Toward Increasing Micropore Volume between Hybrid Layered

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Toward Increasing Micropore Volume between Hybrid Layered Perovskites with Silsesquioxane Interlayers Sho Kataoka, Yoshihiro Kamimura, and Akira Endo Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b04337 • Publication Date (Web): 18 Mar 2018 Downloaded from http://pubs.acs.org on March 18, 2018

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Toward Increasing Micropore Volume between Hybrid Layered Perovskites with Silsesquioxane Interlayers

Sho Kataoka,* Yoshihiro Kamimura, and Akira Endo

National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba,

Ibaraki 305-8565, Japan

*

Corresponding

authors:

Tel.:

+81-29-861-4684;

Fax:

+81-29-861-4660;

e-mail:

[email protected] (Sho Kataoka)

Keywords layered perovskite, micropore, silsesquioxane, pore volume, low-dimensional materials.

1

ACS Paragon Plus Environment

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Abstract Hybrid organic–inorganic layered perovskites are typically non-porous solids. However, the

incorporation of silsesquioxanes with a cubic cage structure as interlayer materials creates

micropores between the perovskite layers. In this study, we increase in the micropore volume in

layered perovskites by replacing a portion of the silsesquioxane interlayers with organic amines. In

the proposed method, approximately 20% of the silsesquioxane interlayers can be replaced without

changing the layer distance owing to the size of the silsesquioxane. When small amines (e.g.,

ethylamine) are used in this manner, the micropore volume of the obtained hybrid layered

perovskites increases by as much as 44%; when large amines (e.g., phenethylamine) are used, their

micropore volume decreases by as much as 43%. Through the variation of amine fraction, the

micropore volume can be adjusted in the range. Finally, the magnetic moment measurements reveal

that the layered perovskites with mixed interlayers exhibit ferromagnetic ordering at temperature

below 20 K, thus indicating that the obtained perovskites maintain their functions as layered

perovskites.

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Introduction Hybrid organic–inorganic perovskites exhibit interesting properties in fundamental research fields and various applications.1-3 For instance, lead halide hybrid perovskites with organic amines have garnered much interest as photovoltaic cells and light-emitting diodes;4-8 copper halide layered perovskites exhibit unique properties in magnetic and optical applications.9-11 When small amine

molecules (A) are used as cations, they fill the cavities of metal halide perovskite structures and create a three-dimensional perovskite with formula ABX3 (B: metal and X: halide). However, when larger amine molecules are used, they produce two-dimensional perovskite structures (A2BX4, see Figure 1).12-14 While many layered perovskites have been reported,15-19 we have developed layered perovskites with silsesquioxane interlayers (Figure 1).20 Silsesquioxanes with a cubic cage-like structure have both a robust cage structure and flexible organic functional terminals;21-23 they are

commonly referred to as a polyhedral oligomeric silsesquioxanes (POSS). A unique feature of the

hybrid layered perovskites is their porous structure, which is attributed to the rigidity of the POSS

interlayer. To the best of our knowledge, only POSS interlayers can create pores between perovskite layers.3 These pores have potential for a wide range of applications. When these pores are filled with certain compounds, the functions of layered perovskites are expected to be altered.24 However, their

insufficient micropore volume makes filling the pores with target molecules difficult and limits the further applications of these hybrid layered perovskites.20

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In this study, we widen and narrow micropores of hybrid layered perovskites by replacing a portion

of POSS interlayers with organic amines. Ethylamine is selected as a small amine for widening the

micropores; phenethylamine is selected as a large amine for narrowing the micropores. When amines

are excessively small, they may create three-dimensional structures, as previously mentioned.

However, on the basis of the tolerance factor, these amines can maintain the structure of a layered perovskite structure.12-14, 25, 26

Figure 1. Schematics of the organic–inorganic hybrid layered perovskite, POSS–inorganic hybrid

perovskite with micropores, and the layered perovskite with POSS/organic mixed interlayer.

