH+→ [XH]+ + Lut (protonation) (1)
[XH] + [CoCp*2] →[XH] [CoCp*2]+(reduction) (2)
Here equation 1 and 2 represent protonation and reduction step in the catalytic cycle and
X refers to intermediates. The reaction energy for the first protonation (Eproton) is given in
equation 3 and accordingly for other protonation steps
Eproton= E(BLin--N2+H+ E(BLin--N2 E(H+) (3)
Likewise the reaction energy for first reduction step (Ereduct) is given in equation 4 and
accordingly for other reduction steps,
Ereduct = E(BLin--N2 H E(BLin--N2+H+ E(e ) (4)
Binding energy (EB) was calculated according to the below equation:
EB = E(cluster+N2) E(cluster E(N2) (5)
where E(cluster+N2), E(cluster) and E(N2) are the total energies of N2 bonded with the cluster
and the energy of cluster and N2 molecule in isolation respectively. In case of cluster supported
on surface, adsorption energy (E ads) was calculated as
 Eads = Esurface/cluster Esurface Ecluster (6)
where E surface/cluster, Esurface and Ecluster are total energy of the cluster deposited over the surface and
the energy of isolated surface and cluster respectively. The computational model of graphene
nanosurface consists of 54 carbon atoms and that of BN-sheet has 27 nitrogen and 27 boron
atoms, the dangling atoms of both the model structures were passivated with hydrogen.
3. Result and Discussion
Literature reports suggest that BLi5, BLi+6, BLi7 and BLi+8 are the most stable species of BLin
family compared to the neighboring cluster species. This can be explained by magic numbers of
phenomenological shell model, BLi5 and BLi+6 have noble gas configuration with 8 valence
electrons required for shell closure. These clusters have high VIE, large HOMO–LUMO gaps
and high degree of aromaticity than the other members of the series [31-32]. The present study
considers cluster size of n = 5-7 for BLin clusters because of the stability of the system and
previous reports suggest that BLin is catalytically active for n value of 5 or more [33].
3.1. Interaction of N2 with BLin
The BLin cluster with boron trapped inside Li alliance is investigated here as a novel catalyst for
nitrogen fixation. The foremost step in the fixation process is the activation of strong N≡N triple
bond, interaction of N2 with cluster sizes (n=5-7) is thus investigated to look for possible
activation of this bond. The BLi5 cluster has a square pyramidal (C4V) geometry and to study its
interaction with N2, various relative configurations of N2 with respect to BLi5 were considered.
It was observed that N2 interacts through end-on with one of the Li in BLi5 cluster (Fig. 1a)
within a distance of 2.04Å and binding energy of -11.84kcal/mol. A small charge transfer of
0.07e from BLi5 to antibonding orbital N2 (KK(σ2s)2(σ2s*)2(σ2pz)2(ᴫ2px)2 (ᴫ2py)2(ᴫ2px*) (ᴫ2py*)) is
noticed with trivial elongation of N≡N bond and no significant change in N≡N stretching
frequency. Thus BLi5 binds with N2 but performs inadequately as a catalyst for N2 activation.
In a similar fashion, possibility to bind and activate N2 over the most stable geometry of
BLi6 (Oh) and BLi7 (D5h) was explored by considering various relative orientations. Our
calculations suggest that N2 binds with BLi6 and BLi7 in a side-on fashion, N2 interacts with three
Li atoms of BLi6 with binding energy of -18.17kcal/mol (see Fig. 1b) and with four Li atoms of
BLi7 with binding energy of -18.90kcal/mol (see Fig. 1c). The BLi6-N2 system shows transfer of
0.66e from BLi6 to N2 with elongation of N≡N bond from 1.10Å (isolated N2) to 1.19Å and
transfer of 1.00e charge with elongation up to 1.22Å in case of BLi7-N2 system. Corresponding
decrease in N2 stretching frequencies from 2455cm-1 to the N2 bonded with (BLi6 N2) and BLi7
(BLi7 N2) were 1858cm-1 and1593cm-1 respectively. These observations indicate activation of
N2 after its binding with BLi6 and BLi7 clusters. But comparing the structural parameter of BLi6
and BLi7 after binding of N2 (Fig. 1b and 1c), the BLi6 cluster does not show much structural
changes, but the pentagonal bipyramidal geometry of BLi7 gets distorted after binding with N2.
Though BLi7 activates N2 but it cannot hold its structural integrity after interaction with N 2
making its regeneration difficult.
The above discussed facts suggest that BLi6 is a promising catalyst for activation of N2, it
has an electronic shell structure closely similar an alkali atom (1s22s22p63s1), its IE (3.84eV) is
lower than that of BLi5 (4.27eV), BLi7 (4.23eV) and the most electropositive element Cs
(3.90eV). Thus BLi6 can be considered as a super alkali atom with a high charge transfer
capacity. The average binding energy (ABE) of the BLi6 cluster ((ABE = nE(Li) + E(B) -
E(BLin))/n) is higher (1.41eV) than BLi5 (1.31eV) and BLi7 (1.38eV). Since BLi6+ is considered
to be the most stable species of BLin family with highest ABE value of 1.65eV, catalytic cycle
for nitrogen fixation by the cluster has been initiated with the reduction of BLi6+ (X+) to BLi6(X)
(Fig.4).

