The Synthesis and Some Properties of New Compound Cu13fe4v10o44

J Therm Anal Calorim (2012) 110:1161–1166 DOI 10.1007/s10973-011-2082-8

The synthesis and some properties of new compound Cu13Fe4V10O44

Anna Blonska-Tabero

Received: 23 September 2011 / Accepted: 16 November 2011 / Published online: 4 December 2011 Ó The Author(s) 2011. This article is published with open access at Springerlink.com

Abstract A new compound with the formula Cu13Fe4V10O44 forming as a result of reactions of the above vana- has been obtained as a result of a solid-state reactions dates(V) will also prove attractive from the catalytic occurring during heating the mixtures both of oxides: CuO, application point of view. Thus, the system CuO–V2O5– V2O5,Fe2O3 and vanadates: Cu5V2O10,Cu3Fe4V6O24. The Fe2O3 seems as a reasonable choice in the search for new DTA measurements were used to choose the heating tem- potential catalysts of selective oxidation of organic peratures as well as for determination of thermal stability compounds. of the new compound. Cu13Fe4V10O44 melts incongruently It is known that in one of the cross sections of the CuO– at 790 ± 5 °C. The new phase crystallizes in the mono- V2O5–Fe2O3 system, i.e. in the system FeVO4–Cu3V2O8,a clinic system. The indexing results and the calculated unit double vanadate(V) of the formula Cu3Fe4V6O24 is formed cell parameters for Cu13Fe4V10O44 are given. Its infra-red [3–5]. This compound is met in two crystallographic spectrum and image obtained by means of an electron modiﬁcations. The a-Cu3Fe4V6O24 form is a mineral called scanning microscope are presented. lyonsite [6]. The synthesis of Cu3Fe4V6O24 by the conventional solid-state reaction leads to its another form, i.e.

Keywords Copper iron vanadate DTA b-Cu3Fe4V6O24 [3–5] whose structure is like that of min- Solid-state reaction XRD eral howardevansite, NaCuFe2V3O12 [7]. According to Belik et al. [8], the phase of the lyonsite type structure can be obtained by the conventional method of sintering, but Introduction the phase thus obtained has a composition different from that describing the mineral, and moreover, it has a certain

Vanadates(V) of di- and trivalent metals belong to the few range of homogeneity as expressed by Cu3?1.5xFe4-xV6O24 catalysts which one able to stop the process of oxidation of (0.667 B x \ 0.778). The two minerals were discovered in some organic compounds at the intermediate stage, e.g. the summit crater fumaroles of the Izalco volcano [6, 7]. corresponding to oleﬁns or aldehydes. It is known, for The phases of the structures of lyonsite and howardevansite example, that copper(II) vanadates(V) are catalytically also form in other analogous ternary systems [8–11]. active in the reaction of oxidative dehydrogenation of Belik et al. [8] studied the reactivity of oxides only for a isobutane to isobutene [1], whilst iron(III) orthovana- limited range of concentrations of FeVO4–Cu3V2O8 sys- date(V) catalyses methanol oxidation to formaldehyde [2]. tem, i.e. from 14.29 to 50.00 mol% Cu3V2O8 in the initial In view of the above, it can be expected that the phases mixtures. Interestingly, diffractograms of some samples

containing from 30.15 to 50.00 mol% Cu3V2O8, have revealed a number of unidentiﬁed reﬂexes besides those

characteristic for Cu2V2O7 and for lyonsite structure phase A. Blonska-Tabero (&) [8]. This observation could mean that besides the phases of Department of Inorganic and Analytical Chemistry, West lyonsite and howardevansite structures, there is one more Pomeranian University of Technology, Szczecin, Al. Piastow 42, 71-065 Szczecin, Poland phase in the ternary system CuO–V2O5–Fe2O3 in which e-mail: [email protected] all components are engaged. The authors [8] have not 123