Experimental Details Materials: Methanol, 1-propanol, hydrochloric acid, and copper(II) chloride, dihydrate

4


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(CuCl2·2H2O) were purchased from Kishida Chemical Co. (Japan); ethylamine (EA), phenethylamine (PEA), butylamine (BA), cyclohexylamine (CHA), and 4-phenylbutylamine (PBA)

were purchased from Tokyo Chemical Industry (Japan); 3-aminopropyltriethoxysilane (APTES) was

purchased from Shin-Etsu Chemical Co. (Japan). Water from a Milli-Q ultrapure water system

(Direct-Q, Millipore, Billerica, MA) was used. All chemicals were used as received. EA, PEA, BA,

CHA, and PBA were neutralized with hydrochloric acid to obtain ammonium chlorides before the preparation of perovskites.17, 27

Preparation

of

POSS–Metal

Halide

Perovskites:

Octa(3-aminopropyl)silsesquioxane

hydrochloride salt (A–POSS) was synthesized from APTES, hydrochloric acid, and methanol via a reported method.28-30 Mixtures of CuCl2·2H2O, A–POSS, and ammonium chlorides were first dissolved in a small amount of H2O and subsequently precipitated through the addition of a copious amount of 1-propanol. The amounts of CuCl2·2H2O, A–POSS, and amines are listed in Tables 1 and 2.

Characterization of Products: An inductively coupled plasma atomic emission spectrometer

(ICP-AES, SPS-7800, SII Nanotechnology Inc., Japan) was used for analyzing the Cu and Si

contents of the products. For the ICP-AES analysis, the products were dissolved in dilute

hydrochloric acid solution; Cu and Si concentrations were measured. Powder X-ray diffraction

(XRD) patterns of layered perovskites were obtained using an X-ray diffractometer (D8 Advance,

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Bruker, USA) equipped with a Cu–Kα radiation source (λ = 0.15406 nm, 40 kV, 40 mA). The nitrogen (N2) adsorption/desorption isotherms were collected at 77 K using a Belsorp-mini (Microtrac-BEL Inc., Japan). The specific surface area was calculated on the basis of Brunauer–

Emmett–Teller (BET) theory. Before the measurements, the samples were degassed at room

temperature (25 °C) for 24 h. The micropore volume was estimated using the t-plot method based on the Harkins–Jura equation.31, 32 Magnetic moments were measured using a superconducting quantum

interference device (SQUID, MPMS-5s: Quantum Design Inc., USA) equipped with a reciprocating

sample option system. Results and Discussion Small Amine for Widening Pores: Hybrid layered perovskites were prepared using various

fractions of CuCl2·2H2O, EA, and A–POSS, as listed in Table 1 (cases 1 to 6). In case 1, only A– POSS was inserted between CuCl42- perovskite layers as an interlayer material, resulting in the formation of a layered perovskite with a chemical formula [Si8O12(C3H6NH3)8][CuCl4]4; in this case, the Si/Cu ratio was 2.03, which was consistent with the ideal value (Si/Cu = 2). In case 2, only EA

was inserted between the perovskite layers, the Si/Cu ratio was 0; this results in a chemical formula,

EA2CuCl4. When both A–POSS and EA were included in the products (cases 3 to 6), the Si/Cu ratios were expected to be in the range from 0 to 2. The replacement ratio x defined in the chemical

formula [Si8O12(C3H6NH3)8](1−x)EA8x[CuCl4]4 was calculated from the Si/Cu ratio (Table 1). For example, in case 3, 7.4% of the A–POSS interlayers was replaced by EA; in case 6, 21.4% of the A– 6


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POSS interlayer was replaced by EA. Notably the replacement ratio, x, was considerably less than

the amount added to the preparation solution; this discrepancy was attributed to the difference in

solubility between A–POSS and EA.

The powder XRD patterns of the products are presented in Figure 2. In the pattern for case 1,

sharp peaks at 5.17°, 10.3°, and 17.9° are characteristic of 00l type reflections corresponding to a

layer distance of 1.71 nm as determined from Bragg’s equation. This distance indicates the formation

of layered perovskites with an A–POSS interlayer. Small peaks other than 00l type reflections are

presumably attributed to the in-plane diffractions. In case 2, sharp peaks at 8.38°, 16.7°, 25.2°, and

33.8° represents the formation of layered perovskites with an EA interlayer (layer distance: 1.06 nm).33 Because EA is smaller than A–POSS, the corresponding layer distance is smaller than that of

the A–POSS interlayer. In case 3, peaks attributed to A–POSS interlayers were predominant in the

XRD pattern even though the replacement ratio indicated that EA was included in the interlayer. This

result suggests that the layer distance of the product was determined by the size of the A–POSS (i.e.,

1.71 nm), when a small amount of EA (7.4%) was included in the interlayers. In case 4, although

tiny peaks attributable to EA interlayers (8.34° and 15.6°) are present, the majority of the products

maintain the layer distance because of the size of the A–POSS. In case 5, small peaks attributable to

EA interlayers are observed along with those from A–POSS interlayers, thus indicating that the

product had both 1.06-nm (EA) and 1.71-nm (A–POSS) layer distance in case 5.

