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Physical Insights into Chemistry, Catalysis, and Interfaces

Silicon and Phosphorous Co-doped Bipyridine-linked Covalent
Triazine Framework as a Promising Metal-Free Catalysts for
Hydrogen Evolution Reaction: A Theoretical Investigation
Biswajit Ball, Chandrima Chakravarty, and Pranab Sarkar
J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.9b03876 • Publication Date (Web): 05 Feb 2020
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Page 1 of 27 The Journal of Physical Chemistry Letters

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8 Silicon and Phosphorous Co-doped
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11 Bipyridine-linked Covalent Triazine Framework as
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15 a Promising Metal-Free Catalysts for Hydrogen
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18 Evolution Reaction: A Theoretical Investigation
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22 Biswajit Ball, Chandrima Chakravarty, and Pranab Sarkar

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25 Department of Chemistry, Visva-Bharati University, Santiniketan- 731235, India
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28 E-mail: [email protected]
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31 Abstract
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34 The electrocatalytic water spliting is the most attractive route for hydrogen production, but
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36 the development of nonprecious, stable, and high-performance catalysts for hydrogen evolu-
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38 tion reaction reaction (HER) to replace the scarce platinum group metal-based electrocatalysts
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is still a challenging task to the scientific community. In this work, within the framework of
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41 density functional theory computations, we have predicted that a silicon and phosphorous co-
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43 doped bipyridine-linked covalent triazine framework, followed by substitution of bipyridine
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45 hydrogens at P-site by fluorine atoms, may be a potential catalyst for hydrogen evolution re-
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47 action (HER). Our predicted model system (SiPF-Bpy-CTF) exhibits very low band gap (7
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49 meV), which may facile charge transfer kinetics during HER. Using the Gibbs free energy
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51 for the adsorption of atomic hydrogen (∆G0H ) as the key descriptor, we have found that our
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proposed model system (SiPF-Bpy-CTF) exhibits superior HER catalytic activity, with ∆G0H
54 being close to ideal value (0 eV).
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TOC Graphic
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9 H+

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H2 H2
H+
H+
HER
11 H2

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18 The development of sustainable and renewable energy resources to replace the carbon-based
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20 fuels is becoming increasingly important to resolve the energy problems of using fossil fuels.
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22 Molecular hydrogen is regarded as the cleanest energy carrier due to its high energy density and
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24 environmental friendliness. Although hydrogen is the simplest of all chemicals, it plays an im-
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26 portant role in energy production (e.g., fuel cells) as well as in reduction processes in synthetic
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28 chemistry. 1 Thus, a sustainable form of production of hydrogen is needed as an alternative to hy-
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30 drocarbon fuels. 2 One of the most promising route to that direction is the electrochemical water
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32 splitting. Currently, platinum is the most widely used electrocatalysts due to its outstanding ther-
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34 modynamics and kinetics in the electrocatalytic hydrogen evolution reaction (HER). 3 However,
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36 the application of noble metals as catalysts for large-scale hydrogen generation is hindered due to
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38 their limited resources and high cost. The generation of hydrogen in an economically viable path-
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40 way is still to be developed. 1 The major problems in achieving hydrogen in an economically viable
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42 pathway is the lack of low cost and efficient catalysts. 1 In this context, it is a challenging task to
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44 the scientists to develop cost-effective and earth-abundant catalysts that perform comparable to or
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46 even better than noble metals. 4
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48 Two-dimensional materials have attracted the attention of the researchers because of their fas-
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50 cinating physical and chemical properties. 5,6 Some of the 2D materials have the promise to re-
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52 place Pt-comparable catalysts for HER, such as transition-metal dichalcogenides (TMDs), 2,7–9
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54 MXenes, 10,11 carbon nanotubes, 12 metal-organic frameworks (MOFs), 13–18 and doped graphene. 3
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56 Gao et al. have shown that some 2D MXenes terminated by oxygen atoms exhibit excellent per-
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formance in HER. 11 Tsai et al. have demonstrated how the HER catalytic activity of the edge-
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site of MoS2 can be tuned via support interactions. 2 Sahoo et al. have explored the electrocat-
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alytic activity of a wide range of transition-metal single atoms on TiC support. 19 Besides these