3.2. Catalytic Reduction of N2 on BLi6

All the key reaction steps in the catalytic cycle of N2 conversion to NH3 through two possible
pathways i.e. enzymatic and distal have been investigated in detail. The mechanistic route has
seven steps, there are six consecutive protonation-reduction steps followed by release of NH3
(Fig. 2). The distal pathway involves successive hydrogenation at one N till release of first NH 3
molecule, and then hydrogenation of second nitrogen to form second NH 3. In the enzymatic
pathway, hydrogenation occurs alternatively on both the N atoms with the release of NH 3
molecules at the last two consecutive steps.
The reaction proceeds with reduction of BLi6+ (X+) to neutral BLi6 (X), this step (step 1 in
Fig.4) was uphill in the energy profile by 12.62kcal/mol. The activation of N2 after its binding
with neutral BLi6 has been discussed above, N2 binds with BLi6 in side-on fashion forming X-
N2*, (step 2 in Fig.4) with the release of 18.16kcal/mol energy. The activated N 2 * was then
hydrogenated by consecutive protonation and reduction via two distinct routes. The distal-
pathway is first elucidated in detail, structure of all the intermediates are depicted in Fig. 3. The
energies of all the species in the catalytic cycle are with reference to the energy of initial state
that has been taken as 0kcal/mol [E(BLi6+) + E(N2) + 7E(e-) + 6E(H+) = 0kcal/mol]. he first
hydrogenation step of distal mechanism leads to N2H*(step 3 in Fig.4) with N-H and N=N
bond lengths 1.05Å and 1.26Å (Fig.3a) respectively. In this step the energy goes downhill by
18.65kcal/mol. The addition of second H+ and e at the same N-atom (step in ig leads to
N2H2*(Fig. 3b) with the release of energy cal mol and elongation of N N bond to
1.34Å. The subsequent addition of H+ and e (step in ig leads to formation of N--NH3*
(Fig.3c) with the release of energy cal mol and N N bond elongation to 1.46Å. The next
step involves hydrogenation of 2 nd N atom (step 6D in Fig. 4) and the simultaneous release of 1st
NH3 molecule. This step is accompanied with release of large amount of energy (72.01kcal/mol)
owing to dissociation of the N N bond, releasing first NH3 molecule. he subse uent
hydrogenation steps (step and in ig leading to the formation of NH2*and
NH3*(Fig.3 e and f) are also exothermic. In the final step, release of second NH 3 molecule from
the cluster species needs to overcome a barrier of 19.31kcal/mol (step 9 in Fig.4). This
mechanistic pathway predicts remarkable catalytic activity of BLi6 with a limiting-potential of
only 19.31kcal/mol. Since, bond length is used as criteria to decide about bond dissociation, Fig
5. incorporates all the bond length variations in the reaction sequence with successive
hydrogenation. The separate energy profile given in the supplementary information (Fig 1S)
depicts energy change with each protonation and reduction steps.
Further, the reaction route is elucidated according to enzymatic mechanism, with alternate
hydrogenation on the N atoms (structure of all the intermediates given in Fig. 3). The first three
steps (step 1- 3 in Fig. 4) of this route are the same as discussed above, i.e. reduction of BLi6+,
activation of N2 followed by first hydrogenation step (i.e. addition of first H ++ e to the N2 to
give N2H*,Fig. 3a). Next steps involve successive hydrogenation at the two nitrogen
alternately leading to the release of first NH3 molecule in the 7th step (step 7E Fig. 4). The last
two steps of enzymatic mechanism (step 8 and 9 in Fig. 4) are again the same as that observed in
case of distal route. It is to be noted that both the mechanistic possibilities need the limiting-
potential of 19.13kcal/mol, but at the junction of step 3 that offers two different routes to the
reaction, addition of 2nd hydrogen via enzymatic pathway (i.e. 4E step in Fig.4) is more
exothermic than through distal pathway (step 4D in Fig.4). Moreover, the subsequent steps in
enzymatic pathway lie lower than the corresponding steps of the distal mechanism and there is
no crossing of two reaction routes. This confirms that the hydrogenation of dinitrogen will
follow the thermodynamically more favorable enzymatic pathway. However, enzymatic
mechanism presents the likelihood of hydrazine formation as an unwanted side product [39,48],
but this possibility was ruled out when we studied if the hydrazine gets released (at step 6E) or
the reaction follows its normal course. The energetics reveal that liberation of hydrazine form the
BLi6 cluster needs an energy of 30.10kcal/mol (Fig. 2S) which is very high when compared to
the subsequent reaction steps towards ammonia formation, so formation of hydrazine is very
unlikely.
The catalytic performance of BLi6 has been further interpreted in terms of variation of