Unauthenticated | Downloaded 09/24/21 09:26 PM UTC 1162 A. Blonska-Tabero attempted to determine of the composition of this unknown was performed on the base of their XRD characteristics phase. contained in the PDF cards. The powder diffraction pattern The aim of the study presented was to establish the of the new compound was indexed by means of the Dicvol composition of the new phase forming in the CuO–V2O5– program [18], using a-Al2O3 as the internal standard. The Fe2O3 system and determine its some physicochemical parameters of the unit cell were reﬁned by the Reﬁnement properties. program of DHN/PDS package. The density of the new phase was determined using the method described in the work [19]. Experimental The IR measurement (Specord M 80; Carl Zeiss, Germany) was conducted in the wavenumber range of Samples were obtained from the following oxides: CuO 1,400–250 cm-1, applying the technique of pressing pellets

(p.a., Fluka), V2O5 (p.a., Riedel-de Hae¨n), and a-Fe2O3 of the new compound with KBr in a ratio 1:300 by weight. (p.a., POCh). Only one sample was prepared from vana- The investigations by SEM/EDX methods were carried dates: Cu5V2O10 [12, 13] and b-Cu3Fe4V6O24 [3–5]. These out by means of an electron scanning microscope vanadates were obtained as a result of sintering the stoi- (JSM-1600, Jeol, Japan) with an X-ray energy dispersive chiometric mixtures of appropriate oxides in the following analysis (ISIS-300, Oxford). stages: – synthesis of Cu V O : 560 °C(20 h) ? 750 °C(20 h) 5 2 10 Results and discussion 9 2 – synthesis of b-Cu Fe V O : 560 °C(20 h) ? 590 °C 3 4 6 24 The compositions of the samples prepared for investiga- (20 h) ? 610 °C(20 h) ? 625 °C(20 h) [4] tion, the methods of their heating, and XRD analysis results

The XRD characteristics of Cu5V2O10 and b-Cu3 of these samples after their last heating stage are given in Fe4V6O24 obtained this way were consistent with PDF data Table 1. The position of the investigated samples in the (cards: 70-1326 and 80-0220, respectively). component concentration triangle of the CuO–V2O5–Fe2O3 The reactions, both amongst oxides as well as between system is shown in Fig. 1. The position of Cu3Fe4V6O24 Cu5V2O10 and b-Cu3Fe4V6O24, were carried out in the [3–5] and the lyonsite structure phase [8] are also marked. solid state by conventional method of sintering samples The study was started with checking if the composition [14–17]. The initial mixtures of reactants, after homogen- of the unknown phase (hereafter X-phase) corresponds to ising by grinding, were heated in porcelain crucibles in the the formula Cu2FeVO6, as according to the literature in atmosphere of air for several stages until the state of some analogous ternary systems, the compounds of the equilibrium was attained. On completion of each heating general formula M2AVO6 are formed, e.g. Ni2FeVO6 [20], stage, the samples were gradually cooled down in furnace Cu2BiVO6 [21], Cd2InVO6 [22]. to room temperature, ground and investigated by XRD A mixture of the composition corresponding to the method with respect to their compositions. Some of the formula Cu2FeVO6 was prepared (Table 1 sample 1). The samples were investigated by DTA method too. This pro- diffractogram of this sample, being in the state of equi- cedure was repeated until the compositions of the samples librium, showed a set of reflexes which could not have been did not change after two consecutive heating stages. The assigned to any of the known phases forming in the heating temperatures were about 60 °C below the melting CuO–V2O5–Fe2O3 system, besides the reflexes attesting to points of the samples, as determined by DTA method. The the presence of a-Fe2O3 and Cu5V2O10. It was assumed melting temperatures of the samples were read as the onset that this set of reflexes characterises the unknown X-phase. temperature of the first endothermic effect recorded in the According to the results, the sample was not monophase, DTA curve of given sample. Accuracy of reading these and so the composition of the new phase must be different temperatures (±5 °C) was determined by repetitions. from that described by the formula Cu2FeVO6. The DTA/TG investigations (the Paulik–Paulik–Erdey In the ternary system, the composition of the forming type derivatograph; MOM, Hungary) were performed in air phase corresponds often to the point of intersection of the atmosphere at a rate of 10 °C min-1. Samples of 500 mg system’s cross sections. Three mixtures were prepared for were heated in quartz crucibles in the temperature range the study. Their compositions (Table 1) correspond to the

