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Manuscript-Catalysts 2022 Corrected
Manuscript-Catalysts 2022 Corrected
Manuscript-Catalysts 2022 Corrected
Said Arhzaf 1, Jamal Houssaini 1, Mohammed Naciri Bennani 1,* and Marwa Alaqarbeh 2,* 5
1 Laboratory of Chemistry and Biology Applied to the Environment, URL-CNRST 13, Research Team "Materi- 6
als and Applied Catalysis," Chemistry Department, Moulay Ismail University, BP. 11201 Zitoune, Meknes- 7
50000, Morocco; arhzafcom@hotmail.fr (S.A.); jamal.houssaini@edu.umi.ac.ma (J.H.); m.naciriben- 8
nani@umi.ac.ma (M.N.B.) 9
2 National Agricultural Research Center, Al-Baqa 19381, Jordan; marwa.alaqarbeh@narc.gov.jo (MA.) 10
* Correspondence: m.naciribennani@umi.ac.ma; marwa.alaqarbeh@narc.gov.jo 11
Abstract: The aldol condensation reaction of Furfural (F) with acetone (A) yielding 4-(2-Furyl)-3- 12
buten-2-one (FA), which is used as a flavoring in the food field, is usually catalyzed by liquid bases. 13
To preserve the environment, substituting the homogeneous base with solids is highly desirable. 14
For this purpose, a series of layered double hydroxides (LDHs) containing different interlayer ani- 15
ons MgAl-X LDHs (X: NO3-, CO32-, CH3COO-), were prepared by the co-precipitation method. Mixed 16
oxides obtained by heat treatment at 450°C in an atmospheric stream were evaluated in the liquid 17
phase on the aldol condensation of Furfural and acetone at 60 and 90 °C in the absence of solvent. 18
Citation: Arhzaf, S.; Houssaini, J.; These mixed oxides show very different catalytic activity and indicate a significant effect of interla- 19
Naciri. Bennani, M. Effect of Inter- mellar anions and precursor activity (LDHs). Also, the influence of interlamellar anions on the struc- 20
layer Anions on Catalytic Activity tural properties of (LDHs) was determined. X-ray diffraction (XRD) analysis measured interlamel- 21
using Mg-Al Layered Double Hy-
lar distance and crystallite size. At the same time, infrared spectroscopy (FT-IR) was used to explore 22
droxides in Aldolic Condensation
bands corresponding to the different compensation anions. The specific surface area, pore volume 23
between Furfural and Acetone. Cata-
of the corresponding precursor (LDHs), and the mixed oxides derived from them were determined 24
lysts 2022, 12, x.
by nitrogen adsorption (BET). Reaction kinetics were performed by taking samples at regular inter- 25
https://doi.org/10.3390/xxxxx vals; the samples were analyzed using gas chromatography. The derived oxides of LDHs whose 26
Publisher’s Note: MDPI stays neu- Keywords: Layered double hydroxides; Hydrotalcite; Mixed oxide; Aldolic condensation; Furfural; 32
tral with regard to jurisdictional Acetone. 33
claims in published maps and institu-
34
tional affiliations.
1. Introduction 35
Copyright: © 2022 by the authors.