NBO charge density in each step along the most feasible pathway (Fig. 6). Each intermediate is
considered to be a combination of two moieties i.e. BLi6 (moiety 1) and NxHy (moiety 2). The
species at step 0 represent the isolated BLi6 cluster and N2 molecule, step 1 (binding of N2 to
BLi6) shows gain of 0.66e charge by N2 from BLi6. In the subsequent hydrogenation steps moiety
1 has some net positive charge and moiety 2 has net negative charge, so overall moiety 1 servers
as electron reservoir and the moiety 2 acts as electron acceptor. In Step 4, there is abrupt charge
variation in which both moieties became almost neutral, this corresponds to the formation of
stable hydrazine molecule, and finally NH3 is released in the last step and the neutral cluster
moiety BLi6 is ready for activation of more N2 molecules.
3.3. Graphene and BN-Sheet supported BLi6
Present computations provide enough evidence in favor of BLi6 cluster as an efficient and active
catalyst for N2 fixation, but it’s important to note here that catalytic activity of the cluster in gas
phase may have little relevance for experimental situations, the cluster need to be deposited on a
substrate. We have considered graphene and BN-sheet as the possible nanosurfaces to support
the cluster. Different orientations of BLi6 over both the surfaces were studied and the most stable
ones are given in Fig. 7 I and II, in which three lithium atoms faces the surface with minimum
adsorption height of 2.45Å and 2.54Å over graphene and BN-sheet respectively. The adsorption
energies of -114.00kcal/mol and -77.54kcal/mol over graphene and BN sheet respectively are
sufficient to prevent cluster aggregation [21].
In terms of adsorption energies, both the nanosurfaces are well suited to graft the cluster but
it necessary to ensure that stabilizing the cluster on the surface does not affect its capacity to
activate the N2. It was noticed that N2 interacts with Li atoms of the graphene supported cluster
at the minimum distance of 2.14Å and in the case of BLi6 supported on the BN-sheet, N2 is at the
distance of 1.97Å from the cluster atoms (Fig. 7 III and IV). It was further observed that N-N
bond elongation is up to 1.15Å and 1.18Å in the case of BLi6 supported on graphene and BN-
sheet respectively. It is thus concluded that BN sheet is the compatible nanosurface to graft the
BLi6 cluster catalyst as it binds the cluster without changing its catalytic activity towards
nitrogen fixation.
It is pertinent to mention here that in the quest for efficient N 2 fixation catalysts, recently,
number of transition metal catalysts with great activity like single metal catalysts embedded in a
support [36-37], transition metal complexes [38-40], carbene based organo-catalysts [5] etc have
been designed through first principle calculations. However, heavy metal catalysts present
environmental hazards that need to be checked. A controlled size cluster can be cost effective as
it acts as individual active site, while in traditional catalysts, reaction occurs at the surface and
the bulk atoms often not participate in the reaction leading to significant increase in cost of
catalysts for expensive metals. Furthermore, controlled size model cluster can be treated with the
highest level quantum mechanical methods to gain fundamental understanding of the molecular
level interaction occurring in the catalytic process that is crucial in order to make significant
advance in this field.
4. Conclusions
In the present study, we investigated the possibility of using BLin (n=5-7) cluster as catalysts for
N2 fixation to ammonia. Both the mechanistic pathways i.e. distal and enzymatic routes have
been traced on the basis of first principle calculations. Out of the three model cluster, BLi 6 is
found to be the best suited catalyst for N2 activation without destroying its structural integrity.
With the purpose to mimic the experimental set up, grafting of the cluster catalyst on graphene
and BN-sheet has been explored. Our calculations predict that BN-sheet stabilizes the BLi6
without altering its catalytic activity towards N2. It is hoped that present findings will provide a
new avenue for the development of nitrogen fixation catalysts and motivate more research in this
stimulating field.
5. Acknowledgements
MR is grateful to the University Grants Commission (UGC) for the junior research fellowship
and NG thanks SERB, DST, India for financial support via grant, SERB/F/8589/2014-2015.
6. Supporting Information
Schematic energy profile corresponding to each protonation and reduction steps through both the
pathways, the energy profile for dissociation of hydrazine from BLi6 and the calculated relative
energies of the intermediates involved in all the steps of the catalytic cycle.