20–1,000 °C. intersection points of the cross section of Cu3V2O8–Fe2O3 Samples were studied by means of an X-ray diffrac- with the systems: FeVO4–Cu5V2O10 (sample 2), Cu5V2O10 tometer HZG4/A2 (Carl Zeiss, Germany). The source of –Cu3Fe4V6O24 (sample 3) and FeVO4–Cu11V6O26 (sample radiation used was a copper tube equipped with a nickel 4). According to the above data, the new phase is most

ﬁlter. The identiﬁcation of phases occurring in the samples probably formed in the Cu5V2O10–Cu3Fe4V6O24 system. 123

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Table 1 Composition of initial mixtures, their heating conditions and state, there is an excess of Cu5V2O10 in this sample. Two results of XRD analysis of samples after their last heating stage other samples were prepared of the compositions corre-

No. Composition of initial Heating conditions Phases at sponding to the Cu5V2O10:Cu3Fe4V6O24 ratio of 2.5:1 mixtures (mol%) equilibrium (sample 5) and 2:1 (sample 6). In sample 6, at the state of state CuO V2O5 Fe2O3 equilibrium neither the initial reagents nor any of the phases known to form in the CuO–V2O5–Fe2O3 were found. The 1 66.66 16.67 16.67 560 °C (20 h) ? 600 °C (20 h) X, Fe O , 2 3 diffractogram of this sample showed only the set of reﬂexes ? 700 °C (20 h) ? 720 °C Cu5V2O10 (20 h) 9 2 2 68.18 22.73 9.09 X, Fe2O3, assumed to correspond to the unknown X-phase. Cu5V2O10 Three more samples were prepared of compositions 3 69.23 23.08 7.69 X, Cu5V2O10 similar to that of sample 6 (Table 1, samples 7–9). In all 4 71.74 23.91 4.35 X, Cu3V2O8, these samples at the state of equilibrium, the presence of Cu V O 11 6 26 X-phase along with the other phases known to form in the 5 67.39 23.91 8.70 X, Cu V O 5 2 10 ternary system studied was conﬁrmed. 6 65.00 25.00 10.00 X 7 62.96 25.93 11.11 X, lyonsite- Analysis of all above data permits concluding that as a type phase result of heating a mixture of the composition 65.00% mol

8 65.00 23.00 12.00 X, Fe2O3, CuO, 25.00% mol V2O5 and 10.00% mol Fe2O3 (sample Cu5V2O10 6), a new phase has been formed whose composition can be 9 65.33 26.67 8.00 X, Cu2V2O7 described by the formula Cu13Fe4V10O44. Hence, the new phase is formed in the solid–state reaction according to the equation:

13CuOðsÞ þ 5V2O5ðsÞ þ 2Fe2O3ðsÞ ¼ Cu13Fe4V10O44ðsÞ ð1Þ The composition of sample 3 expressed in the components of the Cu5V2O10–Cu3Fe4V6O24 system corresponds to the The new phase was also synthesised using as initial Cu5V2O10:Cu3Fe4V6O24 ratio of 3:1. At the equilibrium reagents the components of the system Cu5V2O10–

Fig. 1 The position of Cu3Fe4V6O24, lyonsite type •4 phase and the investigated 3 samples in the component •• 2 CuO •5 •1 concentration triangle of the • •9 •6 •8 CuO–V2O5–Fe2O3 system 90 •7 10

Cu5V2O10 • 80 Cu V O 20 11 6 26 • Cu V O 3 2 8• • 70 30 • Cu V O • 2 2 7 • • • • • • 60 40

50 CuV O 50 CuFe O 2 6 • • 2 4 o• Lyonsite type phase 40 60 5 O Cu3Fe4V6O24 2 • 30 70 mol% V

20 80

10 90

• •• Fe•O V225O5 10 20 30 40 50 60 70 80 90 2 3 Fe2V4O13 FeVO4

mol% Fe2O3

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Table 2 Indexing results for the Cu13Fe4V10O44 powder diffraction pattern

No. dobs/nm dcalc/nm hklI/%

1 0.8916 0.8894 0 2 0 44 2 0.5724 0.5725 -121 8 3 0.5372 0.5366 2 2 0 9 4 0.4455 0.4453 2 0 1 14 5 0.4353 0.4350 3 1 0 6 6 0.3711 0.3710 2 4 0 16 7 0.3663 0.3660 -212 24 8 0.3542 0.3543 -241 16 9 0.3362 0.3363 -302 34