In the field of fine chemistry, many important industrial reactions are catalyzed by 36
Submitted for possible open access
homogeneous bases, such as: (condensation, alkylation, and addition). The most common 37
publication under the terms and con-
catalysts used with solvents are liquid bases (NaOH, KOH, metal alkoxides, …etc.). Also, 38
ditions of the Creative Commons At-
tribution (CC BY) license (https://cre-
it has a major drawback because their use on an industrial scale leads to a significant pro- 39
ativecommons.org/licenses/by/4.0/). duction of saline effluents that harm the environment and require subsequent high-cost 40
treatment [1]. 41
Substitution of liquid bases for basic solids, such as lamellar double hydroxides 42
(LDHs), has an ecological interest by allowing decreased corrosion, improving regenera- 43
tion, and facilitating recovery. Numerous attempts have been undertaken in recent years 44
to try to replace the typical basic liquid catalyst with solid catalysts, which have many 45
advantages, to avoid ecological, economic, and technical problems [2,3]. 46
The aldol condensation between Furfural (F) and acetone (A) led essentially to two 47
products which are 4-(2-furyl)-3-buten-2-one (FA) and 1,5-difuran-2-yl-enta-1,4-dien-3- 48
one (F2A). The production of Furfural worldwide comes from the transformation of co- 49
products from the agro-food industries (corn cobs, wheat straw, sugar cane bagasse,... etc.) 50
by aldol condensation reaction associated with catalytic hydrodeoxygenation, which has 51
led to the development of the chemistry of furanic products as well as other potential 52
applications in the field of petrochemistry and biofuel production [4]. Several food man- 53
ufacturers also use the FA as a flavoring for beverages, candies, gelatins, flavors, …etc. In 54
this axis, the aldol condensation of Furfural and acetone without solvent was performed 55
in the presence of solid catalysts based on hydrotalcite [5]. 56
Hydrotalcite-like compounds belong to a class of anionic clay minerals known as lay- 57
ered double hydroxides (LDHs), and they are represented by the chemical formula [M2+1- 58
x M3+x(OH)2]. [Xn-x/n], where the divalent Metal ion M2+ may be (Mg2+, Zn2+, Ni2+…), and the 59
trivalent Metal ion M3+ (Al3+, Fe3+, Ga3+…). The compensating anions X n- may be (CO32-, 60
NO3-, organic anions,…) and x is equal to the ratio of M3+/ M3++ M2+ with a value varying 61
in the range of 0.2 < x ≤ 0.33 [6–8]. Brucite-like layers of Mg constitute their structure (OH)2, 62
where the substitution of M2+ by M3+ of relatively similar sizes (rM2+ - rM3+) < 0.18 Å leads 63
to a net positive charge of the layer, compensated by anions, in the interlayer space with 64
water molecules [7]. Therefore, the preparations of hydrotalcite with inorganic or organic 65
anions are described in the literature [8]. Due to the catalytic properties, the mixed oxides 66
derived from hydrotalcite have a particular interest. The nature and ratio of cations pre- 67
sent in brucite layers, the nature of the anions present in the intermediate layer of the 68
hydrotalcite precursor, and the thermal decomposition temperature [9–11] notably influ- 69
ence the density of the basic sites [12]. However, less attention has been paid to the influ- 70
ence of interlayer anions in hydrotalcite precursors on the catalytic activity of hy- 71
drotalcite-derived mixed oxides, particularly concerning aldol condensations [13]. 72
This work aims to synthesize hydrotalcite MgAl-X with Mg/Al molar ratio equal to 3 73
and have different interlayer anions (X). By co-precipitation method at constant pH, and 74
study the influence of different interlayer anions on the catalytic activity of the derived 75
mixed oxides in the aldol condensation of Furfural with acetone. However, X-Ray diffrac- 76
tion (XRD), Fourier transform infrared (FT-IR) spectroscopy, Brunner Emmett and Teller 77
method (BET), thermogravimetric analysis (TGA/DTA), and Scanning Electron Micros- 78
copy-Emission with Energy Dispersive Spectroscopy (SEM-EDS) were used to character- 79
izing the structural modifications. 80
k. λ 1
D= × 91
β cos (θ)
Catalysts 2022, 12, x FOR PEER REVIEW 3 of 13
Where (k) is a constant related to the crystallite shape, normally taken to be equal to 92
