A new complex alkali metal aluminium amide borohydride, Li₂Al(ND₂)₄BH₄: synthesis, thermal analysis and crystal structure

Abstract

The mixtures of alkali metal aluminium amide MAl(ND₂)₄ and alkali metal borohydride MBH₄ were synthesized using ball-milling. Thermal analysis and phase identifications of the MAl(ND₂)₄–MBH₄ system were performed by differential scanning calorimetry-thermogravimetric analysis, temperature programmed desorption-residual gas analysis, in situ synchrotron radiation powder X-ray diffraction and Fourier transform infrared spectroscopy. A previously unknown phase, Li₂Al(ND₂)₄BH₄, was formed in the samples of LiAl(ND₂)₄ + 2LiBH₄ and NaAl(ND₂)₄ + 2LiBH₄. Its crystal structure was solved and refined in the monoclinic space group P2₁/c, with a = 6.8582(3) Å, b = 11.3128(5) Å, c = 11.2117(4) Å, β = 124.186(5)°. Li₂Al(ND₂)₄BH₄ is the first reported compound containing both [Al(ND₂)₄]⁻ and BH₄⁻ anions. The ball-milling of NaAl(ND₂)₄ + 2NaBH₄ and KAl(ND₂)₄ + 2KBH₄ gave mixtures of the starting materials. The synthesized samples desorbed ammonia in the temperature range between 50 and 200 °C and hydrogen above ∼300 °C.

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Introduction

Complex hydrides, e.g., metal alanates (MAlH₄), borohydrides (MBH₄) and amides (MNH₂), are ionic compounds of metal cations and covalently bonded complex anions (AlH₄⁻, BH₄⁻, NH₂⁻). They have been studied as hydrogen storage materials possessing high gravimetric and volumetric hydrogen densities.¹ Research has been focused on tailoring the properties of the system to have favourable kinetics and thermodynamics for hydrogen desorption and absorption at moderate temperature.^2,3

Lithium amide (LiNH₂) desorbs ammonia on thermal decomposition above ∼300 °C, while the mixture with LiH desorbs hydrogen at lower temperature (>200 °C).⁴ The dehydrogenated product is Li₂NH and higher temperature (>320 °C) is necessary for complete dehydrogenation into Li₃N.⁵ The reversible hydrogen desorption/absorption reactions are described as follows:

LiNH₂ + 2LiH ↔ Li₂NH + LiH + H₂ ↔ Li₃N + 2H₂.

In the LiNH₂–LiBH₄ mixture it has been assumed that Li₃BN₂ is the hydrogen-free dehydrogenated state:^6,7

2LiNH₂ + LiBH₄ → Li₃BN₂ + 4H₂.

As a result of the stabilization of the dehydrogenated state, less positive enthalpy (23 kJ per mol H₂) for the dehydrogenation reaction would be required compared to pure LiBH₄ (75 kJ per mol H₂) according to DFT calculations.⁷ This results in release of ∼10 wt% hydrogen at relatively low temperature around 250 °C.⁶ It is also reported that an intermediate phase (Li₄BN₃H₁₀) is formed after ball milling of the mixture of LiNH₂ and LiBH₄.⁸

Metal aluminium amide (MAl(NH₂)₄), are compounds where H⁻ in metal alanate are substituted by NH₂⁻ ions. They desorbs ammonia at around 100 °C for M = Li, Na and K.^9,10 In analogy to the LiNH₂–LiH system, the LiAl(NH₂)₄–LiH system has been studied. The ball-milled mixture of LiAl(NH₂)₄ + 4LiH desorbed >5.0 wt% of H₂ at 130 °C.¹¹ In the present study, the mixtures of alkali metal aluminium amides and borohydrides were prepared and thermal analysis and phase identification of the mixtures were performed.