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9 transition metal-based electrocatalysts, Liu et al. have explored 2D boron sheets as a promising
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11 metal-free catalysts for the electrolysis of water. 3 Another popular candidate for the electrocatal-
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13 ysis/photocatalysis of water is graphitic carbon nitride g C3 N4 . Peng et al. have investigated
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15 the effect of ruthenum ion complexation on the catalytic activity of g C3 N4 nanosheets towards
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17 HER. 20 Graphitic carbon nitride (g C3 N4 ) coupled with nitrogen-doped graphene (NG) results in
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19 an electrocatalyst whose catalytic activity is comparable to MoS2 . 21 Gao et al. pointed out strain
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21 to be the reason for the experimentally-observed high HER catalytic activity of nitrogen-doped
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23 graphene suported g C3 N4 . 21,22
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25 In addition to porous g C3 N4 , two new porous materials, namely, metal-organic frameworks
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27 (MOFs) and covalent organic frameworks (COFs) provide the opportunity to design nonprecious
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29 electrocatalysts for HER. These porous materials have emerged with a large degree of variabil-
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31 ity for inorganic nodes, organic linkers and ligands. Because of these structural diversity, the
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33 MOF/COF-based materials can be precisely modulated and functionalized. MOFs and COFs have
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35 attracted the attention of researchers because of their highly porous nature, which facilitate the dif-
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37 fusion of substrates/products, hence, improving the diffusion kinetics and large surface area, which
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39 provide large amount of active sites to participate in a catalytic reaction. 23 Moreover, the substrates
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41 get maximal access to the catalytic sites due to the homogeneous dispersion of open active cen-
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43 ters. 23 Molecular catalysts are widely used as potential candidates for electrocatalytic hydrogen
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45 generation. 23 But, these catalysts suffer from poor recoverability and reusability. 23 In this context,
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47 MOFs, featuring metal sites with well-coordinated organic ligands, integrate the merits of both
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49 homogeneous and heterogeneous catalysts with high selectivity, activity, and stability. 23 Clough
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51 et al. have shown that integration of the cobalt dithiolene catalysts into metal organic surfaces
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53 (MOS) give rise to an active electrocatalyst for HER. 17 Sun et al. have explored the application
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55 of Bis(aminothiolato)nickel nanosheets (CONASHs) as an electrocatalyst for HER. 24 Wang et al.
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have unrevealed the effect of the electrolyte on the electrocatalytic activity of a one-dimensional
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cobalt-dithiolene metal organic framework (MOF). 14
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COFs, a recently emerged crystalline porous material, display some advantages over MOFs as
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9 an electrocatalyst due to their enhanced thermal stability and rich electronic properties. 23 COFs
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11 are of fully organic nature in which the organic ligands are linked by strong covalent bonds of
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13 lightweight elements (H, B, C, N, O, and Si). 25 2D COFs are widely used as an application for
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15 gas storage, 26,27 catalysis, 28,29 gas seperation, 25,30 supercapacitors, 31 proton conduction, 32 op-
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17 toelectronic devices, 33 sensing, 34 batteries, 35,36 and semiconductors. 37 Despite of their diverse
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19 applications in various fields, electrocatalysts based on COFs are rarely reported. Bhunia et al.
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21 have explored the HER catalytic activity of pyrene-porphyrin-based covalent organic framework. 38
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23 COFs are also used as a host or support to fabricate a water-splitting electrocatalyst. 23 Aiyappa et
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25 al. have investigated the electrocatalytic activity of a bipyridine-linked COF (TpBpy) towards
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27 oxygen evolution reaction (OER) by incorporating Co(II) ions into its porous framework. 39 COFs
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29 as electrocatalysts is still in its infancy and there is much free space for the development of new
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31 COF-based electrocatalysts 23 for HER.
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33 In the quest for searching electrocatalysts based on COFs, we have herein performed den-
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35 sity functional theory calculations on a bipyridine-linked covalent triazine framework (Bpy-CTF),
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37 which has been synthesized by Hug et al. 40 We have investigated the electronic properties of Bpy-
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39 CTF and found that the triazine framework is a direct band gap semiconductor with the band gap of
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41 1.93 eV. In order for a system to become electrochemically active, 23,41 a low band gap is desired.