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Figure 2. XRD patterns of hybrid layered perovskites with A–POSS and EA interlayers. Table 1. Experimental conditions and summary of the results for layered perovskites with A–POSS and EA interlayers. Case 1 2 3 4 5 *

CuCl2·2H2O* 1.0 1.0 1.0 1.0 1.0

A–POSS 0.250 0 0.125 0.0625 0.0400

EA 0 2.00 1.00 1.50 1.68

Si/Cu 2.037 0 1.851 1.677 1.596

x** – – 0.074 0.161 0.202

Vol*** 0.0988 – 0.129 0.134 0.142

BET**** 226 – 304 352 367

For CuCl2·2H2O, A–POSS, and EA chloride, the amount added to the preparation solution [mmol].

**

x: replacement ratio, where Si8O12(C3H6NH3)8](1−x)EA8x[CuCl4]4.

***

Micropore volume [ml g−1].

****

BET surface area [m2 g−1].

The N2 isotherms of the products are presented in Figures 3a and 3b. According to the International Union of Pure and Applied Chemistry (IUPAC) recommendation,34-36 pores are classified into three

groups: micropores, pores with widths less than 2 nm; mesopores, pores with widths between 2 nm

and 50 nm; macropores with widths greater than 50 nm. Since type I isotherms were observed in all 8


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cases except case 2 in Figure 3,34-36 this result indicates the existence of micropores smaller than 2

nm in diameter, which was consistent with the layer distance (1.71 nm). When only EA was present

in the interlayer (case 2), the product was non-porous, which was consistent with the results of previous reports.3 When EA was mixed in A–POSS interlayers with the layer distance of 1.71 nm

(cases 3 to 5), the N2 adsorption amount for these products was greater than that in case 1 (i.e., pure A–POSS interlayer). In comparison with case 3, the product in case 4 exhibited a larger pore volume.

In case 5, the pore volume was approximately the same that in case 4. Further details about the

change in pore volume and BET surface area are discussed later in this study (in the section of “Pore

Volume and Surface Area Evaluations”).

Figure 3. N2 sorption isotherms at 77 K for the obtained hybrid layered perovskites with A–POSS and EA interlayers: (a) cases 1, 4; (b) cases 2, 3, 5.

Large Amine for Narrowing Pores: A large amine, PEA was included in the A–POSS interlayer between CuCl42− perovskite layers in a similar manner. The amount of CuCl2·2H2O, PEA, and A– POSS added to the preparation solutions and the replacement ratios are listed in Table 2. In cases 7,

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8, and 9, 4.6%, 8.8%, and 17.4% of the A–POSS interlayers was replaced by PEA. Powder XRD

patterns of the obtained products are presented in Figure 4. In case 6, sharp peaks at 4.6°, 9.2°, 13.8°, 18.4°, and 23.0° indicate the formation of a layered perovskite with a pure PEA interlayer.33 Notably,

the corresponding layer distance (1.86 nm) was greater than that in case 1 (1.71 nm). In cases 7 and

8, sharp peaks due to A–POSS interlayers (5.2°, 10.3°, and 17.9°) were mainly observed in the

patterns, while small peaks due to PEA interlayers (4.6°, 9.2°, and 13.8°) were observed in the

pattern of case 9. This result also indicates that the layer distance was determined by the size of the

A–POSS when a small amount of PEA (less than 8.8%) was included in the interlayers. This implies

that that the A–POSS interlayers with eight ammonium terminals were bound to two perovskite

layers more strongly than the PEA interlayers. More importantly, the PEA molecules were confined

in a small space created by the A–POSS interlayers. Table 2. Experimental conditions and summary of the results for layered perovskites with A–POSS and PEA interlayers. Case 6 7 8 9 *

CuCl2* 1.0 1.0 1.0 1.0

A–POSS 0 0.150 0.125 0.0625

PEA 2.00 0.80 1 1.50

Si/Cu 0 1.91 1.82 1.65

x** – 0.046 0.088 0.174

Vol*** – 0.0879 0.0769 0.0565

BET**** – 196 179 166

For CuCl2, A–POSS, and PEA chloride, the amount added to the preparing solution [mmol].

**

x: replacement ratio: Si8O12(C3H6NH3)8](1−x)PEA8x[CuCl4]4.

***

Micropore volume [ml g−1].

****

BET surface area [m2 g−1].

10


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Figure 4. XRD patterns of hybrid layered perovskites with A–POSS and PEA interlayers.

Figure 5. N2 sorption isotherms for the obtained hybrid layered perovskites with A–POSS and PEA interlayers: (a) cases 6, 8; (b) case 7; (c) case 9.