Experimental

LiBH₄ (≥95%), NaBH₄ (≥99%) and KBH₄ (≥98%) were purchased from Sigma-Aldrich and LiAl(ND₂)₄, NaAl(ND₂)₄ and KAl(ND₂)₄ were synthesized as described elsewhere.¹² Mixtures of LiAl(ND₂)₄–LiBH₄ (denoted as S1), NaAl(ND₂)₄–LiBH₄ (S2), NaAl(ND₂)₄–NaBH₄ (S3) and KAl(ND₂)₄–KBH₄ (S4) in 1 : 2 molar ratios were ball-milled for 1 h (15 min milling + 15 min rest, 4 cycles) under 0.1 MPa Ar atmosphere using a Pulverisette 7 (Fritsch). The samples studied in this paper are shown in Table 1. Sample handling was carried out in a MBraun Unilab glovebox filled with purified Ar (<1 ppm O₂ and H₂O).

Table 1 The samples and their hydrogen contents

Notation	Materials	Molar ratio	H content^a wt%
a wt% in non-deuterated sample.
S1	LiAl(ND2)4–LiBH4	1 : 2	11.3
S2	NaAl(ND2)4–LiBH4	1 : 2	10.1
S3	NaAl(ND2)4–NaBH4	1 : 2	8.4
S4	KAl(ND2)4–KBH4	1 : 2	6.7

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Powder X-ray diffraction (PXD) patterns were collected using Cu Kα radiation in a Bruker-AXS D8 Advance diffractometer equipped with a Göbel mirror and a LynxEye 1D strip detector. The samples were contained in rotating boron glass capillaries (0.8 mm ϕ) filled and sealed under Ar atmosphere.

Fourier transform infrared (FTIR) spectrometer (ALPHA, Bruker) equipped with a 45° diamond attenuated total reflectance (ATR) accessory was used to collect IR spectra at room temperature (RT). The spectra were obtained in the range of 4000–400 cm⁻¹ with a resolution of 2 cm⁻¹ without any dilution of the samples.

Temperature programmed desorption (TPD) was performed under dynamic vacuum up to 500 °C using an in-house built setup. The samples were heated from RT to 500 °C with a ramp rate of 2 °C min⁻¹. The desorbed gas was analyzed with a MKS Microvision-IP residual gas analyzer (RGA).

Combined differential scanning calorimetry-thermogravimetric analysis (DSC-TGA) was carried out using a Netzsch STA 449 F3 Jupiter instrument with an Al sample crucible covered by a lid with a small hole. The samples were heated from RT to 500 °C with a ramp rate of 5 °C min⁻¹ under a 50 mL min⁻¹ Ar flow.

In situ synchrotron radiation (SR) PXD measurements (λ = 0.694118 Å) were carried out using a pixel area detector (Pilatus 2M, DECTRIS) at the Swiss-Norwegian Beamlines (SNBL, BM01A) at the European Synchrotron Radiation Facility (ESRF), Grenoble, France. The samples were mounted in boron glass capillaries (0.5 mm ϕ) fixed in a Swagelok fitting and kept under dynamic vacuum. A diffraction pattern was collected every 40 s (exposure time 30 s). The capillary was rotated 30° during exposure to improve the powder averaging. Measurements were carried out between RT and 500 °C with a ramp rate of 5 °C min⁻¹. The two-dimensional data were integrated to one-dimensional diffraction patterns using the Fit2D program.¹³

The Dicvol¹⁴ and Chekcell¹⁵ programs were used for unit cell and space group determination. The global optimization approach with parallel tempering as implemented in the FOX program^16,17 was used for crystal structure determination. The structure refinements were carried out using the GSAS¹⁸ software package with the EXPGUI¹⁹ user interface based on the Rietveld method.^20,21 The backgrounds were fitted by a 36-term Chebyshev polynomial. A pseudo-Voigt function²² with asymmetry correction²³ was used to model the peak profile. Isotropic displacement parameters were refined with a common U_iso value for D- and H-atoms, respectively. The crystal structures were illustrated using the VESTA program.²⁴