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43 we have adopted co-doping and substitution strategy for reducing the band gap of the framework.
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45 We have co-doped the triazine framework with silicon and phosphorous atoms, followed by sub-
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47 stitution of bipyridine hydrogens at P-site by fluorine atoms. After co-doping and substitution
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49 engineering, the band gap (7.0 meV) of the framework almost vanishes. Such lowering of band
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51 gap of the framework may facile charge transfer kinetics during HER. Next as revealed by many
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53 previous studies, using the Gibbs free energy of binding of atomic hydrogen (∆G0H ) as the key de-
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55 scriptor, we have concluded that our predicted model system (SiPF-Bpy-CTF) may be a potential
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candidate as electrocatalysts for HER.
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All the calculations were performed within the framework of density functional theory (DFT)
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as implemented in the Vienna ab initio simulation package (VASP) code, 42,43 which is based on
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9 the projector augmented wave (PAW) method. 44 To describe the exchange-correlation Exc [ρ ] inter-
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11 actions, generalized gradient approximation 45 (GGA) with the Perdew-Burke-Ernzerhof 46 (PBE)
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13 functional was employed. A large vacuum space of 20 Å was added along z-direction to prevent
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15 the interaction between periodic images. The plane-wave cutoff energy was set to 400 eV. For
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17 geometry optimizations, the Brillouin zone was sampled with the Monkhorst-Pack 47 mesh with
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19 the k-point grid of 3  3  1, while for the electronic structure calculations a comparatively more
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21 dense k-point grid of 7  7  1 was used. The energy convergence tolerance was set to 1  10 4
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23 eV and the structures were optimized until the force on each atom becomes less than 0.02 eV/Å.
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25 As we know, under standard conditions, the overall HER pathway 11 consists of an initial state
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27 H+ + e , an intermediate adsorbed H*, and the final product 12 H2 , which is described by the fol-
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29 lowing equation
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31 1
H+ (aq) + e = H2 (g) (1)
32 2
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34 The total energies of H+ + e and 12 H2 are equal. The Gibbs free energy of adsorption of
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36 intermediate hydrogen (∆G0H ) on the catalyst is considered as the key factor to evaluate the HER
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38 activity of the catalyst. The Gibbs free energy of adsorption of atomic hydrogen 11 is defined by
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40 the equation given below
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44 ∆G0H = ∆EH + ∆EZPE T∆SH (2)
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47 where ∆EH is the differential hydrogen adsorption energy. ∆EZPE and ∆SH are the difference
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49 in zero-point energy and the entropy between atomic hydrogen adsorption on the catalyst and
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51 hydrogen in the gas phase, respectively. The differential hydrogen adsorption energy 11 ∆EH is
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53 calculated by the following equation
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∆EH = EnH E(n 1)H EH (3)
6 2 2
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8 where the catalyst is defined by the asterisk. EnH and E(n 1)H are the total energies of the
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10 catalyst with n and (n - 1) adsorbed hydrogens, respectively. EH2 is the total energy of H2 molecule
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12 in the gas phase. The difference in zero-point energy between atomic hydrogen adsorption 11 on
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14 the catalyst and hydrogen in the gas phase is calculated by the equation shown below
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17 1)H
18 ∆EZPE = EnH  EZPE
(n 1 H2
E (4)
ZPE
19 2 ZPE
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where EnH 
22 ZPE is the zero-point energy of n adsorbed atomic hydrogen without any contribution
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from the catalyst and EH 2
ZPE is the zero-point energy of H2 molecule in the gas phase. Another
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parameter to calculate ∆G0H , namely, ∆SH is given by the following equation
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29 1 0
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∆SH = S (5)
2 H2
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where S0H2 is the entropy of H2 gas under standard condition. 14
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In the volcano curve, the average Gibbs free energies of atomic hydrogen adsorption 11 (∆GaH )
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36 on the catalyst are used to calculate the theoretical exchange current (i0 ). ∆GaH is given by the
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38 same equation as equation 2, in which ∆EH is replaced by ∆EaH . ∆EaH is given by the following
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40 equation
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42 n
∆EaH = EnH Ecat EH (6)
43 2 2
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45 where Ecat is the total energy of the catalyst. Calculations of the exchange current (i0 ) are done
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based on the Norskov's assumption. 48 If ∆GaH  0, the exchange current (i0) at pH = 0 is given by
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1
i0 = ek0 (7)
52 1 + exp( ∆GaH =kb T)
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54 and when ∆GaH > 0, the following expression is used to calculate the exchange current (i0 )
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i0 = ek0 (8)
6 1 + exp(∆GaH =kb T)
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8 where k0 is the rate constant, which is set to unity for our calculations.
