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Oxygen and Lithium Doped Hybrid BoronNitride/Carbon Networks for Hydrogen Storage Farzaneh Shayeganfar, and Rouzbeh Shahsavari Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.6b02997 • Publication Date (Web): 23 Oct 2016 Downloaded from http://pubs.acs.org on October 24, 2016

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Oxygen and Lithium Doped Hybrid Boron-Nitride/Carbon Networks for Hydrogen Storage

Farzaneh Shayeganfar1,2 and Rouzbeh Shahsavari1,3,4,* 1

Department of Civil and Environmental Engineering, Rice University, Houston, TX 77005

2

Institute for Advanced Technologies, Shahid Rajaee Teacher Training University, 16875-163, Lavizan,

Tehran, Iran. 3

Department of Material Science and NanoEngineering, Rice University, Houston, TX 77005

4

Smalley Institute for Nanoscale Science and Technology, Rice University, Houston, TX 77005

*Corresponding author email: [email protected]

Keywords: pillared boron nitride, pillared graphene , hydrogen storage, doping

Abstract. Hydrogen storage capacities have been studied on newly designed three-dimensional

pillared boron nitride (PBN) and pillared graphene boron nitride (PGBN). We propose these novel materials based on the covalent connection of BNNTs and graphene sheets, which enhance the surface and free volume for storage within the nanomaterial and increase the gravimetric and volumetric hydrogen uptake capacities. Density functional theory and molecular dynamic simulations show that these lithium- and oxygen-doped pillared structures have improved gravimetric and volumetric hydrogen capacities at room temperature, with values on the order of 9.1-11.6 wt% and 40-60 g/L. Our findings demonstrate that the gravimetric uptake of oxygen- and lithium-doped PBN and PGBN have significantly enhanced the hydrogen sorption and desorption. Calculations for O-doped PGBN yield gravimetric hydrogen uptake capacities

1 ACS Paragon Plus Environment

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greater than 11.6 wt% at room temperature. This increased value is attributed to the pillared morphology, which improves mechanical properties and increase porosity, as well as the high binding energy between oxygen and GBN. Our results suggest that hybrid carbon/BNNT nanostructures are as an excellent candidate for hydrogen storage, owing to the combination of the electron mobility of graphene and the polarized nature of BN at heterojunction, which enhance uptake capacity, providing ample opportunities to further tune this hybrid material for efficient hydrogen storage.

Introduction The widespread adorption and application of hydrogen as a vehicular fuel is limited by storage system capabilities, as well as the production of hydrogen at rapid rates. A significant number of theoretical and experimental investigations have been conducted to investigate the enhancement of gravimetric and volumetric hydrogen sorption and desorption properties to meet the US Department of Energy criteria. To overcome the key technical barriers in hydrogen storage, several groups have developed strategies to enhance the hydrogen capacity such as carbon based nanomaterials (e.g. graphene, carbon nanotube, pillared graphene, 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 boron-nitride nanomaterials (BN) (e.g. porous BN, BN nanotube),

17 , 18

metal

organic

frameworks

(MOFs),19,20,21,22 covalent organic frameworks (COFs),23,24,25,26,27,28,29,30 porous aromatic frame works (PAFs),31 a n d porous polymer networks (PPNs).32 Research conducted by Burres et.al has revealed the potential of graphene oxide frameworks (GOFs) as a gas storage material,33 while MOFs and COFs are a l s o good candidates, due to their ability to take up and release hydrogen with fast kinetics.27 Zhang and his collaborators recently reported that porous BN


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exhibits excellent structural and electronic properties for hydrogen production a n d storage.17 Sun et al. propsed porous organic frameworks such as the lithium tetrazolide group can enhance hysdrogen storage due to much more stable and polarized than the aromatic groups with lithium atoms.34 Pillared materials such as 3D pillared graphene (PG) 35 , 36 , 37 , 38 and pillared covalent organic frameworks (PCOF)27 have large hydrogen uptakes. In the case of pillared materials, Li-doping significantly increases the interaction between hydrogen and t h e substrate.35, 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46

This work builds upon previous research we have conducted on the anisotropic

mechanical properties of 3D porous BN nanostructures,39 focusing now on the potential of such materials for use in hydrogen storage. Both experimental and theoretical studies have demonstrated that BN nanophases have better properties than their carbon-based counterparts for hydrogen storage, due to stronger interactions between H2 molecules and the heteropolar BN, as well as the wide energy band gaps of BN materials (5-6 eV). 47 , 48 , 49 , 50 For example, multi-walled (MW) carbon nanotubes can gravimetrically adsorb ( 200 ps. From Figure 2g,h, it can be concluded that temperature could control charging/releasing or sorption/desorption process (MD method). In the case of the heating regime, gravimetrical uptake values decrease with temperature while in the cooling regime hydrogen uptake values increase even before the desorption process. Finally, to better put our results into the perspective and enable comparison with other material classes, Figure 3 illustrate an overlay map of various hydrogen storage with two different computational tools: Molecular Dynamic (MD) and Monte-Carlo (MC) simulation. The gravimetric uptake is indicated at the vertical axis, such as Metal Oxide Framework,1 Metal Organic Framework (MOF),6 Pillared graphene,35 Graphene Oxide Framework,7 Pillared Li-dispersed boron carbide,11 Single-walled Boron nitride nanotube,9 Graphene hollow walls,2 Li/O doped boron nitride