Results and discussion

Fig. 1 shows PXD patterns of the samples after ball-milling. For sample S1, Bragg peaks from new phase(s) were observed, while no peaks remained from the starting materials. This indicates a complete chemical reaction. Similar for S2, the starting materials were not observed, and peaks from a new phase as well as NaBH₄ were found. The unidentified peaks in S2 are a subset of the unidentified peaks in the S1 sample. This indicates the possibilities that S1 contain the new phase observed in S2 in addition to other unidentified phase(s) or that the crystal structure of the phase in S1 has a superstructure of the one in S2. To our knowledge, the unidentified peaks from S1 and S2 do not match the reported structure of the Li–Al–B–N–H related compounds, such as LiNH₂BH₃,²⁵ LiBH₄NH₃,²⁶ Li₄BH₄(NH₂)₃,⁸ Li₂BH₄NH₂,²⁷ Al(BH₄)₃,²⁸ Al(NH₃)₆Li₂(BH₄)₅,²⁹ Al(BH₄)₃NH₃ (ref. 30) and Al₃Li₄(BH₄)₁₃.³¹ For S3 only peaks from the starting materials were observed. For S4 the main peaks are also from the starting material, but in addition a small amount of a partially decomposed product⁹ of KAl(ND₂)₄, i.e., KAl(ND₂)₂ND is observed. This indicates that no chemical reaction occurred between the reactants during ball-milling.

Fig. 1 PXD patterns (Cu Kα) of ball-milled sample of (a) LiAl(ND₂)₄ + 2LiBH₄ (S1), (b) NaAl(ND₂)₄ + 2LiBH₄ (S2), (c) NaAl(ND₂)₄ + 2NaBH₄ (S3), and (d) KAl(ND₂)₄ + 2KBH₄ (S4). Bragg peak positions for the starting materials, as well as for NaBH₄ in S2, are marked with vertical ticks.

ATR-IR spectra of S1, S2 and the starting materials of each sample as references are shown in Fig. 2. The peak positions are summarized in Table 2. Peaks corresponding to N–D and B–H stretching modes were observed in the IR spectra of both S1 and S2. Isotopic exchange between ND₂ and BH₄ groups was negligible since no peaks of N–H or B–D stretching mode were observed. The peak profile of B–H stretching mode in S1 was different from pure LiBH₄ (Fig. 2b). Two main peaks were observed at 2303 and 2273 cm⁻¹ in LiBH₄, while three peaks (2299, 2261 and 2247 cm⁻¹) were present in S1. Peaks corresponding to asymmetric stretching of ND₂ at 2537, 2530 and 2450 cm⁻¹ in LiAl(ND₂)₄ (Fig. 2c) were not apparent in S1 but the peaks at 2509 and 2426 (shoulder) might be due to ND₂ stretching. Peak splitting (2499 and 2493 cm⁻¹) and slight red-shift were observed for symmetric stretching mode of ND₂ in S1. For sample S2, two main peaks in B–H region were observed at 2306 and 2236 cm⁻¹, respectively, and the most intense peak in NaBH₄ (2291 cm⁻¹) was present as a shoulder. Peaks corresponding to N–D stretching modes were almost the same as those in S1 and different from NaAl(ND₂)₄. Therefore, the unidentified phase(s) in S2 could contain both BH₄ and ND₂ ions. Here, we assume the composition of the phase to be Li₂Al(ND₂)₄BH₄. From the PXD-data (Fig. 1), it is suggested that the following reaction occur during preparation of S2:

NaAl(ND₂)₄ + 2LiBH₄ → Li₂Al(ND₂)₄BH₄ + NaBH₄

Fig. 2 ATR-IR spectra of N–D and B–H stretching regions for: (a) LiAl(ND₂)₄ + 2LiBH₄ (S1), (b) LiBH₄, (c) LiAl(ND₂)₄, (d) NaAl(ND₂)₄ + 2LiBH₄ (S2), (e) NaBH₄, and (f) NaAl(ND₂)₄. All spectra were recorded under an Ar atmosphere at RT.

Table 2 IR frequencies in cm⁻¹ for N–D and B–H stretching modes and their assignments

S1	LiBH4	Mode^a	LiAl(ND2)4	Mode^b	S2	NaBH4	Mode^a	NaAl(ND2)4	Mode^b
a From ref. 32.b From ref. 33. The subscript a and s denotes asymmetric and symmetric vibration, respectively. The description (a) and (b) corresponds to two types of different ND2 groups.
			2537	νaND2(a)
2509			2530		2509			2522	νaND2
2499			2501	νsND2(a)	2499			2512
2493					2496
2426sh			2450	νaND2(b)	2427sh			2438	νsND2
2417			2420	νsND2(b)	2418			2430
	2397	ν2 + ν4(A′′)/2ν(A′)				2396	ν2 + ν4
2299	2303	ν3(A′)			2306	2291	ν3
2261	2273
2247
	2177	2ν4(A′′)			2236	2222	2ν4