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10 Before we discuss the HER catalytic properties of our proposed model system (SiPF-Bpy-
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12 CTF), we have investigated the electronic properties of bare Bpy-CTF. Then, in order to make the
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14 system electrochemically active, modification of bare Bpy-CTF has been carried out through co-
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16 doping of Si and P at the docking site of bipyridine and substitution of bipyridine hydrogens at the
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18 P-site by F atoms. Finally, we have demonstrated the HER catalytic property of our model system.
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20 The optimized geometric structure of 2  2  1 supercell of monolayer Bpy-CTF is shown in
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22 Figure 1. The unit cell is indicated by the hexagonal box. Our calculated optimized lattice constant
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24 is 21.84 Å. As displayed in Figure 1, the framework is composed of two building blocks, namely,
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26 triazine and bipyridine. The C–C bond length joining these two building blocks is 1.47 Å, which
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28 is the average of C–C (1.39 Å) and C=C (1.54 Å) bond lengths. This indicates the partial double
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30 bond character of the C–C bond connecting the two building blocks. Next, we turn our attention
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32 towards the electronic properties of Bpy-CTF. From the electronic band structure, plotted in Figure
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34 2a, we have seen that Bpy-CTF is a direct band gap semiconductor with the band gap value of 1.93
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36 eV. The electronic band structure suggests the flat-band nature of valence band maximum (VBM)
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38 and conduction band minimum (CBM) states. As revealed by many previous studies, 33,34,36,49 the
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40 flat-band nature of VBM and CBM states can be explained by the band-decomposed charge density
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42 plot. The band-decomposed charge density plot of CBM and VBM states (Figure 2b) indicate that
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44 the wave function corresponding to the CBM and VBM states are localized and this fact may be
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46 attributed to our observed flat-band nature of those states from the band structure (Figure 2a).
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48 Previously, many research works have witnessed the remarkable applications of metal anchored
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50 bipyridine-linked porous organic frameworks in the field of catalysis. 50–52 They have shown that
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52 bipyridine nitrogens imbedded in a porous framework can welcome various metal ions. But, to
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54 the best of our knowledge, non-metal co-ordinated with bipyridine linker in the porous organic
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56 framework has yet not been reported. In the quest for systems with almost vanishing band gap, we
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have attached silicon atoms to the bipyridine moiety of Bpy-CTF. Our calculated band gap for this
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silicon-doped Bpy-CTF is 0.82 eV, which is still higher than our desired material. Recently, Wu et
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al. 53 have reported a covalent organic framework, in which one bipyridine unit is co-ordinated with
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9 Fe2+ ions and another with Co2+ ions, for constructing multifunctional electrocatalyst. Inspired
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11 by this research work, we have co-doped Bpy-CTF with Si (attached with two chlorine atoms) and
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13 phosphorous at the docking site of bipyridine linker. From the electronic band structure analysis,
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15 we have found that this co-doped system has a band gap of 0.012 eV. To further reduce the band
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17 gap, we have substituted two hydrogen atoms of P-doped bipyridine moiety with fluorine atoms and
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19 we denote this system as our model system (SiPF-Bpy-CTF). The optimized geometric structure
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21 of 2  2  1 supercell of our model system is displayed in Figure 3. To check the energetic stability
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23 of the system, we have calculated the formation energy (Ef ), which is defined by
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25
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27 Ef = Emodelsystem (nC EC + nH EH + nN EN + nSi ESi + nP EP + nF EF + nCl ECl )=n (9)