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nanotube,12 Carbon nanoscroll,10 Carbon nanotube,5 Porous BN,3 C60-intercalated graphite.4 Several techniques and devices as presented in Figure 3 are applied to improve the gravimetric and volumetric hydrogen storage. For instance, the metal-organic, covalent-organic, carbon- and BN-based devices can take up and release hydrogen with fast kinetics, but work effectively at low temperature as conclusion of low hydrogen binding. In our proposed model for PGBN and PBN-based hydrogen storage, the hydrogen binding energy with host nanomaterial at room temperature is around 300-600 meV, which provides reasonable stability for loading and unloading hydrogen molecules as a result of improved polarization in the hybrid BN/GE junction. Our findings show that the gravimetric uptake for new designed nanostructure as one can be seen in Figure 3 has been enhanced.

Atomistic simulation results. To illustrate the hydrogen molecule adsorption on BNNT and graphene, variation of potential energy at fix point of z=0 and z=1/2L is plotted in 3D in Figure 4a,b. Here, L is the total length of BNNT. As can be seen in Figure 4a, there is some minimal potential energy at z=0 to adsorb an H2 molecule, however for z=1/2L the surface potential energy shows no preference for the adsorption of H2 molecules near the octagonal junction. These findings support our results in section 3-1,3-2 about adsorption of hydrogen near the junction curvature and BN and graphene sheets. To investigate the surface energy of hydrogen molecule adsorption in the x-z or y-z planes, we calculated and plotted the total energy for x=0 in Figure 5a,b. This figure demonstrates that there is a maximum surface potential energy near the junction with BN and graphene sheets, confirming our previous results in section 3-1,3-2.


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Summary and Conclusions This work proposes new 3D nanopillared structures based on BNNT and graphene with high performance for hydrogen storage. The structural stability and hydrogen adsorption of both PBN and PGBN are investigated by first principles calculations, while the storage capacity of the materials are determined using molecular dynamics simulations and representative thermodynamic conditions. This research was further extended using atomistic and continuum models (Supporting information Section II). One of the key characteristics that influence hydrogen storage is the surface area and pore volume at room temperature. In this context, both PBN and PGBN have a larger surface area compared to other porous materials. These nanopillared structures are demonstrated as a good candidate for fast loading and unloading of hydrogen by physisorption. Moreover, doping PBN and PGBN with O and Li atoms can significantly increase their storage as a result of polarization of H2 due to O and Li charges, followed by dipole interactions between hydrogen and host atoms which act as a strong connection instead of weak van der Waals forces in physisorption. Our MD results reveal that the gravimetric as well as volumetric uptake of pristine PBN at ambient conditions are less than the hybrid PGBN, due to the delocalized graphene electron clouds. For pristine PBN, the computed hydrogen storage reached to 4.8 wt% and in the case of pristine PGBN values up to 5.7 wt% were obtained. Furthermore, we investigated the effect of O and Li decoration of nanopillared structures on hydrogen storage capacity. For chemisorbed OPBN with 2.12 eV adsorption energy, H2 molecules tend to adsorb onto oxygen atoms of PGBN with higher adsorption energy (Ead = -558 meV) than pristine PBN (Ead = -483 meV). One oxygen atom can adsorb a maximum of six H2 molecules and the adsorption energy reduces to about 345 meV (due to repulsion between H2 molecules). Three of the H2 molecules are near the O atom and


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the rest of molecules are far away from O. For O-PBN, the hydrogen storage at 77 Kwas calculated to be 13.61 wt% while that of O-PGBN can exceed 14.77 wt%. H2 molecules tend to adsorb on the center of physisorbed Li-PBN and Li-PGBN with adsorption energies of 432 meV and 510 meV, respectively. The Li decorated PBN at 77 K leads to 11.3 wt% hydrogen storage capacity, compared to the 12.2 wt% of Li-PGBN. It can be concluded that hydrogen adsorption can be increased significantly in O-doped nanopillared structures. This work demonstrated the novel hybrid carbon/BNNT nanostructure as an excellent candidate for hydrogen storage, owing to the combination of the electron mobility of graphene and the polarized nature of BN at heterojunction, which enhance hydrogen uptake capacity, providing ample opportunities to further tune this hybrid material.

