A novel nitrogen rich porous aromatic framework for hydrogen and carbon dioxide storage

Article abstract of DOI:10.1039/c3ta13194g

A nitrogen rich, p-phenylenediamine based, porous aromatic framework (NPAF) with 1790 m² g^-1 BET surface area has been synthesized by using a Yamamoto coupling technique. The NPAF has shown a hydrogen uptake of 1.87 and 0.33 wt% at 7

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A novel nitrogen rich porous aromatic framework for hydrogen and
carbon dioxide storage
Derviꢀ Emre Demirocak,*a Manoj K. Ram,a Sesha S. Srinivasan,b,a D. Yogi Goswamia and Elias K.
Stefanakosa
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
The nitrogen rich, pꢀphenylenediamine based, porous aromatic framework (NPAF) with 1790 m2/g BET
surface area has been synthesized by using Yamamoto coupling technique. NPAF has shown hydrogen
uptake of 1.87 and 0.33 wt. % at 77 K/1 atm and 298 K/80 bar, respectively. The CO2 uptake and
10 selectivity of NPAF at 273 K/1 atm is 3.64 mmol/g and 48, respectively.
material should have high gravimetric (55 g H2/kg system) and
volumetric density (40 H2/L system near ambient
g
)
Introduction
temperature.8 Porous materials can only achieve high storage
50 capacity at cryogenic temperatures (77 K) because of the weak
interaction (low adsorption enthalpy due to physisorption) of
hydrogen molecules with the porous material. Hydrogen storage
capacity of a material is a function adsorption enthalpy, pore
size/volume and surface area.23, 24 To achieve significant storage
55 capacity near room temperature, an optimal porous material
Hydrogen storage1 and carbon capture and storage (CCS)2 are the
key technologies to mitigate the adverse effects of global
warming induced by the anthropogenic CO2 emission as a result
15 of an excessive fossil fuel consumption. According to the
International Energy Agency, approximately twoꢀthirds of the
total CO2 emission is due to generation of electricity and heat (41
%) and transportation (22 %) sectors.3 Fossil fuel based power
plants are considered as large CO2 point sources and are suitable
20 sites for the application of the CCS technology.4 Currently, stateꢀ
ofꢀtheꢀart CCS technology relies on wet scrubbing by
26
should have an adsorption enthalpy of 15ꢀ20 kJ/mol H2.25,
Adsorption enthalpy can be tailored by optimizing the pore size
(0.6ꢀ0.7 nm) and doping with impurity atoms such as nitrogen
and boron.
alkanolamines; however, high energy penalty of this process
60
Nitrogen rich porous polymers are highly desirable for both
hydrogen storage and CCS applications. Basic nitrogen groups
can enhance the interaction of acidic CO2 gas with the porous
polymer matrix.27ꢀ29 On the other hand, increased nitrogen
content can increase the adsorption enthalpy of hydrogen as
65 shown by theoretical and experimental studies.30ꢀ33 To date,
hydrogen and CO2 storage characteristics of various porous
polymers such as hypercrosslinked polymers14, 15, 34ꢀ37, polymers
limits its widespread application.4, 5 On the other hand, vehicles
are considered as distributed CO2 sources and application of the
25 CCS technology is neither practical nor economical.6 Hence,
significant reduction of CO2 emission in the transportation sector
can only be achieved by replacement of oil with alternative
energy carriers such as hydrogen; however, hydrogen storage is
the bottleneck in utilization of hydrogen as an energy carrier in
30 the mobile applications.7 Therefore, novel materials and methods
that can satisfy the US Department of Energy (US DOE)
40
of intrinsic porosity38, porous aromatic frameworks (PAF)39,
and
covalent
organic
polymers
with
borazine41ꢀ45
,
hydrogen storage8 and CCS9 targets have yet to be discovered.
70 benzimidazole46ꢀ50, triazine51ꢀ57 and porphyrin58, 59 building blocks
as well as functionalized porous polymer networks60ꢀ67 with post
synthetic modifications29, 65, 68ꢀ74 were reported.