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30 where Emodelsystem is the total energy of our proposed model system. EC , EH , EN , ESi , EP ,
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32 EF , and ECl are the total energies of a single carbon, hydrogen, nitrogen, silicon, phosphorous,
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34 fluorine, and chlorine atoms, respectively. nC , nH , nN , nSi , nP , nF , and nCl are the total number
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36 of carbon, hydrogen, nitrogen, silicon, phosphorous, fluorine, and chlorine atoms, respectively
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38 in our proposed triazine framework. Here n is the total number of atoms of the model system. A
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40 negative value of Ef indicates the energetic stability of the system. Our calculated formation energy
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42 for the system is -0.23 eV/atom, which indicates that our predicted triazine framework (SiPF-
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44 Bpy-CTF) is energetically stable. Although we have not performed phonon calculation for the
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46 dynamic stability of SiPF-Bpy-CTF, we have predicted a synthetic route inspired by the research
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48 work carried out by Bhadra et al. 54 They have synthesized a Pd metal-anchored covalent organic
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50 framework, in which Pd atoms were capped with the bipyridine nitrogens before the reaction. Here,
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52 in our case, the reaction between 2,2'-bipyridine-5,5'-dicyano silicon chloride and phosphorous
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54 docked 6,6'-difluoro-5,5'-dicyano-2,2'-bipyridine may result in our model system. The schematic
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56 representation for the experimental synthesis of SiPF-Bpy-CTF is shown in Figure S2. Next,
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we have investigated the electronic properties of SiPF-Bpy-CTF. The electronic band structure of
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SiPF-Bpy-CTF is plotted in Figure 4a. From this electronic band structure, we infer that the band
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gap (7 meV) of the system almost vanishes. As the PBE functional underestimates the band gap,
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9 we have also calculated the band structure using HSE06 functional. 55 The HSE06 band structure
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11 of our model system is shown in Figure S1. But, the band gap of the system remains almost
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13 same. Such low band gap of the system may facile transfer of electrons from the VBM to the
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15 CBM and as a result the electrical conductivity of the material increases as mentioned by previous
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17 studies. 56–58 Deng et al. have reported that such diminished band gap nature improves the electrical
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19 conductivity of the material, which is very much desired for an effective HER catalyst. 59 Such
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21 increased electrical conductivity may facile charge transfer kinetics during HER. From Figure 4b,
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23 we see that SiPF-Bpy-CTF shows electronic density of states very close to the Fermi level and that
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25 states mainly arises from the framework carbon, nitrogen, and impurity phosphorous atoms.
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27 Pursuing earlier research works, 1,3,4,11,22 the Gibbs free energy of adsorption of atomic hydro-
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29 gen (∆G0H ) has been devoted as a key factor to examine the HER catalytic activity of SiPF-Bpy-
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31 CTF. Firstly, we have identified the various possible adsorption sites for the adsorption of atomic
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33 hydrogen. From previous investigations on graphitic carbon nitride (g C3 N4 ), it is known that
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35 atomic hydrogen can bind with the N atom of triazine. Inspired by these research works, 20–22
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37 we have considered ten various possible adsorption sites (Figure 5) on SiPF-Bpy-CTF ,namely,
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39 (i) Si-site (ii) P-site (iii) Bpy N Si-site (iv) Bpy N P-site (v) triazine N1 (vi) triazine N2 (vii) tri-
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41 azine N3 (viii) triazine N4 (ix) triazine N5 (x) triazine N6. At all these sites, we have calculated
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43 the atomic hydrogen adsorption energy (Ead ) using the following equation:
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45
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47 1
Ead = EH SiPF Bpy CTF ESiPF Bpy CTF EH (10)
48 2 2