Associated Content Supporting Information Complete system setup for creating the pillared structures and continuum model for adsorption of hydrogen molecule on pillared GBN is available free of charge via the Internet at http://pubs.acs.org.

Acknowledgement FS would like to thank Iran Science Elites Federation for grant number 11/66332. RS acknowledges the financial support from Rice University. The supercomputer machines utilized in this work were supported in part by NIH award NCRR S10RR02950 and an IBM Shared University Research (SUR). Author Contributions F.S. and R.S. designed the research; F.S. and R.S. performed the computational research and


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analyzed the data; and R.S. and F.S. wrote the paper. Competing Financial Interest The authors declare no competing financial interest.


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Constants and Interlayer Interactions of Complex Hydrated Oxides: Case Study of Tobermorite and Jennite, J. Am. Ceram. Soc. 2009, 92 (10), 2323-2330. 62

Kharche, N.; Nayak, S. K. Quasiparticle Band Gap Engineering of Graphene and Graphone on

Hexagonal Boron Nitride Substrate. Nano Lett. 2011, 11, 5274-5278. 63

Wuest, J.D.; Rochefort, A. Strong adsorption of aminotriazines on graphene. Chem. Commun.

2010, 46, 2923-2925. 64

Han, S. S.; Kang, J. K. and Lee, H. M.The Theoretical Study on Interaction of Hydrogen with

Single-Walled Boron Nitride Nanotubes. I. The Reactive Force Field ReaxFF(HBN) Development. J. Chem. Phys. 2005, 123, 114703.

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Van Duin, A. C. T.; Dasgupta, S.; Lorant, F.; Goddard, W. A. J. ReaxFF: A Reactive Force

Field for Hydrocarbons. Phys. Chem. A 2001, 105, 9396-9409.

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Weismiller, M. R.; Van Duin, A. C. T.; Lee, J.; Yetter, R. A. J. ReaxFF Reactive Force Field

Development and Applications for Molecular Dynamics Simulations of Ammonia Borane Dehydrogenation and Combustion. Phys. Chem. A 2010, 114, 5485-5492.

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Maitland, G. C.; Rigby, M.; Smith, E. B. and Wakeham, W. A.1981 Intermolecular Forces—

Their Origin and Determination (Oxford: Clarendon).

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Cromwell, P. R.Polyhedra; Cambridge University Press: New York, 1997. 26 ACS Paragon Plus Environment

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Shayeganfar, F. and Rochefort, A. Electronic Properties of Self-Assembled Trimesic Acid

Monolayer on Graphene. Langmuir 2014, 30, 9707-9716. 71

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Surface by Self-Assembling of Trimesic Acid. J. Phys. Chem. C, 2015, 119 (27), 15742–15748.

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Shayeganfar, F. Columnar Organization of Stack-Assembled Trimesic Acid on Graphene. J.

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Shayeganfar, F. Energy Gap Tuning of Graphene Layers with Single Molecular F2 Adsorption.

J. Phy. Chem. C 2015, 119 (22), 12681-12689.


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TABLE 1. Adsorption energy (Ead) and hydrogen molecule distance dBN-H2 and hydrogen bond dH-H. Numbers in parenthesis are calculated based on PBE+D function. (PBN) Ead (meV) dBN-H2 (Å) dH-H (Å) -76 (-92) 2.35 0.78 H2 - tN -63 (-78) 2.52 0.83 H2 - tB -71 (-86) 2.47 0.81 H2 - bBN -85 (-102) 2.22 0.79 H2 - co (PGBN) Ead (meV) dBN-H2 (Å) dH-H (Å) -92 (-116) 2.25 0.82 H2 - bCN -88 (-104) 2.31 0.81 H2 - bCB -112 (-131) 2.15 0.80 H2 - co -67 (-81) 2.52 0.80 H2 - tC -78 (-93) 2.43 0.80 H2 - bCC

TABLE 2. Adsorption energy of O- and Li- doped PBN and PGBN. Numbers in parenthesis are calculated based on PBE+D function. X-doped Pillared O-PBN Li-PBN O-PGBN Li-PGBN

Ead (eV) -2.11 (-2.23) -0.95 (-1.11) -2.32 (-2.49) -1.13 (-1.29)

TABLE 3. Adsorption energy Ead and molecule X-doped pillared structures distance dBN-X and hydrogen bond dH-H. Numbers in parenthesis are calculated based on PBE+D function. H2-X-doped (PBN) Ead (meV) dBN-H2 (Å) dH-H (Å) -483 (-497) 2.42 0.82 H2 - tON -417 (-431) 2.54 0.80 H2 - tOB -357 (-376) 2.71 0.79 H2 - tLiN -318 (-332) 2.74 0.81 H2 - tLiB H2-X-doped (PGBN) Ead (meV) dBN-H2 (Å) dH-H (Å) -558 (-571) 2.35 0.83 H2 - tON -521 (-539) 2.52 0.80 H2 - tOB -463 (-484) 2.75 0.79 H2 - tLiN -449 (-466) 2.79 0.82 H2 - tLiB