0.9, with (λ) the X-ray wavelength, (β) is the width of the diffraction peak at half maxi- 93
mum, and (θ) is the value of the theta angle relative to a line (003). 94
The results show that the size of the crystals varied depending on the sort of inter- 95
calated anion, as seen above. For HT-CO3 and HT-NO3, the diffraction patterns consist of 96
more extensive reflections at higher 2θ values and crisp, symmetric, and strong basal re- 97
flections at low 2θ values, which correspond to consecutive orders of the interlayer spac- 98
ing. The basal reflections for HT-CH3COO are more diffuse and less intense, which sug- 99
gests less crystallinity and a likely disorder of the layered structure. As a result, the anion's 100
type determines the hydrotalcite's crystallinity and layering sequence. The layered hy- 101
drotalcite structure vanishes after the calcination of hydrotalcite at 450 °C, according to 102
XRD patterns of cHT-X. The only reflections in the XRD pattern pertain to the MgO phase, 103
indicating the development of Mg-Al mixed oxide with the MgO periclase-type structure. 104
The results of these calculations are shown in (Table 1). 105
The lattice parameter a is practically the same for all the solids since they are the same 106
types of metal atoms, Mg and Al. The significant difference in the basal spacing is the type 107
of anions intercalated in the different solids. From the point of view of charge and size, 108
the smallest value of parameter c is that which corresponds to the HT-CO3 because the 109
carbonate anions are doubly charged and cause a solid electrostatic attraction, whereas 110
for the monocharged anions like NO3- and CH3COO- the increase in parameter c is due to 111
their sizes. The intercalation of acetate anions, with an average spacing of 12.1 Å (2θ = 112
7.2°), corresponds to the (003) reflection in acetate intercalated LDHs, like the report of El 113
Malki et al [16]. The higher order basal reflections, (006) and (009), are observed at 7.6 Å 114
(2θ = 11.5°) and 4.2 Å (2θ = 21.3°), respectively. The turbostratic disorder appearing in the 115
middle region (30° < 2θ < 50°) is due to the disordered insertion of water molecules in the 116
interlayer galleries of HT-CH3COO. 117
A B
(200)
(003)
(220)
(015)
(110)
(006)
(113)
(018)
(009)
cHT-CO3
HT-CO3
Intensity (a.u)
Intensity (a.u)
cHT-NO3
HT-NO3
HT-CH3COO cHT-CH3COO
10 20 30 40 50 60 70 10 20 30 40 50 60 70
2 q (degree) 2q (degree)
118
Figure 1. X-ray diffraction patterns of the fresh hydrotalcite (A: HT-X) and calcined hydrotalcites 119
(B: cHT-X). 120
Table 1. Lattice parameters and size crystallite of the hydrotalcite samples. 121
420
1561
3600-3400
1412
554
643
805
1637
1022
1712
HT-CH3COO
Absorbance (a.u)
432
1382
655
836
1580
HT-NO3
426
662
1370
1642
HT-CO3
DTA (uV)
80
140°C
70
436°C
60
397°C
50 205°C
100 200 300 400 500 600 100 200 300 400 500 600
Temperature (°C) Temperature (°C)
Sample Surface BET (m2.g-1) Pore diameter (nm) Pore volume (cm3. g-1)
HT–CO3 73 10 – 20 0.41
HT–NO3 21 11 – 15 0.09
HT–CH3COO 25 9 – 17 0.11
cHT–CO3 179 14 – 18 0.74
cHT–NO3 69 10 – 12 0.12
cHT–CH3COO 121 12 – 16 0.27
165
The large specific surface of calcined HDLs based on carbonates and acetates is due 166
to the new particle size distribution of the material after heat treatment. 167
the expected one (Mg/Al = 1.98). This could be from the total precipitation in the acetate 176
anion case. 177
Figure 4. SEM images at 20 µm and EDS analysis of the hydrotalcite: (a) HT-CO3, (b) HT-NO3, and 178
(c) HT-CH3COO. 179
boiling point, caused poorer starting materials conversions to Furfural and selectivity de- 184
sirable condensation selectivity products FA and F2A. The critical reaction step is forming 185
alcohol intermediate in the early stages of the reaction, which is then dehydrated to give 186
the first desired condensation product, FA. This is condensed with another furfural mol- 187
ecule and dehydrated to produce F2A. According to Lukas Hora et al. [27], low-tempera- 188
ture operation does not encourage dehydration of the alcoholic intermix during the initial 189
stage of the reaction, which lowers the reaction's selectivity towards FA and F2A at the 190
expense of the alcoholic intermediate. Operation at high temperature (60–90) °C favors 191
