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The effect of high pressure on the structure of orthorhombic Mn3(VO4)2 is investigated using in situ Raman spectroscopy and X-ray powder diffraction up to high pressures of 26.2 and 23.4 GPa, respectively. The study demonstrates a pressure-induced structural phase transition starting at 10 GPa, with the coexistence of phases in the range of 10–20 G...
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... Properties at Ambient Conditions. The crystal structure of A 3 (VO 4 ) 2 in the orthorhombic Cmca space group is depicted in Figure 1, which contains AO 6 octahedra and VO 4 tetrahedra in which each octahedron shares its edge with the three adjacent octahedra and forms layers perpendicular to the [010] direction, and these layers are interconnected by isolated VO 4 tetrahedral units. 17 The unit cell contains two formula units in which the A-atoms reside at two crystallographically distinct (A1 at 4a, A2 at 8e) Wyckoff sites, while the vanadium atoms reside at the 8f site and the oxygen atoms reside at 8f and 16g sites. ...
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... modes below 200 cm −1 are rigid motions of VO 4 tetrahedra and A−O 6 octahedra. Major Raman modes of lt-Mn 3 (VO 4 ) 2 are assigned in accordance with our earlier polarized Raman studies on Ni 3 (VO 4 ) 2 , 28 and, accordingly, the V−O symmetric stretching modes (A gsymmetry) in lt-Mn 3 (VO 4 ) 2 are at 645, 811, and 793 cm −1 in the high-frequency region due to the symmetric stretching of short and long V−O bonds (all three bond lengths are given in Figure 1 taken from the literature 12,14 ). The asymmetries in the Raman spectra at around 686 and 783 cm −1 are the asymmetric V−O stretching modes (B g -symmetry). ...
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... variation of lattice parameters and the unit cell volume with pressure obtained by refinement of X-ray diffraction data for lt-Mn 3 (VO 4 ) 2 is shown in Figure 10a Table 3 for easier comparison) 17,18 where the authors predicted that the anisotropic behavior could be due to the nature of the Kagomeíayered crystal structure. The obtained value of ambient pressure bulk modulus and the pressure derivative of bulk modulus are 116(2) GPa and 2.6(5), respectively. ...
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We report successful coupling of dynamic loading in a diamond anvil cell and stable laser heating, which enables compression rates up to 500 GPa/s along high-temperature isotherms. Dynamic loading in a diamond-anvil cell allows exploration of a wider range of pathways in the pressure-temperature space compared to conventional dynamic compression te...
Citations
... Also, in the same literature [11], they have reported the high pressure behavior of Co 3 (VO 4 ) 2 up to 20 GPa which shows stable orthorhombic structure [11]. Since Co 3 (VO 4 ) 2 belongs to the orthovanadates of family A 3 (VO 4 ) 2 in which most of the orthorhombic members show stable structure at high pressure (for A = Ni, Zn, Mg, Co) [11,[24][25][26], except for orthorhombic Mn 3 (VO 4 ) 2 which transforms to a new recoverable structure under high pressure [27]. The non-orthorhombic members of this family show interesting structural changes; for example-rhombohedral Sr 3 (VO 4 ) 2 shows pressure induced structural transition [28,29], rhombohedral Ca 3 (VO 4 ) 2 shows pressure induced amorphization and/or new structure [30,31], Li 0.2 Mn 2.9 (VO 4 ) 2 shows pressure induced new recoverable phase [32], and triclinic Cu 3 (VO 4 ) 2 shows pressure induced decomposition [33]. ...