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Gas desorption properties of the samples were investigated using TPD-RGA measurement (Fig. 3). By analogy with LiNH₂–LiBH₄ and LiAl(NH₂)₄–LiH systems,^6,11 dominant release of hydrogen is expected, however, ND₃ (m/q = 20) was desorbed from all the samples above 50 °C. H₂ (m/q = 2) desorption was observed only above 250 °C in S1 and S2, 300 °C in S3 and 350 °C in S4. As described above from the IR data, H–D exchange between ND₂ and BH₄ groups was not apparent after ball-milling. HD (m/q = 3) would be released as a result of direct interaction of hydrogen atoms in the amide (ND₂⁻) and borohydride (BH₄⁻) ions. However, HD signals were synchronized with H₂ signals and less intense than H₂. This suggests that HD was generated from H₂ and D from ND₃ in the RGA chamber during ionization as a fragment of H₂ desorption. Small amounts of B₂H₆ (m/q = 27) were also released above 220 °C, 200 °C and 170 °C in S1, S2 and S3, respectively, while only a trace was detected from S4. The H₂ desorption temperature of S3 is much lower compared to the ball-milled NaBH₄ (>490 °C)³⁴ and similar to the NaNH₂–NaBH₄ system (>300 °C).³⁵ For MNH₂–MBH₄ it is proposed that an attraction between protic H^δ+ in NH₂ and hydridic H^δ− in BH₄ could accelerate the hydrogen desorption.³⁶ For the MAl(ND₂)₄–MBH₄ samples an attraction between D^δ+ in ND₂ (or ND in metal aluminium imide MAl(ND)₂) and hydridic H^δ− in BH₄ could lower the hydrogen desorption temperature.

Fig. 3 RGA results of the desorbed gas (m/z = 2 (H₂, blue), 3 (HD, magenta), 20 (ND₃, red), 27 (B₂H₆, green)) from the ball-milled samples (a) LiAl(ND₂)₄ + 2LiBH₄ (S1), (b) NaAl(ND₂)₄ + 2LiBH₄ (S2), (c) NaAl(ND₂)₄ + 2NaBH₄ (S3), and (d) KAl(ND₂)₄ + 2KBH₄ (S4). The heating rate was 2 °C min⁻¹. Intensity of B₂H₆ signals was multiplied by a factor of 10.

TGA-DSC profiles of the samples are shown in Fig. 4. Two endothermic events at 60 and 100 °C without weight change were observed in S1, which might be due to phase transition(s). Ammonia desorption reactions appear as endothermic events in S2 (135 °C), S3 (60 °C) and S4 (150 °C). Weight losses below 250 °C were 23.8, 23.2, 16.7 and 11.8 wt% in the S1–S4 samples, respectively. The theoretical weight loss for 2 mole of ND₃ release which corresponds to decomposition of metal aluminium amides into metal aluminium imides (MAl(NH)₂) are 26.8, 24.2, 20.2 and 16.2 wt% in S1–S4, respectively. Considering the low decomposition temperatures of NaAl(NH₂)₄ and KAl(NH₂)₄, part of the aluminium amides would be decomposed during ball-milling in S3 and S4. Actually, PXD data shows the formation of the partially decomposed product in S4. Moreover, the end points of ammonia desorption are not very well defined, and some desorption continues also above 250 °C. The total mass losses up to 450 °C, which include hydrogen desorption, are 28.5, 27.7, 21.4 and 17.4 wt% for S1–S4, respectively. These are close to values for desorption of 2H₂ in addition to 2 ND₃, which are 29.5, 26.6, 22.3 and 17.9 wt%. This thus matches hydrogen desorption from the BH₄ unit in Li₂Al(ND₂)₄BH₄ in S1 and S2. It also indicate that a similar type of reaction takes place at elevated temperature in S3 and S4, since unreacted NaBH₄ and KBH₄ should not emit hydrogen in the investigated temperature range. The inconsistency of the temperatures for ammonia desorption between TGA-DSC and RGA resulted from different experimental conditions in these measurements. While the samples were under dynamic vacuum in the RGA measurements, an Al sample container was covered by a lid with a small hole in the TGA-DSC measurements. Thus, for TGA-DSC the decomposition can be suppressed by ammonia partial pressure around the sample. Moreover, faster heating rate was used in the TGA-DSC experiments (5 °C min⁻¹) than in RGA (2 °C min⁻¹).