10 0.3227 0.3227 3 2 1 3 Fig. 2 SEM image of Cu13Fe4V10O44 11 0.3147 0.3147 2 4 1 13 12 0.3039 0.3041 -251 40 13 0.2967 0.2965 060100 14 0.2749 0.2750 -511 15 15 0.2692 0.2692 5 0 0 3 16 0.2658 0.2657 -521 10 17 0.2593 0.2594 -103 4 18 0.2483 0.2482 0 1 3 22 19 0.2467 0.2468 2 6 1 18 20 0.2439 0.2439 -522 24

21 0.2361 0.2361 -162 6 Transmittance 22 0.2298 0.2298 -333 8 23 0.2274 0.2275 1 2 3 12 24 0.2243 0.2243 6 0 0 7 25 0.2225 0.2224 4 6 0 35

Cu3Fe4V6O24. A mixture of the composition 66.67 mol% Cu5V2O10 and 33.33 mol% Cu3Fe4V6O24 was heated for 1000 800 600 400 two 20 h stages at 720 °C. The diffractogram of the sample –1 taken after the ﬁrst 20 h of heating showed only the set of Wavenumber/cm reﬂexes characteristic for the phase Cu13Fe4V10O44. Fig. 3 IR spectrum of Cu13Fe4V10O44 Therefore, the new phase was obtained in the solid–state reaction according to the equation: crystals are of the order of 20 lm, whereas the sizes of the smaller crystals do not often exceed 10 lm. The results of 2Cu5V2O10ðsÞ þ Cu3Fe4V6O24ðsÞ ¼ Cu13Fe4V10O44ðsÞ ð2Þ experimental determination of composition by EDX anal- Cu13Fe4V10O44 has a brown sort of colour, its density ysis of monophase sample showed that the Cu:Fe:V ratios 3 amounts to dobs = 3.97(5) g/cm . The powder diffracto- are near 13:4:10 (on average: 48.28 at% Cu, 13.97 at% Fe gram of the new phase was subjected to indexing, results of and 37.75 at% V) and correspond to the values from for- which are given in Table 2.Cu13Fe4V10O44 crystallizes in mula of the new compound, i.e.: 48.15 at% Cu, 14.81 at% the monoclinic system, its primitive unit cell parameters Fe and 37.04 at% V. are as follows: a = 1.3976(2) nm, b = 1.7788(3) nm, Figure 3 shows the IR spectrum of the new compound. c = 0.7810(1) nm, b = 105.65(2)°. The unit cell vol- In the light of information on the literature, the absorp- ume V = 1.8696 nm3; the number of stoichiometric units tion bands located in the wave number range of in the unit cell Z = 2; the XRD calculated density d = 1,050–600 cm-1 can be ascribed to the stretching vibra- 3 4.02 g/cm . tions of the V–O bonds in the VO4 and VO5 polyhedra A SEM image of Cu13Fe4V10O44 (Fig. 2) shows the [23–26]. They can be due to the stretching vibrations of presence of only one of crystals’ habit. Crystals of the new the Fe–O bonds in the FeO5 and FeO4 polyhedra, too compound are differentiated in size. The sizes of the larger [24, 26, 28]. The absorption bands recorded in the 123

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with separation of the second solid phase of melting point similar to that of Cu Fe V O . Because of the closeness 790 13 4 10 44 of temperatures of these two endothermic effects in the experiment conditions (‘‘freezing’’ at 780, 800 and 820 °C); no reliable assignment of the second product of melting of the new compound has been made. At this stage Endo of the study, it can be supposed that it is Cu5V2O10 with the melting point at 805 ± 5 °C. Studies aimed at resolving this question will be continued. 840

Conclusions 850 Reaction occurring in the solid state between oxides CuO,

V2O5 and Fe2O3, taken at a molar ratio 13:5:2, yielded new compound with the formula Cu13Fe4V10O44. This new 700 750 800 850 900 950 phase crystallizes in the monoclinic system, and its unit Temperature/°C cell parameters are as follows: a = 1.3976(2) nm,

Fig. 4 Fragment of DTA curve of Cu13Fe4V10O44 b = 1.7788(3) nm, c = 0.7810(1) nm, b = 105.65(2)°. Cu13Fe4V10O44 melts incongruently at 790 ± 5 °C. The new compound can be also obtained as a result of solid– -1 remaining wave number, i.e. 600–300 cm can be asso- state reaction between Cu5V2O10 and Cu3Fe4V6O24, taken ciated with stretching vibrations of the M–O bonds within at a molar ratio 2:1.