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50 where EH SiPF Bpy CTF and ESiPF Bpy CTF are the total energies of our model triazine frame-
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52 work with and without atomic hydrogen adsorption, respectively. EH2 is the total energy of a hy-
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54 drogen molecule. A more negative value of adsorption energy implies facile adsorption of atomic
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56 hydrogen on SiPF-Bpy-CTF. The atomic hydrogen adsorption energies (Ead ) at various possible
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sites are given in Table 1. From the tabulated values, we have found that atomic hydrogens stick at
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the Si-site of SiPF-Bpy-CTF with the highest negative adsorption energy value of -0.36 eV. Simi-
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lar to previous studies, 20–22 atomic hydrogen also interacts favourably with the N atom of triazine
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9 ring. Table 1 indicates that the adsorption energy is negative at six adsorption sites among the
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11 ten considered adsorption sites. The optimized geometric structures of SiPF-Bpy-CTF at differ-
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13 ent hydrogen coverages (θ ) are shown in Figure 6. Here, it is to be mentioned that we have also
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15 calculated adsorption energy at the Si-site using DFT-D3 method 60 and the calculated adsorption
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17 energy remains almost same as the GGA-PBE method. Now, we proceed to calculate the key
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19 factor, ∆G0H for determining the HER catalytic activity of SiPF-Bpy-CTF, considering these six
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21 adsorption sites. An ideal HER catalyst provide catalytic sites, where the atomic hydrogen is ad-
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23 sorbed neither too strongly nor too weakly, i.e, the value of ∆G0H should be equal to zero. The
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25 Gibbs free energies for the adsorption of atomic hydrogen (∆G0H ) at different hydrogen coverages
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27 are displayed in Figure 7a. The calculated ∆G0H value for SiPF-Bpy-CTF at (θ = 1/6) is -0.06
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29 eV, which is very close to an ideal HER catalyst. As the coverage (θ ) increases, the interaction
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31 between H and SiPF-Bpy-CTF slightly decreases with the ∆G0H values of -0.05 and 0.09 eV at
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33 H coverages of 1/3 and 1/2, respectively. 11 Therefore, we can say that our predicted model system
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35 may be a potential catalyst for HER at a wide range of hydrogen coverages.
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37 Finally, to compare the HER catalytic activity of our model system with other previously re-
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39 ported catalysts, 4,11,61 a volcano curve is plotted as given in Figure 7b. The average Gibbs free
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41 energy of adsorption of atomic hydrogen (∆GaH ) at θ = 1/2 is used to obtain the theoretical ex-
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43 change current (i0 ). It is known that the closer the position of the catalyst to the peak of the volcano
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45 curve, the better the catalyst. Catalysts with positive ∆GaH lies at the right leg of the volcano curve
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47 while catalysts with negative value of ∆GaH resides at the left leg of the volcano curve. From
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49 figure 7b, it is clear that our predicted triazine framework lies almost at the peak of the volcano
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51 curve with theoretical exchange current (logi0 ) of -0.39 Acm 2 . We know that Si-Cl bond is very
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53 prone to hydrolysis and therefore, we have also calculated the HER catalytic activity of our model
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55 system with Cl atoms removed by -OH groups. The calculated ∆G0H at θ = 1/6 is -0.06 eV, which
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is exactly the same as mentioned earlier when Si is attached with chlorine atoms. The hydrolysed
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triazine framework also lies almost at the peak position of the volcano curve with the ∆GaH value
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of 0.029 eV at θ = 1/2 and theoretical exchange current (logi0 ) of -0.62 Acm 2 . Therefore, based
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9 on the results of almost vanishing band gap, nearly zero value of ∆G0H , and large theoretical ex-
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11 change current, we can say that our proposed triazine framework may be a potential candidate for
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13 HER catalyst.