Fig. 4 DSC (solid line) and TGA (dashed line) profiles of the ball-milled (a) LiAl(ND₂)₄ + 2LiBH₄ (S1), (b) NaAl(ND₂)₄ + 2LiBH₄ (S2), (c) NaAl(ND₂)₄ + 2NaBH₄ (S3), and (d) KAl(ND₂)₄ + 2KBH₄ (S4). The heating rate was 5 °C min⁻¹.

Selected diffraction patterns of in situ SR-PXD data for the S1 sample are shown in Fig. 5 (the rest of the in situ SR-PXD data for S1 and S2 are given as ESI†). The peaks that were not observed in S2 disappear around 50 °C on heating S1 under vacuum. The remaining peaks, thus corresponding to those observed from S2, were successfully indexed with a monoclinic unit cell, P2₁/c, a = 6.8582(3) Å, b = 11.3128(5) Å, c = 11.2117(4) Å, β = 124.186(5)° at 53 °C. Crystal structure determination and refinement was performed, confirming the suggested composition Li₂Al(ND₂)₄BH₄. For the structure refinement, ND₂ and BH₄ units were treated as rigid bodies and the positions of hydrogen atoms are uncertain. N–D and B–H distances of 1.01 and 1.25 Å, D–N–D and H–B–H angles of 98.19 and 109.47°, respectively, were applied for the rigid bodies. The fit obtained in the Rietveld refinement based on the in situ SR-PXD data at 53 °C for S1 is shown in Fig. 6. Table 3 summarizes the structural parameters of Li₂Al(ND₂)₄BH₄ and the structure model is visualized in Fig. 7. Al is tetrahedrally coordinated by ND₂ groups and the average Al–N distance is 1.974 Å which is slightly longer than that in LiAl(ND₂)₄ (1.868 Å).¹² The average Li–N distance (2.16 Å) of Li₂Al(ND₂)₄BH₄ is almost the same as that of LiAl(ND₂)₄ (2.100 Å). In LiBH₄, BH₄ group is tetrahedrally coordinated by Li atoms (average Li–B distance, 2.515 Å),³⁷ while planar Li₂B₂ units are linked by corner sharing where each B is shared between 2 planar units in Li₂Al(ND₂)₄BH₄ (average Li–B distance, 2.63 Å), yielding a 4-coordination which is neither tetrahedral nor planar. The average distance between N in ND₂ group and B in BH₄ group is 3.955 Å, and ND₂ and BH₄ groups are well-separated (3.77 Å or more).

Fig. 5 Selected in situ SR-PXD patterns of LiAl(ND₂)₄ + 2LiBH₄ (S1) at (a) RT, (b) 53 °C and (c) 80 °C with λ = 0.694118 Å. “*” denotes diffraction peak from Li. Bragg peak positions for the monoclinic phase Li₂NaAl(ND₂)₄BH₄ are marked with vertical ticks.

Fig. 6 Rietveld refinement of the in situ SR-PXD pattern of LiAl(ND₂)₄ + 2LiBH₄ (S1) at 53 °C with λ = 0.694118 Å. The region from 16.2 to 16.4° was excluded because of the reflection from Li phase. The black dot, red and blue lines are the observed, calculated and difference between observed and calculated patterns, respectively. Vertical tick marks show the position of the Bragg peaks.