synthesizing condensation products with better selectivity than FA (Table 3). Similarly, 192
when operating at an average temperature of 60 °C, an intermediate (P) appears next to 193
FA. 194
According to the study made by R. E. O’Neill et al. [28], during the study of this aldol 195
condensation reaction between acetone and Furfural in the homogeneous catalysis, he 196
found that the by-product P, which forms in parallel with the FA, is due to the condensa- 197
tion of 3 molecules of Furfural with two molecules of Acetone. By working at a tempera- 198
ture of 90 °C, the only products formed are FA and F2A. In contrast, the intermediary 199
products do not appear because a high reaction temperature facilitates the dehydration of 200
alcohol and the decomposition of the intermediate product P into FA and F2A. 201
Table 3. Conversion and selectivity of calcined HDLs, in the aldol condensation between acetone 202
and Furfural at 60 and 90°C, after two hours of reaction. 203
The large specific surface of calcined HDLs based on carbonates and acetates gives 204
them excellent activity for the condensation reaction of Furfural with acetone but with a 205
difference in selectivity in FA and F2A. For this purpose, under the condition (T= 90°C), 206
this reaction gives rise to a conversion of nearly 99% after 2 hours and a selectivity of 76% 207
in FA and 18% in F2A when the calcined solid is used based on carbonates. In contrast, 208
the calcined solid based on acetates had a selectivity conversion of 65% in FA and 32% in 209
F2A. This difference can be explained by the difference in numbers and natures of the 210
acid-base sites of the synthesized solids. 211
3.2. Mechanism of the aldol condensation reaction of Furfural with acetone 212
The aldol condensation between acetone and Furfural using the hydrotalcite-type 213
solid catalysts is according to the following reaction scheme 1 [27]. 214
215
Catalysts 2022, 12, x FOR PEER REVIEW 8 of 13
Scheme 1. Reaction scheme of the aldol condensation between Furfural and Acetone. 216
The time evolution of the reaction, as illustrated in the GC chromatograms (Figure 217
5), indicates that the product (P) disappears over time, decomposing into FA and F2A. In 218
this study of the same reaction in homogeneous catalysis, as shown in the following reac- 219
tion scheme 2 [29]. 220
221
Scheme 2. Scheme of the formation and disappearance of the intermediate product (P). 222
It can be seen that when working at high temperatures, the only condensation products 223
formed are FA and F2A, while the intermediate and unstable product (P) does not appear. 224
The chromatogram (Figure 5) was obtained by GC analysis on the studied reaction after 2 225
hours at T = 60 °C on cHT-CH3COO. The peaks observed at retention times 1.09; 2.63; 7.11, 226
and 14.53 minutes correspond, respectively, to the acetone and furfural reagents (unre- 227
acted) and the FA and F2A products. 228
229
Figure 5. Chromatogram of Furfural and acetone condensation reaction products after 2 h reaction 230
time at 60 °C on cHT–CH3COO catalyst. 231
For the aldol condensation reaction of Furfural with acetone on the cHT-CO3 catalyst, 232
the reaction rate was determined at two different temperatures 60 °C and 90 °C. Thus, we 233
found that the apparent activation energy (Ea) of the aldol condensation reaction of Fur- 234
fural with acetone over the same catalyst is equal to 24.8 KJ. mol -1 [26]. 235
Magnesium nitrate (Mg(NO3)2. 6H2O; 99%), aluminium nitrate (Al(NO3)3. 9H2O; 238
99%), sodium carbonate (Na2CO3; 99.9%), sodium hydroxide (NaOH; 99.8%), sodium 239
acetate (NaCH3CO2; 99.9%), ammonia solution (NH4OH; 25%), Acetone (C3H6O; 99.8%) 240
and (Furfural C5H4O2; 99.8%) were purchased from Loba Chemie (India). (Mg(CH 3CO2)2. 241
4H2O; 99.8%), (Al(CH3CO2)2 . OH; 99.8%), (Decane; C10H22; 99.9%), and (FA: C8H8O2; 242
99.8%) were purchased from Sigma-Aldrich. All of the reagents were of an analytical 243
grade and were employed directly. This reaction is carried out in an autoclave reactor 244
with a volume of 100 ml and a temperature sensor. 245
4.2. Preparation of MgAl-X LDHs 246
The MgAl-CO3 LDH was prepared by the co-precipitation method with a constant 247
pH. Two aqueous solutions (250mL), the first one containing 0.15 mol of (Mg(NO3)2.6H2O) 248