The last decade has witnessed expansive growth in the design
and synthesis of novel porous materials such as MOFs10,
,
11
35 COFs12, 13, porous polymers14ꢀ18 and templated carbons19, 20 for
gas storage applications. Considering CCS technology, porous
solid sorbents have the potential to lower the energy penalty of
the alkanoalamine based carbon capture process since these
materials can be regenerated simply by the pressure swing
40 adsorption and do not require high temperatures (100ꢀ140 °C for
alkanoalamines4) for regeneration.5 On the other hand, porous
solid sorbents should have considerable CO2 capacity (3 mmol/g)
at flue gas exhaust temperature and pressure (50ꢀ75 °C at 1 bar)
in the presence of water and other acidic impurities as well as
Herein, we have investigated for the first time the hydrogen
storage and CCS characteristics of pꢀphenylenediamine based
75 nitrogen rich porous aromatic framework (NPAF) at low and high
pressure.
Experimental details
Chemicals
Starting material 1,4ꢀBis(diphenylamino)benzene (1), reagents
80 for Yamamato coupling, 1,5ꢀCyclooctadiene, Bis(1,5ꢀ
cyclooctadiene)nickel(0) and 2,2′ꢀBipyridyl, and anhydrous
45 high selectivity towards CO2 to be a viable alternative to
alkanoalamines.4,
Furthermore, an ideal hydrogen storage
21, 22
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solvents tetrahydrofuran (THF) and N,NꢀDimethylformamide
(DMF) were purchased from SigmaꢀAldrich and used without
and pore volume of NPAF was calculated by the nonꢀlocal
density functional theory (NLDFT). The high pressure hydrogen
further purification. All materials were handled in an argon filled 60 and CO2 pressureꢀconcentrationꢀtemperature (PCT) isotherms
glove box in which oxygen and water levels were below 0.1 ppm.
were collected with SetaramꢀHyEnergy PCTPro 2000, Sievert’s
type apparatus. The sample loading was 1.5 g or more to limit the
uncertainty of the high pressure measurements. The uncertainties
associated with the hydrogen storage measurements are
65 thoroughly discussed in our previous work.77
5
Synthesis
Synthesis of, N, N, N’, N’ꢀTetrakis(4ꢀbromophenyl)ꢀpꢀ
phenylenediamine, compound 2, was accomplished by
a
procedure similar to the one reported previously.75 Briefly, 4.66 g
(29 mmol) of bromine dissolved in 50 ml of CHCl3 added
Results and discussion
10 dropwise to a 3 g (7.3 mmol) of 1,4ꢀBis(diphenylamino)benzene
dissolved in 50 ml of CHCl3. After refluxing the solution for 20
min, the hot solution was filtered. Upon cooling to room
temperature compound 2 was precipitated, and the product was
washed with cold CHCl3 (white powder, yield: 2.92 g, 55%).
Synthesis of NPAF and its structural, spectroscopic and
thermal characteristics
Synthetic route for the synthesis of NPAF is given in Scheme 1.
70 Successful sythesis of compound 2 is confirmed by TGA and
FTIR. The melting point of commpound 2 is 298 °C which is in
accordance with the reported value (Fig. S1, ESI†).75 Moreover,
FTIR analysis showed strong CꢀBr stretching peak around 500ꢀ
600 cmꢀ1 (Fig. S2, ESI†). The synthesis of NPAF was
75 accomplished by Yamamoto coupling which was proved to be an
15
Synthesis of NPAF was carried out in an argon filled glove
box at room temperature. Briefly, 1.2 g (1.65 mmol) of
compound 2, 1.03 g (6.6 mmol) of 2,2′ꢀBipyridyl, 0.72 g (6.6
mmol) of 1,5ꢀCyclooctadiene and 1.65 g (6.6 mmol) of Bis(1,5ꢀ
cyclooctadiene)nickel(0) were added to a 60 ml THF / 90 ml
effective method for synthesizing high surface area porous
20 DMF solution and stirred overnight. After removing the flask
from the glove box, 4 M HCl (100 ml) was added slowly to the
solution to dissolve the nickel atoms. After filtering the solution,
product was washed with CHCl3, THF and water (yellow powder,
yield: 0.61 g, 90%). As discussed in results and discussion
25 section, to remove the Clꢀ ions from NPAF, 0.6 g of NPAF was
refluxed in 100 ml of triethanolamine (TEA) for 8 h. Upon
cooling to room temperature, TEA treated NPAF was filtered and
washed with copious amount of water.