... The non-orthorhombic members of this family show interesting structural changes; for example-rhombohedral Sr 3 (VO 4 ) 2 shows pressure induced structural transition [28,29], rhombohedral Ca 3 (VO 4 ) 2 shows pressure induced amorphization and/or new structure [30,31], Li 0.2 Mn 2.9 (VO 4 ) 2 shows pressure induced new recoverable phase [32], and triclinic Cu 3 (VO 4 ) 2 shows pressure induced decomposition [33]. Raman spectroscopy is a non-destructive technique which can detect nucleation of new phases at different thermodynamical conditions; for example-high pressure Raman spectroscopic investigation is carried out in Ni 3 (VO 4 ) 2 , Co 3 (VO 4 ) 2 , Mg 3 (VO 4 ) 2 , Sr 3 (VO 4 ) 2 , Ba 3 (VO 4 ) 2 , Ca 3 (VO 4 ) 2 , lt-Mn 3 (VO 4 ) 2 and Li 0.2 Mn 2.9 (VO 4 ) 2 and anomalies observed in their respective Raman modes; were later correlated with structural phase transition/stability using high pressure X-ray diffraction investigations [11,[26][27][28][29][30]. At present, no report exists for the high temperature vibrational behavior of Co 3 (VO 4 ) 2 which can be used to study anharmonicities of these Raman active modes. ...
... The highest intensity mode at 814 cm − 1 in Co 3 (VO 4 ) 2 moves towards high frequency side with a slope of 1.97 cm − 1 /GPa which was earlier reported to be 3 cm − 1 /GPa [11]. The pressure dependencies of the frequency of the highest intensity mode in the orthorhombic members Mg 3 (VO 4 ) 2 , Mn 3 (VO 4 ) 2 , Ni 3 (VO 4 ) 2 and Co 3 (VO 4 ) 2 (at 864, 811, 826 and 814 cm − 1 respectively) varies as 3.7, 2.8, 2.6 and 2.0 cm − 1 /GPa respectively [11,26,27] and their isothermal mode Grüneisen parameters varies as 0.6, 0.4, 0.4 and 0.3 respectively indicating similar pressure effect on the VO 4 tetrahedra among these members although the VO 4 tetrahedral distortion indices of these compounds as indicated in Ref. [26] varies as 7.04, 6.64, 6.98 and 6.92 (×10 − 4 respectively). In this family, octahedral distortion is lowest in Ni 3 (VO 4 ) 2 and Co 3 (VO 4 ) 2 . ...
Polarized Raman spectroscopic investigation on oriented single crystal of orthovanadate Co3(VO4)2 is carried out. We have observed and identified symmetries of 32 out of 36 expected Raman active modes of Co3(VO4)2 in different polarization directions. Evolution of frequencies of observed Raman active modes in Co3(VO4)2 are also investigated under variable thermodynamical conditions. The isothermal high pressure Raman spectroscopic investigation indicates stable orthorhombic (Cmca) structure up to 15.7 GPa consistent with reported literature. The isobaric high temperature Raman spectroscopic investigation up to 823 K is used to estimate the total anharmonicity of all the observed Raman active modes. Evolution of Raman spectra indicates structural stability in the temperature and pressure range investigated. By a combination of high pressure and temperature dependent Raman spectroscopic data, the analysis of anharmonicity of observed Raman modes are calculated. Our measurements indicate dominant contribution of three phonon decay process for almost all the observed Raman active modes in Co3(VO4)2. The anharmonicity information along with symmetry of these observed modes can be used as an input in the analysis of expected spin-phonon anomalies around the magnetic transition in Co3(VO4)2 in future investigations.
... X-ray diffraction (XRD) and Raman methods were used to study Mn 3 V 2 O 8 in its orthorhombic low-temperature structure; an irreversible phase transition at 10 GPa was discovered, but the new phase has not been identified yet. 21 In contrast, it has been demonstrated that Zn, Ni, and Mg orthovanadates are stable up to 15, 22 23, 23 and 25.7 GPa, 24 respectively. With different structures but the same stoichiometry, Ca and Sr orthovanadates were found to undergo different phase transitions at 9.7(1) GPa 25 and 13.8 GPa, 26 respectively. ...
... We also present the first HP XRD analyses of Co 3 V 2 O 8 . As it is situated in the periodic table between Mn (which undergoes a phase transition at 10 GPa 21 ) and Ni (which remains stable up to 23 GPa 23 ), it is of great interest to find out what structural changes occur under pressure. The experimental data are also supported by the corresponding DFT calculations. ...