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N2 sorption isotherms of the layered perovskite materials are presented in Figures 5a, 5b, and 5c. For a pure PEA interlayer (case 6), no N2 adsorption was confirmed, which is similar to case 2 (Figure 5a). When PEA was included in A–POSS interlayers (cases 7, 8, and 9), type I isotherms similar to

those in Figure 3 were observed; however, the adsorption amount was slightly less than that of the

perovskite with a pure A–POSS interlayer (case 1 in Figure 3). The adsorption amount was slightly

decreased with an increase in PEA fractions (cases 7, 8, and 9).

Pore Volume and Surface Area Evaluations: For a deep understanding of the effect of the amine

addition on the pore volume, the micropore volume and BET surface area were evaluated from the N2 sorption data (see also Tables 1 and 2).31, 32 The results are plotted against the replacement ratio, x, in Figure 6. Some additional data were included in the graph (cases 10 to 16; experimental details

are described in the supporting information). Both the micropore volume and BET surface area

linearly increased with an increase in the EA replacement ratio (less than 20%). The increment was as much as 44% at the replacement ratio = 0.202 (from 0.0988 to 0.142 ml g−1). In addition, when

the EA replacement ratio was greater than 20%, the XRD results suggested an increase in the amount

of non-porous layered perovskites in the present method as previously mentioned. If the EA

replacement ratio further increased, the fraction of non-porous layered perovskites would increase,

which would imply the decrease in the micropore volume and BET surface area. On the other hand,

the micropore volume and BET surface area clearly decreased with an increase in the PEA

12


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replacement ratio. The decrement was as much as 43% at the replacement ratio = 0.174 (from 0.0988 to 0.0565 ml g−1). There is some variance in PEA data in Figure 6 owing to the fractions of

non-porous layered perovskites. In cases 9, 13, and 15, the diffraction peak at 4.6° was appreciable,

which resulted in small micropore volumes (Figure 4 and Figure S1). On the basis of these results,

the micropores were widened upon the introduction of small amines (EA) and were narrowed upon

the introduction of large amines, as summarized in Figure 7. To demonstrate the aforementioned

trend, we tested other amines, BA, CHA, and PBA in a similar manner as EA and PEA (cases 17 to

28; experimental details are described in the supporting information). In addition, the perovskite

layer distance was 1.52 nm for the pure BA interlayer (case 17) and 1.46 nm for the CHA interlayer

(case 23), which was smaller than that of the pure A–POSS interlayers (1.71 nm). In both cases, the

micropores were widened upon the introduction of BA and CHA to the A–POSS interlayers;

however, the increases in the micropore volume and BET surface area were less than those in the

cases in which EA was added (See Figure 6). On the other hand, the perovskite layer distance was

2.31 nm for the pure PBA interlayer (case 26), which was greater than that of the pure A–POSS

interlayers (1.71 nm) and that of the PEA interlayers (1.86 nm). In cases 27 and 28, the micropores

were narrowed upon the introduction of PBA to the A–POSS interlayers, similar to the cases with the

addition of PEA. Overall, the micropore volume increased when a portion of the A–POSS interlayers

was replaced with small organic amines (i.e., EA, BA, or CHA in this study) and decreased when a

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portion of A–POSS interlayers was replaced with large amines (i.e., PEA or PBA in this study).

These amines can be classified with the perovskite layer distance of the pure amine interlayer

compared to that of the POSS interlayer.

Figure 6. Micropore volume and BET surface area plotted against the replacement ratio, x for layered perovskites with EA, PEA, BA, CHA, and PBA mixed interlayers.

Figure 7. Schematics of hybrid layered perovskites with mixed interlayers. Functions as Layered Perovskites: The obtained layered perovskites with mixed interlayers contained micropores; however, the added organic amines may have created defects in the perovskite 14


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layers, thus compromising their magnetic properties of the layered perovskite materials. To confirm

the properties of the layered perovskites, the magnetic moments of selected samples (cases 1, 3, and

8) were recorded at 5 K in a field ranging from 0 to 10 kOe (Figure 8a). The magnetic moments

rapidly increased in a weak magnetic field, which indicates ferromagnetic ordering. Thus, the

obtained layered perovskites with mixed interlayers maintained their functions as layered

perovskites. The saturation magnetization of the layered perovskites with mixed interlayers of EA and A–POSS (case 3) was approximately the same as the net spin magnetic moment of a Cu2+ ion (1.07 µB/each).37 Although this value were slightly better than those in other cases (pure A–POSS interlayers in case 1 and PEA and A–POSS mixed interlayers in case 8), the difference was

insignificant. We assume that the difference in the saturation magnetization is not directly related to

the micropore volume. The temperature dependence of the molar susceptibility of these layered perovskites, χmol was measured from 100 to 2 K at 1000 Oe in a field-cooling manner (Figure 8b). When the temperature was less than 20 K, the susceptibility increased, thus supporting the presence

of ferromagnetic ordering in the obtained layered perovskites. The phase transition temperature (Curie temperature) was approximately constant in all cases. Notably, when EA and PEA were added to A–POSS interlayers, the resulting layered perovskites maintained their functions as layered

perovskites.