79
polymers.78,
The structure of NPAF was probed by 13C
CP/MAS NMR experiment. 13C CP/MAS NMR spectrum of
NPAF is given in Fig. 1, and in good agreement with the
80 predicted spectrum, showing that crossꢀcoupling reaction was
succesful under the given conditions. The peaks around 30 and
230 ppm are due to spinning side bands.
Characterization
30 The powder Xꢀray diffraction (XRD) of the samples was carried
out by a customꢀbuilt air tight stainless steel sample holder76
using a Philips X’pert diffractometer with CuKα radiation of
λ=1.54060 Å. The samples were prepared inside the glove box
and sealed with Kapton® film. Scanning electron microscopy
35 (SEM), Hitachi S800, with energy dispersive Xꢀrays (EDX)
attachment was utilized to investigate the chemical composition
of the elements. The 13C crossꢀpolarization magicꢀangle spinning
nuclear magnetic resonance (CP/MAS NMR) experiment was
performed on a Bruker DSX 300 spectrometer operating at a
40 magnetic field strength of 7.0 T. The resonance frequencies for
1H and 13C at this field strength are 300.13 MHz and 75.47 MHz,
respectively. A Bruker 4 mm MAS probe was used to acquire 13
C
CP/MAS NMR spectra at 7.5 kHz spinning. The chemical shifts
were externally referenced to adamantane for 13C. The
45 gravimetric weight loss and melting point were analyzed by a TA
Instrument’s SDTꢀQ600, and the data was analyzed with a TA
Universal Analysis 2000 software. All low pressure (P ≤ 1atm)
adsorption and desorption isotherms of hydrogen, nitrogen and
CO2 were measured by a Quantachrome AS1C. The measurement
50 accuracy and repeatability of the Quantachrome AS1C were
verified with the Quantachrome standard reference material
(SARMꢀ2012) before the measurements. The test value was
within the reproducibility limit (± 5 %) of the expected value.
The adsorption data was analyzed by a Quantachrome AS1Win
55 software. The specific surface area (SSA) of the samples was
calculated from nitrogen adsorption at 77 K using the Brunauerꢀ
EmmettꢀTeller (BET) equation. The pore size distribution (PSD)
Scheme1. Synthetic route for NPAF.
85
FTIR analysis showed CꢀBr peaks in NPAF also, indicating
unreacted Br upon Yamamoto coupling. SEMꢀEDX analysis
confirmed the residual Br impurities, less than 0.1 at. %; in
2
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addition, showed Cl impurities due to HCl washing (Fig. S3,
ESI†). Chlorine ions can interact with the electron rich nitrogen
dominant pore sizes. On the other hand, nitrogen at 77 K showed
dominant pore sizes at 0.6 and 1 nm. Overall, pore size
atoms; therefore, can limit the NPAF’s CO2 and hydrogen uptake. 45 distributions determined by nitrogen and CO2 are in accordance.
To remove Clꢀ ions, NPAF was refluxed in triethanolamine
5
(TEA). Indeed, both hydrogen and CO2 uptakes were increased
around 10% upon TEA treatment (Fig. S4, ESI†).
Fig. 2. Nitrogen adsorption and desorption isotherms of NPAF at 77 K.
The proposed ideal structure of NPAF given in Scheme 1 is
Fig. 1. Experimental and predicted 13C NMR spectra of NPAF.
further studied using Spartan software. The pore size of the
50 optimized geometry is found to be 1.05 nm which is in good
agreement with the experimental pore size. The smaller pores
Thermal stability of NPAF was tested by thermogravimetric
10 analysis (TGA) (Fig. S5, ESI†). TGA shows that NPAF is highly
stable and starts to decompose around 550 °C under nitrogen
flow. Moreover, as mentioned in the introduction, solid sorbent
for CCS technology should be stable under moisture since flue
gas includes 5% water vapour. After storing NPAF under ambient
15 air over a month we did not observe any noticeable change in the
surface area, and hydrogen and CO2 uptakes (not shown). On the
other hand, Xꢀray diffraction (XRD) analysis revealed the
amorphous nature of the NPAF material (Fig. S6, ESI†).
revealed from the experimental data should be related to the
deviation from the ideal structure given in Scheme 1 (i.e., pores
formed by cross coupling of three building blocks instead of four
55 and/or Br atoms attached to the orthoꢀ or metaꢀ positions instead
of the paraꢀ position in the benzene ring).