and 0.05 mol of (Al(NO3)3.9H2O) for a composition Mg/Al=3 and the second one contain- 249
ing 0.4 mol of NaOH and 0.025 mol of Na 2CO3, were mixed at 50°C under vigorous stir- 250
ring, maintaining the pH close to 10. At the end of the addition, the mixture was refluxed 251
at 65°C for 18 hours. The precipitate was formed and washed several times until the solu- 252
tion was free of nitrate ions, then dried at 80°C. This sample is referred to as HT-CO3. 253
The MgAl-NO3- LDH was prepared, keeping the same arrangement and the exact 254
proportions of the metal salts, the NaOH/ Na2CO3 precipitating agent was simply replaced 255
by NH4OH (2M), and no inert gas, such as nitrogen, was bubbled through the reaction 256
mixture. This sample is referred to as HT-NO3. 257
The MgAl-CH3COO- LDH was prepared by the co-precipitation method. Two aque- 258
ous solutions (200 mL), the first one containing 0.15 mol of (Mg (CH3CO2)2.4H2O), and 0.05 259
mol of (Al (CH3CO2)2.OH) for a composition Mg/Al= 3 and the second one containing 0.4 260
mol of NaOH and 0.05 mol of (NaCH 3CO2), were slowly mixed at 50°C under vigorous 261
stirring, maintaining the pH close to 10. At the end of the addition, the mixture is refluxed 262
at 65°C for 18 hours. The precipitate was washed several times, and the products were 263
dried at 80°C. This sample is referred to as HT-CH3COO. 264
They were made active by employing a tube furnace to calculate the catalysts, HT- 265
CO3, HT-NO3, and HT-CH3COO, to 450 °C in the air. The temperature was maintained at 266
450 °C for 8 hours while increasing by 5 °C/min. The catalyst-produced mixed oxides are 267
used to condense the Furfural and acetone. 268
4.3. Catalyst Characterizations 269
Monochromatized Cu-K radiation (λ = 1.5406 Å, 40 kV, and 20 mA) was used in a 270
PW 1800 Philips automated goniometer (Bragg-Brentano) to record the powder X-ray dif- 271
fraction patterns of hydrotalcite samples. The data were gathered using angular incre- 272
ments of 0.04° to 2S per increment over the 2θ angular diffraction range of 5° to 70°. The 273
hydrotalcite samples' Fourier transformed infrared (FT-IR) spectra were captured using 274
the KBr pellet technique and a Shimadzu (IR AFFINITY-1S) instrument, with a resolution 275
of 4 cm-1 for each sample. The KBr pellets were made by combining 98 wt% KBr with 276
extensively dried hydrotalcite that had around 2 weight percent of KBr. 277
They used a Shimadzu thermogravimetric and differential thermal analyzer (TG- 278
DTA) analyses (TA-60). Samples weighing a few milligrams were heated at a rate of 10 279
°C/min till 600 °C. The samples' surface and pore sizes were determined by employing the 280
BET method and nitrogen adsorption at -196°C on a Micromeritics ASAP-2010 system. 281
Pore size was determined using the BJH (Barrett-Joyner-Halenda) technique applied to 282
the desorption branch. All samples were outgassed under vacuum at either 100 °C for 283
fresh LDHs (HT-X) or 200 °C for calcined LDHs prior to analysis (cHT-X). 284
Using a scanning electron microscope, TESCAN Vega3-EDAX apparatus with an ac- 285
celerating voltage of 20 kV examined the morphology of the Hydrotalcites powder. Our 286
materials' elemental makeup was identified using energy-dispersive X-ray spectroscopy 287
(EDS). 288
4.4. Reaction conditions and analysis 289
Catalysts 2022, 12, x FOR PEER REVIEW 10 of 13
In a stirred auto-clave agitation reactor set to the reaction temperature, Furfural was 290
aldol condensation with acetone. For each experiment, the reactor is filled with 29 g of 291
acetone (A) and 4.8 g of Furfural (F) (molar ratio A/F = 10). Acetone was added more than 292
Furfural to produce FA with remarkable selectivity [30] and then given 1g of freshly cal- 293
cined HT-An- hydrotalcite. GC is used to track the dissolution of Furfural and the devel- 294
opment of condensation products (FA and F2A), using decane as an internal standard. 295
The injector and detector temperatures were set at 250 °C. The temperature of the column 296
was programmed by heating it at 50 °C for 3 minutes, then ramping up at a rate of 20 297
°C/min to 150 °C, leaving it at this temperature for 3 minutes, then ramping up at a rate 298
of 2 °C/min. The chromatographic analysis was performed using a (Shimadzu-2010) chro- 299