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Figure 8. (a) Isothermal magnetic moment measurements of layered perovskites from 0 to 10 kOe. (b) Temperature dependence of molar susceptibility, χmol at 1000 Oe.

Conclusions In this study, we widened and narrowed micropores between copper chloride layered perovskites

by adding organic amines to A–POSS interlayers. In this method, organic amines were included at

proportions as high as 20% in the interlayers without changing the layer distance attributed to the

size of the A–POSS. Through the addition of the EA and PEA, their micropore volume was altered in the range from 0.0565 to 0.142 ml g-1. Despite the addition of amines to the interlayers and the

formation of the expanded micropores, the layered perovskites maintained the functions as low

dimensional materials.

Acknowledgment This work was supported by JSPS KAKENHI (Grant Number: 16K05902).

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characterization of a novel layered perovskite-type organic/inorganic hybrid material containing silica

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Figure and Table Legend: Figure 1: Schematics of the organic–inorganic hybrid layered perovskite, POSS–inorganic hybrid

perovskite with micropores, and the layered perovskite with POSS/organic mixed interlayer.

Figure 2: XRD patterns of hybrid layered perovskites with A–POSS and EA interlayers.

Figure 3: N2 sorption isotherms for the obtained hybrid layered perovskites with A–POSS and EA interlayers: (a) cases 1, 4; (b) cases 2, 3, 5.

Figure 4: XRD patterns of hybrid layered perovskites with A–POSS and PEA interlayers.

Figure 5: N2 sorption isotherms for the obtained hybrid layered perovskites with A–POSS and PEA interlayers: (a) cases 6, 8; (b) case 7; (c) case 9.

Figure 6: Micropore volume and BET surface area plotted against replacement ratio, x for layered

perovskites with EA, PEA, BA, CHA, and PBA mixed interlayers.

Figure 7: Schematics of hybrid layered perovskites with mixed interlayers.

Figure 8: (a) Isothermal magnetic moment measurements from 0 to 10 kOe. (b) Temperature dependence of molar susceptibility, χmol at 1000 Oe. Table 1: Experimental conditions and result summary of layered perovskites with A–POSS and EA

interlayers.

Table 2: Experimental conditions and result summary of layered perovskites with A–POSS and PEA

interlayers.

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Figure 1: Schematics of the organic–inorganic hybrid layered perovskite, POSS–inorganic hybrid perovskite with micropores, and the layered perovskite with POSS/organic mixed interlayer. 147x99mm (150 x 150 DPI)


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Figure 2: XRD patterns of hybrid layered perovskites with A–POSS and EA interlayers. 89x107mm (150 x 150 DPI)


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Figure 3: N2 sorption isotherms for the obtained hybrid layered perovskites with A–POSS and EA interlayers: (a) cases 1, 4; (b) cases 2, 3, 5. 189x74mm (150 x 150 DPI)


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Figure 4: XRD patterns of hybrid layered perovskites with A–POSS and PEA interlayers. 89x118mm (150 x 150 DPI)


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Figure 5: N2 sorption isotherms for the obtained hybrid layered perovskites with A–POSS and PEA interlayers: (a) cases 6, 8; (b) case 7; (c) case 9. 188x149mm (150 x 150 DPI)


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Figure 6: Micropore volume and BET surface area plotted against replacement ratio, x for layered perovskites with EA, PEA, BA, CHA, and PBA mixed interlayers. 197x72mm (150 x 150 DPI)


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Figure 7: Schematics of hybrid layered perovskites with mixed interlayers. 149x112mm (150 x 150 DPI)


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Figure 8: (a) Isothermal magnetic moment measurements from 0 to 10 kOe. (b) Temperature dependence of molar susceptibility, χmol at 1000 Oe. 197x73mm (150 x 150 DPI)


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Table of Contents 122x68mm (150 x 150 DPI)


Toward Increasing Micropore Volume between Hybrid Layered

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