... This fact agrees with the observations reported in the HP Raman section (3.4), where it was concluded that Ni 3 V 2 O 8 behaves as a pressurized version of Co 3 V 2 O 8 . Overall, Ni and Co vanadates show bulk moduli within the range of all other Kagome-staircase orthovanadates, with Mg 3 V 2 O 8 being the highest (152(4) GPa) 23 and Mn 3 V 2 O 8 , the lowest (106(3) GPa) 21 to date. ...
The vibrational and structural behaviors of Ni3V2O8 and Co3V2O8 orthovanadates have been studied up to around 20 GPa by means of X-ray diffraction, Raman spectra, and theoretical simulations. Both materials crystallize in an orthorhombic Kagomeś taircase structure (space group: Cmca) at ambient conditions, and no phase transition was found in the whole pressure range. In order to identify the symmetry of the detected Raman-active modes under high pressure, single crystal samples of those materials were used in a polarized Raman and infrared setup. Moreover, high-pressure powder X-ray diffraction measurements were performed for Co3V2O8 , and the results confirmed the structure stability also obtained by other diagnostic techniques. From this XRD analysis, the anisotropic compressibilities of all axes were calculated and the unit-cell volume vs pressure was fitted by a Birch−Murnaghan equation of state, obtaining a bulk modulus of 122 GPa.
... The compound Cu 3 (VO 4 ) 2 exists in triclinic phase (P-1) at ambient conditions and has two high temperature polymorphs, of which one is orthorhombic Cmca phase and the other is a monoclinic phase (P2 1 /C) [15]. In literature, only three members (A = Zn, Ni and Mn) of orthorhombic A 3 (VO 4 ) 2 family have been studied under high pressure experimentally [16][17][18]. Both Zn 3 (VO 4 ) 2 and Ni 3 (VO 4 ) 2 are reported to be stable up to the highest pressure of 15 and 23 GPa respectively [16,17], while our investigation on Mn 3 (VO 4 ) 2 (referred as lt-Mn 3 (VO 4 ) 2 ) indicated an irreversible structural phase transition; where the two phases coexisted in the range 10-20 GPa [18]. ...
... In literature, only three members (A = Zn, Ni and Mn) of orthorhombic A 3 (VO 4 ) 2 family have been studied under high pressure experimentally [16][17][18]. Both Zn 3 (VO 4 ) 2 and Ni 3 (VO 4 ) 2 are reported to be stable up to the highest pressure of 15 and 23 GPa respectively [16,17], while our investigation on Mn 3 (VO 4 ) 2 (referred as lt-Mn 3 (VO 4 ) 2 ) indicated an irreversible structural phase transition; where the two phases coexisted in the range 10-20 GPa [18]. We speculated that this observation could be due to lower octahedral distortion of Zn 3 (VO 4 ) 2 and Ni 3 (VO 4 ) 2 in the ambient structure compared to Mn 3 (VO 4 ) 2 [18]. ...
... Both Zn 3 (VO 4 ) 2 and Ni 3 (VO 4 ) 2 are reported to be stable up to the highest pressure of 15 and 23 GPa respectively [16,17], while our investigation on Mn 3 (VO 4 ) 2 (referred as lt-Mn 3 (VO 4 ) 2 ) indicated an irreversible structural phase transition; where the two phases coexisted in the range 10-20 GPa [18]. We speculated that this observation could be due to lower octahedral distortion of Zn 3 (VO 4 ) 2 and Ni 3 (VO 4 ) 2 in the ambient structure compared to Mn 3 (VO 4 ) 2 [18]. Our interest is to substantiate this speculation with study of other compounds of this family under high pressures. ...