matograph equipped with a DB1 capillary column 0.25 mm in diameter and 25 m in 300
length, equipped with a flame ionization detector. The reaction products have been iden- 301
tified by comparing the reaction products to commercial items based on their retention 302
times. 303
The following formulas were used to calculate the conversion rates of Furfural, se- 304
lectivity, and yield to FA and F2A at a given moment. 305
[Product(i)]t 2[F2A]t
Yield product (i) (%) = × 100 Selectivity F2A (%) = × 100 307
[F]0 [F]0 −[F]t
Where [F]0, [F]t, [FA]t, and [F2A]t represents, in turn, the starting concentration of Fur- 308
fural, the concentration at the time of Furfural that has not yet been consumed, and the 309
concentrations of the products FA and F2A. 310
5. Conclusions 311
The phases of type MgAl-X (HT-X) were prepared by the co-precipitation method at 312
constant pH with the same molar ratio (Mg/Al= 3) and with different compensating anions 313
(X: CO32-, NO3- and CH3COO-). Different physicochemical techniques subsequently char- 314
acterized these materials. The XRD diffractograms of the different synthesized lamellar 315
phases show a remarkable similarity with those of the layered double hydroxides and 316
highlight the main reflections characteristic of these compounds with an inter-lamellar 317
distance d003=7.81 Å and 8.67 Å for the HT-CO3 and HT-NO3 phases, whereas, for the HT- 318
CH3COO phase which testifies of a turbostratic character, the inter-lamellar distance is 319
d003=12.10 Å. The electron microscopic observations of these phases highlight the char- 320
acteristic morphology of the double lamellar hydroxides: platelet morphology which dif- 321
fers enormously depending on the intercalated anion. The FT-IR analysis of these materi- 322
als allowed us to identify the molecular vibrations corresponding to the inter-lamellar an- 323
ions' vibrations and the hydroxylated groups' vibrations and to know the vibrations of the 324
network related to the octahedral layers. After heat treatment, we found that compared to 325
the aldol condensation of Furfural with acetone, the mixed oxide cHT-NO3 from HT-NO3 326
has low catalytic activity, while the mixed oxides (cHT-CO3 and cHT-CH3COO) from their 327
precursors HT-CO3 and HT-CH3COO showed excellent conversion to Furfural (≥ 98%), 328
with a difference in selectivity to FA and F2A, such that the cHT-CO3 catalyst is more 329
selective to FA (76 % at T=90 °C) than cHT-CH3COO (65 % at T=90 °C). Furthermore, the 330
conversion and selectivity of both catalysts increase with temperature. 331
Supplementary Materials: The following supporting information can be downloaded at: 332
www.mdpi.com/xxx/s1, Figure S1: X-ray diffraction patterns of the fresh hydrotalcite (A: HT-X), 333
and calcined hydrotalcites (B: cHT-X), Figure S2: FT-IR spectra of the HT-X Hydrotalcites, Figure 334
S3: TGA-DTA profiles in the (25-600) °C range of HT-X hydrotalcite, Figure S4: SEM images and 335
EDS analysis of the hydrotalcite: (a) HT-CO3, (b) HT-NO3, and (c) HT-CH3COO, Figure S5: Chroma- 336
togram of the condensation reaction products of Furfural and acetone after 4 h reaction time at 60 337
Catalysts 2022, 12, x FOR PEER REVIEW 11 of 13
°C on cHT–CH3COO catalyst, Scheme S1. Reaction scheme of the aldol condensation between Fur- 338
fural and Acetone; Table S1: Lattice parameters and size crystallite of the hydrotalcite samples, Table 339
S2: Surface area and porosity are determined by N2 adsorption, Table S3: Conversion and selectivity 340
of calcined HDLs, in the aldol condensation between acetone and Furfural at 60 and 90°C, after two 341
hours of reaction. 342
Author Contributions: Conceptualization, SA and MNB; methodology, SA, MNB, and JH, software, 343
SA, JH, and MNB; validation, JH, and MNB; investigation, SA, and JH, resources, SA, data curation, 344
JH; writing—original draft preparation, SA, and JH; writing—review and editing, SA; JH, MA and 345
MNB; supervision, MNB All authors have read and agreed to the published version of the manu- 346
script. 347
Funding: This research was funded by the Ministry of Higher Education and the National Center 348
for Scientific and Technical Research (CNRST), Morocco. 349
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