Table 3 Results from SR-PXD Rietveld refinement of Li₂Al(ND₂)₄BH₄ (R_wp = 1.70%) at 53 °C. Estimated standard deviations are in parentheses

Space group: P21/c (no. 14), Z = 4, T = 53 °C
a = 6.8582(3) Å, b = 11.3128(5) Å, c = 11.2117(4) Å, β = 124.186(5)°
Atom	Site	x	y	Z	Uiso/Å^2
Li1	4e	0.935(5)	0.477(2)	0.354(3)	0.10(1)
Al	4e	0.1187(8)	0.3074(4)	0.8821(4)	0.060(2)
N1	4e	0.0269(11)	0.1716(7)	0.7549(5)	0.024(3)
D1	4e	0.0314(11)	0.1063(7)	0.6951(5)	0.80(10)
D2	4e	0.1837(11)	0.1554(7)	0.8481(5)	0.80(10)
N2	4e	0.8126(14)	0.3829(5)	0.8405(7)	0.060(3)
D3	4e	0.8421(14)	0.3610(5)	0.9367(7)	0.80(10)
D4	4e	0.8913(14)	0.3125(5)	0.8290(7)	0.80(10)
N3	4e	0.3151(15)	0.2609(6)	0.0817(10)	0.064(4)
D5	4e	0.4121(15)	0.2181(6)	0.1770(10)	0.80(10)
D6	4e	0.4112(15)	0.3360(6)	0.1104(10)	0.80(10)
N4	4e	0.2822(13)	0.4280(6)	0.8437(7)	0.047(3)
D7	4e	0.3745(13)	0.4957(6)	0.8398(7)	0.80(10)
D8	4e	0.1236(13)	0.4469(6)	0.7530(7)	0.80(10)
B	4e	0.6969(17)	0.0906(7)	0.9505(8)	0.013(4)
H1	4e	0.5227(17)	0.0230(7)	0.8924(8)	0.10(2)
H2	4e	0.6572(17)	0.1782(7)	0.0018(8)	0.10(2)
H3	4e	0.7334(17)	0.1244(7)	0.8585(8)	0.10(2)
H4	4e	0.8743(17)	0.0369(7)	0.0492(8)	0.10(2)
Li2	4e	0.560(5)	0.124(2)	0.120(3)	0.15(1)

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Fig. 7 Visualization of the crystal structure of Li₂Al(ND₂)₄BH₄. Li: yellow spheres, Al: in centers of blue tetrahedra, N: gray spheres, B: in centers of green tetrahedra, H(D): pink spheres.

After heating up to ∼80 °C in Fig. 5c, the Bragg peaks of the monoclinic Li₂Al(ND₂)₄BH₄ disappeared as a result of amorphization and/or decomposition. It should be noted that metallic Li was observed in the PXD profile of S1 while it was found neither in the starting material LiAl(ND₂)₄ nor in S2. This indicates that metallic Li is formed in a redox process in conjunction with formation of the unknown phase which is only observed in S1.

Conclusions

Thermal and phase analyses of the MAl(ND₂)₄–MBH₄ systems were carried out by means of TGA-DSC, RGA, PXD and IR measurements. Ball-milled mixtures of LiAl(ND₂)₄ + 2LiBH₄ (S1), NaAl(ND₂)₄ + 2LiBH₄ (S2), NaAl(ND₂)₄ + 2NaBH₄ (S3) and KAl(ND₂)₄ + 2KBH₄ (S4) desorbed ammonia in the temperature range between 50 and 200 °C and hydrogen above ∼300 °C. From the PXD results, mixture of the starting materials were found in the sample of NaAl(ND₂)₄ + 2NaBH₄ (S3) and KAl(ND₂)₄ + 2KBH₄ (S4), while previously undescribed phases were observed in the sample of LiAl(ND₂)₄ + 2LiBH₄ (S1) and NaAl(ND₂)₄ + 2LiBH₄ (S2). Structure determination of the novel phase Li₂Al(ND₂)₄BH₄, found in both S1 and S2, was performed and it is revealed that the phase has the monoclinic unit cell (P2₁/c) which contains [Al(ND₂)₄]⁻ and BH₄⁻ anions.

Acknowledgements

The EU FP7 Marie Curie Action Incoming International Fellowship project MATERHY (FP7-PEOPLE-2009-IIF, no. 253863) is acknowledged for financial support. The authors acknowledge the skillful assistance from the staff of the Swiss-Norwegian Beamline, at the European Synchrotron Radiation Facility, Grenoble, France.

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Footnote

† Electronic supplementary information (ESI) available: In situ SR-PXD data for ball-milled samples of LiAl(ND₂)₄ + 2LiBH₄ and NaAl(ND₂)₄ + 2LiBH₄. See DOI: 10.1039/c6ra00931j

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