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(a)

(b)

(d)

(e)

(c)

(f)

(h)

(g)

N B H2 Li O C


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Figure 1. Hydrogen molecule distribution for (a) PBN and molecular dynamic optimized of hydrogen adsorption (b) in pure PBN and (c) O-doped PBN, (d) the same as (a) plot for PGBN, (e) Li-doped PGBN and (f) O-doped PGBN. Schematic of different H2 molecule adsorption sites for (g) pure PBN and (h) PGBN. Blue color is Nitrogen, pink is Boron, gray is Carbon, green is H2, yellow is Li and red is Oxygen.


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(b)

(a)

16

16

Gravimetric Uptake (% wt)

12 10 8 O-doped Li-doped Pristine

6 4 2 0

0

20

40

60

PGBN

14

Gravimetric Uptake (% wt)

PBN

14

12 10 8

O-doped Li-doped Pristine

6 4 2 0

80

0

20

(c)

80

80 60 O-doped Li-doped Pristine

40 20 0

0

20

40

60

80 60 40 O-doped Li-doped Pristine

20 0

80

Pressure (bar)

(e)

PGBN

100

PBN

Volumetric Uptake (g/l)

Volumetric Uptake (g/l)

60

(d)

100

0

20

40

60

80

Pressure (bar)

(f) 20

20

PBN

Gravimetric uptake (% wt)

Gravimetric uptake (% wt)

40

Pressure (bar)

Pressure (bar)

16

12 77 K 300 K 8

4

200

400

600

800

PGBN 16

12 77 K 300 K 8

4

200

1000

Time (ps)

600

800

1000

(h)

16

16

PBN

12 10 8 6 4

Adsorption Desorption

2 0

50

PGBN

14

100 150 200 250 300 350 400 450

Gravimetric (% wt)

14

0

400

Time (ps)

(g)

Gravimetric (% wt)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Langmuir

12 10 8 6

Absorption Desorption

4 2 0

0

50

Temprature (K)


100 150 200 250 300 350 400 450

Temprature (K)

Langmuir

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Figure 2. Gravimetric hydrogen uptake wt % vs pressure for pure, Li/O-doped of (a) PBN and (b) PGBN at 300 K. Volumetric hydrogen uptake vs pressure for the same nanostructures for (c) PBN and (d) PGBN. Time evolution of hydrogen uptake for O-doped (e) PBN and (f) PGBN at 300 K, 77 K and 5 bar. Sorption/desorption of hydrogen vs temperature ranging from 75 K to 400 K for (g) PBN and (h) PGBN at pressure of 10 bar.

O -doped Pillared Graphene/ Boron-Nitride [this study] C60-intercalated graphite [4] Porous BN [3]

Metal Oxide Framework [1]

Carbon Nanotube [5]

12

Carbon nanoscroll [10]

12 9

Li/O doped Boron Nitride Nanotube [12]

9

12

6

9

3

6

Metal Organic Framwork [6]

Pillared Graphene [35] Figure 1. Pillared graphene. A novel 3-D network nanostructure

3

6

Graphene-Oxide Framework [7]

3 Graphene hollow walls [2]

and b) GOFformation. J .C h e m .P h y s .123,1 1 4

Pillared Li-dispersed boron carbide [11]

˚

Single-walled Boron Nitride Nanotube[9]

Figure 3. Overlay map for hydrogen storage devices with two different computational tools: Molecular Dynamic and Monte-Carlo simulation. Metal Oxide Framework,1 Metal Organic Framework,6 Pillared graphene,35 Graphene Oxide Framework,7 Pillared Li-dispersed boron


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carbide,11 Single-walled Boron nitride nanotube,9 Graphene hollow walls,2 Li/O doped boron nitride nanotube,12 Carbon nanoscroll,10 Carbon nanotube,5 Porous BN,3 C60-intercalated graphite.4

Figure 4. (a) Energy surfaces (ET) in the x–y plane at (a) z = 0 and (b) z=1/2L, which are related to the atomistic (Eq. (1)), i.e. ET (x, y, (0,1/2L).

Figure 5. Energy surfaces (ET)in the y-z plane at x = x0 which are related to the atomistic (Eq. (1)), i.e. ET (x0, y, z).


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TOC Gravimetric Uptake (% wt)

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16

PGBN

12 O-doped Li-doped Pristine

8 4 0

0

20 40 60 80 Pressure (bar)


Carbon Networks

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