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Table 1 Adiabatic and vertical ionization energies (AIE, VIE) of the BLin cluster system
compared with previously reported IE values (Ref. 30 and 34).

cluster Literature value Current value

(in eV) (in eV)
AIE VIE AIE VIE
BLi5 4.3330 4.5730 4.27 4.33
4.5834
BLi6 3.8530 3.8430 3.84 3.83
3.7534
BLi7 4.2730 4.2830 4.23 4.28
4.3234

Fig. 1. Most plausible structure for interaction of N2 with a) BLi5, b) BLi6 and c) BLi7 with the
key bond length in (Å).
Fig. 2. Schematic depiction of the pathways (distal and enzymatic) for conversion of N 2 to NH3
catalyzed by BLi6 (X in the scheme).

Fig. 3. Optimized structures of various intermediates formed along reaction path of nitrogen
fixation over BLi6 through distal mechanism (a-f) and enzymatic mechanism (a, g-j and f).
Fig. 4. Energy profile for the nitrogen fixation over BLi6 through distal and enzymatic mechanism,
(X=BLi6).

Fig.5 N N bond length variation in each step along both the reaction pathways.
Fig. 6. Charge variation during the reduction reaction along enzymatic pathway. Moieties 1 and
2 are BLi6 and NxHy respectively.

Fig. 7. Most plausible adsorption configuration of BLi6 over I) graphene and II) BN-sheet and
III) and IV) figure shows the binding of N2 with adsorbed BLi6 over graphene and BN-Sheet
respectively.