Porous structure of NPAF
20 Figure 2 shows the nitrogen isotherm of NPAF at 77 K which is
of type IV isotherm indicating a microꢀ/mesoporous material
according to IUPAC classification.80 Significant nitrogen uptake
at high relative pressures (i.e., P/Po > 0.1) and the broad
hysteresis in the desorption branch are distinctive features of the
25 porous polymers, and can be attributed to the swelling of the
polymer matrix and the presence of mesopores and intraparticle
81ꢀ82
voids.80,
Brunauer–Emmett–Teller (BET) surface area of
NPAF is 1790 m2/g, and the relative pressure range for BET
surface area calculation was determined using the consistency
30 criteria (Fig. S7, ESI†).82ꢀ84
Pore size distribution of NPAF was probed by nitrogen at 77 K
and CO2 at 273 K, and was calculated by NLDFT based on a
carbon material kernel. The pore size distribution of NPAF is
given in Fig. 3. The nitrogen isotherm at 77 K was fitted using
35 hybrid slit/cylindrical pore model (i.e., slit pore geometry for
pores < 2nm and cylindrical pore geometry for pores > 2nm)
since it resulted in better fit to the experimental data as compared
to using either one alone; whereas, CO2 isotherm was fitted using
slit pore geometry (Fig. S8, ESI†). Utilizing CO2 at 273 K was
40 shown to be useful in determination of the very narrow pores due
to diffusional limitations of nitrogen at 77 K.85 Indeed, CO2 at
273 K revealed pores as small as 0.3, 0.6 and 0.8 nm being the
Fig. 3. Pore size distribution of NPAF.
The micropore and total pore volumes of NPAF were
60 calculated by NLDFT from the nitrogen adsorption isotherm at
77 K using the ranges P/Po < 0.1 and P/Po < 0.99, respectively.
The micropore, mesopore and total pore volumes of NPAF are
1.21, 0.77 and 1.98 cc/g, respectively. The mesopore size
distribution of NPAF is also given in Fig. S9, ESI†.
65 Low pressure CO2, hydrogen and nitrogen uptake of NPAF
Low pressure hydrogen, CO2 and nitrogen uptakes of NPAF are
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given in Fig. 4. Hydrogen uptake of NPAF at 1 atm and 77 K is
212 cc/g (1.87 wt. %) which is one of the highest for porous
worthwhile to note that NPAF has a significant hydrogen uptake
at 1 atm and 77 K although it has a lower adsorption enthalpy
polymers reported so far (Table S1, ESI†).63, 86 Hydrogen uptake 45 than most of the other porous polymers reported so far.
did not reach saturation at 1 atm and 77 K, so it possible to store
more hydrogen at elevated pressures. At 1 atm, CO2 uptake of
NPAF is 81.5 cc/g (3.64 mmol/g) and 52.3 cc/g (2.32 mmol/g) at
273 K and 298 K, respectively. The CO2 uptake of NPAF also
surpasses most of the porous polymers reported so far (Table S1,
ESI†).34
5
Fig. 5. (A) CO2 and (B) hydrogen adsorption enthalpy of NPAF.
CO2/N2 selectivity of NPAF
The CO2/N2 selectivity is an important parameter in evaluating a
50 solid sorbent for CCS applications. Ideal adsorption solution
theory (IAST) has shown to be accurate in calculating the multi
component adsorption isotherm of a mixture based on the single
89
component adsorption isotherms of the components.51,
The
selectivity of NPAF, 0.15/0.85 mole fraction ratio of CO2/N2, at
55 273 K decreases gradually with increasing pressure (48 at 1 atm),
whereas at 298 K selectivity of NPAF (88 at 1 atm) is relatively
constant up to 1 atm as shown in Fig. 6.
10
Fig. 4. Hydrogen (at 77 K), CO2 (at 273 K and 298 K) and nitrogen (at
273 K and 298 K) uptakes of NPAF.
Effect of nitrogen density on gas uptake and adsorption
enthalpy of NPAF
15 As mentioned in the introduction, one of the motivations behind
this work was to synthesize a nitrogen rich porous polymer.