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15 In summary, using density functional theory based calculations, we have predicted a triazine
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17 framework (SiPF-Bpy-CTF), which exhibits good HER catalytic activity. Firstly, we have inves-
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19 tigated the electronic properties of bare Bpy-CTF, which is a direct band gap semiconductor with
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21 the band gap of 1.93 eV. Then, in order to reduce the band gap of the framework, we have adopted
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23 co-doping and substitution strategy. After co-doping of Bpy-CTF with Si and P atoms, followed by
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25 substitution of bipyridine hydrogens at P-site by F-atoms, we have designed a triazine framework
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27 (SiPF-Bpy-CTF) with almost vanishing band gap of 7 meV. The nitrogen atoms of the triazine
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29 moiety and Si-site are found to be the adsorption sites for atomic hydrogen adsorption from the
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31 energetic point of view. Using the Gibbs free energy of binding of atomic hydrogen as the key
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33 factor to determine the HER catalytic activity, we have found that our predicted model system ex-
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35 hibits ∆G0H value of -0.06 eV at θ = 1/6, which is very close to an ideal HER catalyst. To compare
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37 the HER catalytic activity of our model system with other previously reported materials, a volcano
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39 curve is plotted. The predicted triazine framework (SiPF-Bpy-CTF) lies almost at the peak position
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41 of the volcano curve with the ∆GaH value of 0.01 eV at θ = 1/2 and theoretical exchange current
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43 (logi0 ) of -0.39 Acm 2 . Moreover, the hydrolysed triazine framework also exhibits superior HER
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45 catalytic activity. Therefore, based on the above results, we can conclude that SiPF-Bpy-CTF may
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47 be a potential catalyst for HER. We do hope that our results will encourage the experimentalists to
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49 design metal-free electrocatalysts based on covalent organic frameworks.
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The HSE06 band structure plot of SiPF-Bpy-CTF (Figure S1). The route for the experimental
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synthesis of our predicted model system (SiPF-Bpy-CTF) (Figure S2).
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13 Acknowledgments
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16 Financial support from DST NanoMission, Government of India, New Delhi, through Research
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18 Grant SR/NM/NS-1005/ 2016 is gratefully acknowledged. Biswajit Ball is grateful to UGC, New
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20 Delhi for the award of Senior Research Fellowship (SRF) [UGC-Ref. No.: 245/(CSIR-UGC NET
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22 DEC. 2016)]. Chandrima Chakravarty is grateful to CSIR, New Delhi, for the Award of Senior
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24 Research Fellowship (SRF) [CSIR Award No. 09/202(0051)/2015-EMR-I].
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3 Table 1: The calculated atomic hydrogen adsorption energies (eV) on SiPF-Bpy-CTF at various possible ad-
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sorption sites.
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Adsorption sites Adsorption energy (eV)
8 Si-site –0.36
9 P-site +0.07
10 Bpy N Si-site +2.04
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Bpy N P-site +1.73
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13 triazine N1 –0.25
14 triazine N2 +0.10
15 triazine N3 –0.22
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triazine N4 –0.06
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18 triazine N5 –0.02
19 triazine N6 –0.32
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26 Figure 1: Optimized geometric structure of 2  2  1 supercell of Bpy-CTF. The unit cell is indicated by the
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12 CBM

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VBM
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26 Figure 2: (a) Band structure plot of Bpy-CTF. Blue dashed line indicates the Fermi level. (b) The charge
27 density plot of CBM and VBM states of Bpy-CTF. The isovalue is set to 0.002 e/Å3 .
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26 Figure 3: Optimized geometric structure of 2  2  1 supercell of SiPF-Bpy-CTF. The unit cell is indicated by
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26 Figure 4: (a) Band structure plot of our proposed system (SiPF-Bpy-CTF). The Fermi level is indicated by the
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i. Triazine_N5-site
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26 Figure 5: Atomic hydrogen adsorption on SiPF-Bpy-CTF at various possible adsorption sites (a) Si-site (b)
27 P-site (c) Bpy N Si-site (d) Bpy N P-site (e) triazine N1 (f) triazine N2 (g) triazine N3 (h) triazine N4 (i) tri-
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azine N5 (j) triazine N6.
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26 Figure 6: Optimized geometric structure of atomic hydrogen adsorption on SiPF-Bpy-CTF at various hydro-
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8 SnSe-VSn
Ni@1zigzag
GeSe-VGe
9 Pt
Ti3C2O2
10 V2CO2 Nb2CO2

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log(i0/(Acm-2))
Nb4C3O2

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Nb4C3 Ni@2zigzag
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Nb2C
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18 𝑎
∆𝐺𝐻∗ (eV)
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26 Figure 7: (a) Free energy diagram of HER acting on SiPF-Bpy-CTF at three different hydrogen coverages. (b)
27 Plot of volcano curve as a function of average Gibbs free energy of atomic hydrogen adsorption (∆GaH ).
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