FeO6 and CuOx polyhedra as well as with bending vibrations of O–V–O bonds [24–28]. Open Access This article is distributed under the terms of the The DTA curve recorded for Cu Fe V O (Fig. 4) Creative Commons Attribution Noncommercial License which per- 13 4 10 44 mits any noncommercial use, distribution, and reproduction in any shows two endothermic effects beginning at temperatures medium, provided the original author(s) and source are credited. close to each other: at 790 ± 5 °C and about 800 °C, respectively. To establish the type of transformation causing these effects, three samples of Cu13Fe4V10O44 References compound were prepared. They were additionally heated for 2 h at different temperatures from the range 1. Hikazudani S, Kikutani K, Nagaoka K, Inoue T, Takita Y. 780–820 °C, and then rapidly cooled to room temperature, Anaerobic oxidation of isobutane I. Catalysis by Cu–V complex and then they were subjected to XRD study. The first oxides. Appl Catal A. 2008;345:65–72. 2. Ha¨ggblad R, Massa M, Andersson A. Stability and performance sample was heated at 780 °C (close to the beginning of the of supported Fe–V-oxide catalysts in methanol oxidation. J Catal. first endothermic effect), the second at 800 °C (just after 2009;266:218–27. the beginning of the effect), whilst the third sample was 3. Lafontaine MA, Grenećhe JM, Laligant T, Fe´rey G. b-Cu3Fe4(VO4)6: heated at 820 °C (at the temperature corresponding to a structural study and relationships; physical properties. J Solid State half of the height of the first endothermic effect). On Chem. 1994;108:1–10. 4. Wieczorek-Ciurowa K, Rakoczy J, Blonska-Tabero A, Filipek E, removal from the furnace, the samples heated at 800 or Niziol J, Dulian P. Mechanochemical synthesis of double vana- 820 °C were molten, whilst in the one heated at 780 °C, the date in Cu–Fe–V–O system and its physicochemical and catalytic liquid was not observed. The diffractogram of the sample properties. Catal Today. 2010. doi:10.1016/j.cattod.2010.12.007. heated at 780 °C did not differ from that of 5. Zolnierkiewicz G, Guskos N, Typek J, Anagnostakis EA, Blonska-Tabero A, Bosacka M. Competition of magnetic inter- Cu13Fe4V10O44. The diffractograms of the samples heated actions in M3Fe4V6O24 (M(II) = Zn, Cu, Mn, Mg) compounds at 800 and 820 °C were the same and did not show reflexes studied by EPR. J Alloys Compd. 2009;471:28–32. 6. Hughes JM, Starkey SJ, Malinconico ML, Malinconico LL. characteristic for Cu13Fe4V10O44. Thus, it was concluded Lyonsite, Cu2?Fe 3?(VO )3-, a new fumarolic sublimate from that the endothermic effect beginning at 790 ± 5 °Cis 3 4 4 6 Izalco volcano, El Salvador: descriptive mineralogy and crystal related to melting of the new compound and the process of structure. Am Mineral. 1987;72:1000–5. its melting was characterised as incongruent. The only 7. Hughes JM, Drexler JW, Campana CF, Malinconico ML. Ho- wardevansite, NaCu2?Fe 3?(VO )3-, a new fumarolic sublimate solid phase, occurring in the CuO–V2O5–Fe2O3 system, 2 4 3 identified in the samples after their melting, was a-Fe O from Izalco volcano, El Salvador: descriptive mineralogy and 2 3 crystal structure. Am Mineral. 1988;73:181–6. with a melting point above 1,000 °C. As indicated by the 8. Belik AA, Malakho AP, Pokholok KV, Lazoryak BI. Phase for- course of the DTA curve of the new compound, it melts mation in Cu3?1.5xR4-x(VO4)6 (R = Fe and Cr) systems: crystal 123

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