Similar nitrogen rich polymers have been reported previosuly,
triphenylamine based JUCꢀZ2 is the most notable one.87 One of
the advantages of NPAF over JUCꢀZ2 is; NPAF has two nitrogen
20 atoms per five benzene rings, whereas JUCꢀZ2 has one nitrogen
atom per three benzene rings in its building block. Therefore,
NPAF has a higher nitrogen atom density per benzene ring. In
addition, NPAF has narrower pores (1.05 nm) as compared to
JUCꢀZ2 (1.2 nm). Comparing the hydrogen uptake values (77 K
25 and 1 atm) of JUCꢀZ2 (1.62 wt. %) and NPAF (1.87 wt. %) with
nitrogen free triphenylbenzene based COPꢀ351 (1.4 wt. %) porous
polymer, all of which have very similar surface areas, further
proves the favorable effect of nitrogen content on small gas
uptake. Hence, NPAF’s higher nitrogen atom density and
30 narrower pores should be responsible for its superior CO2 and
hydrogen uptake as compared to JUCꢀZ2 and COPꢀ3.
Fig. 6. CO2/N2 (0.15/0.85 mole fraction) selectivity of NPAF at 273 K
60
and 298 K.
High pressure CO2 and hydrogen uptake of NPAF
The high pressure hydrogen and CO2 storage capacities of porous
polymers are important for real world applications but seldom
reported in the literature.18, 49, 51, 59 NPAF has a 28.7 mmol/g CO2
The hydrogen and CO2 adsorption enthalpies of NPAF were
calculated by using ClausiusꢀClapeyron equation from hydrogen
isotherms at 77 K and 87 K, and CO2 isotherms at 273 K and 298
35 K, respectively. Isotherms were fitted by dual site Langmuir
Freundlich (DSLF) equation which was shown to be appropriate
in fitting experimental nitrogen, hydrogen and CO2 isotherms
(Fig S10ꢀ12 and Table S2, ESI†).51, 88 Both hydrogen (5.2 kJ/mol)
and CO2 (19 kJ/mol) adsorption enthalpies of NPAF are
40 relatively low compared to the other porous polymers as shown in
Fig 5. Considering hydrogen storage at 77 K, adsorption enthalpy
claimed to be the most effective parameter at low loadings.23 It is
65 uptake at 57.2 bar and 298 K which surpasses BILPꢀ1049;
however, less than PPNꢀ4 as shown in Fig. 7(a) (Table S1,
ESI†).18 On the other hand, hydrogen storage capacity of NPAF
at 80 bar and 298 K is 0.33 wt. % which is too low for practical
applications, Fig. 7(b). The absolute CO2 and hydrogen
70 gravimetric capacities of NPAF were also calculated using real
gas equation of state90, 91, and are given in Figs. S13 and S14,
respectively (ESI†).
The volumetric capacity of the porous materials is especially
important for mobile applications (i.e., hydrogen storage
75 systems). The absolute (i.e., skeletal) density of NPAF was
4
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determined by a helium adsorption test and found to be 1.05 g/cc,
Notes and references
whereas the tap density of NPAF was 0.07 g/cc. The significant
difference (i.e., 15 fold) between the absolute and tap densities
indicates the inefficient packing of NPAF particles; in addition,
this difference poses engineering challenges in designing system
level hydrogen storage systems and reactors for CO2 capture
applications.
a Clean Energy Research Center, College of Engineering, University of
South Florida, Tampa, FL, 33620, USA. Fax: +1 813-974-2050; Tel: +1
813-409-6864; E-mail: demirocak@mail.usf.edu
50 b Department of Physics, College of Arts and Sciences, Tuskegee
University, Tuskegee, AL, 36088, USA
5
† Electronic Supplementary Information (ESI) available: [BET
consistency plot, TGA, FTIR, XRD, DSLF fits to CO2, nitrogen
and hydrogen uptakes, and excess and absolute gravimetric
55 capacities of NPAF for CO2 and hydrogen] See
DOI: 10.1039/b000000x/
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Fig. 7. (A) High pressure CO2 uptake of NPAF at 273 K and 298 K and
(B) high pressure hydrogen uptake of NPAF at 298 K.
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Acknowledgements
40 The authors wish to acknowledge the US Department of Energy
(Hydrogen Fuel Cell program code: DEꢀFG36ꢀ04G014224),
Florida Hydrogen Initiative (DOEꢀFHI # 20126050) for financial
support. The authors would also like to thank Xisen Wang for his
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Nitrogen rich porous polymer showed enhanced hydrogen and CO2 storage capacities as compared to
similar porous polymers with lower nitrogen content.