... 19 According to the results summarized above, the HP behavior of Ca 3 V 2 O 8 is different from that of other orthovanadates with equivalent chemical formulae. For instance, Zn 3 V 2 O 8 , Ni 3 V 2 O 8 , and Ba 3 V 2 O 8 remain stable up to at least 15, 20 23 21 and 29 GPa 22 respectively. Mn 3 V 2 O 8 and Sr 3 V 2 O 8 exhibit pressureinduced phase transitions around 10 GPa 23 and 13.8 GPa 22,24 respectively, and Cu 3 V 2 O 8 chemically decomposes at 1.35 GPa. 25 Such different results from various HP studies in the M 3 V 2 O 8 family, and the apparent contradictions between different HT studies, clearly show that further investigation into the pressure and temperature evolution of the Ca 3 V 2 O 8 is needed to understand its structural behavior under extreme conditions of pressure and temperature. ...
We present a comprehensive experimental study of the crystal structure of calcium vanadate (Ca3V2O8) under systematic temperature and pressure conditions. The temperature evolution (4 – 1173 K) of the Ca3V2O8...
... From the fundamental point of view, the high-pressure (HP) behavior of M 3 V 2 O 8 vanadates has also been the focus of recent studies [14][15][16]. X-ray diffraction experiments have shown that Zn 3 V 2 O 8 [14] and Ni 3 V 2 O 8 [15] remain stable in the low-pressure phase up to 15 GPa. In Mn 3 V 2 O 8 [16], the onset of a structural phase transition has been located beyond 10 GPa. ...
... X-ray diffraction experiments have shown that Zn 3 V 2 O 8 [14] and Ni 3 V 2 O 8 [15] remain stable in the low-pressure phase up to 15 GPa. In Mn 3 V 2 O 8 [16], the onset of a structural phase transition has been located beyond 10 GPa. On the other hand, the bulk moduli of M 3 V 2 O 8 vanadates have been determined to cover a range of values from 100 GPa to 140 GPa. ...
... In Figure 6, we plot our calculated K 0 versus Z/d 3 . In the figure, we also include available experimental results [15,16]. Results from Cu 3 V 2 O 8 have been excluded, because it has a very different crystal structure where part of the Cu atoms are in highly unusual square-planar geometry [48]. ...
We report herein a theoretical study of the high-pressure compressibility of Cd3V2O8, Zn3V2O8, Mg3V2O8, and Ni3V2O8. For Cd3V2O8, we also present a study of its structural stability. Computer simulations were performed by means of first-principles methods using the CRYSTAL program. In Cd3V2O8, we found a previously unreported polymorph which is thermodynamically more stable than the already known polymorph. We also determined the compressibility of all compounds and evaluated the different contributions of polyhedral units to compressibility. We found that the studied vanadates have an anisotropic response to compression and that the change in volume is basically determined by the compressibility of the divalent-cation coordination polyhedra. A systematic discussion of the bulk modulus of M3V2O8 orthovanadates will also be included.
In this work, new strategies were developed to prepare 1D-V2MoO8 (VMO) rods from 2D V-doped MoSe2 nanosheets (VMoSe2) with good control over morphology and crystallinity by a facile hydrothermal and calcination process. The morphological changes from 2D to 1D rods were controlled by changing the calcination temperature from 300 to 600 °C. The elimination of Se and the incorporation of O into the V-Mo structure were evaluated by TGA, p-XRD, Raman, FE-SEM, EDAX, FE-TEM, and XPS analyses. These results prove that the optimization of the physical parameters leads to changes in the crystal phase and textural properties of the prepared material. The VMoSe2 and its calcined products were investigated as electrochemical sensors for the detection of the antibacterial drug nitrofurantoin (NFT). At a calcination temperature of 500 oC, the modified SPCE proved to be an excellent electrochemical sensor for the detection of NFT in neutral media. Under the optimized conditions, VMO-500 oC/SPCE exhibits low LOD (0.015 µM), wide linear ranges (0.1-31, 47-1802 µM), good sensitivity, and selectivity. The proposed sensor was successfully used for the analysis of NFT in real samples with good recovery results. Moreover, the reduction potential of NFT agreed well with the theoretical analysis using quantum chemical calculations, with the B3LYP with 6-31G(d,p) basis set predicting an E0 value of -0.45 V. The interaction between the electrode surface and NFT via the LUMO diagram and the electrostatic potential surface is also discussed.
