Studies on the power factor of (Ba,Sr)Co2+xRu4−xO11 compounds

[Abstract] We have prepared polycrystalline single-phase ACo2+xRu4−xO11 (A = Sr, Ba; 0 ≤ x ≤ 0.5) using the ceramic method and we have studied their structure, electrical resistivity and Seebeck coefficient, in order to estimate their power factor (P.F.). These layered compounds show values of electrical resistivity of the order of 10−5 Ωm and their Seebeck coefficients are positive and range from 1 μV K−1 (T = 100 K) to 20 μV K−1 (T = 450 K). The maximum power factor at room temperature is displayed by BaCo2Ru4O11 (P.F.: 0.20 μW K−2 cm−1), value that is comparable to that shown by compounds such as SrRuO3 and Sr6Co5O15.Ministerio de Ciencia e Innovación; Project FEDER MAT 2007-6669

Role of the metal cation in the dehydration of the microporous metal–organic frameworks CPO-27-M

The dehydration of the CPO-27-M (M-MOF-74, M = Zn, Co, Ni, Mg, Mn, Cu) metal-organic framework series has been investigated comprehensively using in situ variable temperature powder X-ray diffraction (VT-PXRD) and thermal analysis (TG) coupled with mass spectrometry (MS). Significant differences in the order of water desorption from different adsorption sites on heating are found with varying metal cation in the otherwise isostructural material. For all CPO-27-M (except M = Cu), water is bonded significantly more strongly to the accessible open metal sites, and these water molecules are only desorbed at higher temperatures than the other water molecules. CPO-27-Cu is an exception, where all water molecules desorb simultaneously and at much lower temperatures (below 340 K). MS and TG data show that all CPO-27-M start to release traces of CO2 already at 300–350 K, and thus long before bulk thermal decomposition is observed. Only for CPO-27-Co, the CO2 release is essentially constant on its baseline between 450 and 700 K, and it is the only CPO-27-M member that shows a stable plateau in the TG in this region. Additional rehydration studies on CPO-27-Co show that the MOF incorporates any water molecules present until the pores are fully loaded. CPO-27-Co consequently behaves as an efficient trap for any water present

Apparent colossal dielectric constants in nanoporous Metal Organic Frameworks

[Abstract] In this work, we show that the hybrid material Co2(1,4-bdc)2(dabco)•[4DMF•1H2O], shows an apparent colossal dielectric constant at room temperature (r5000 at 300 K for =100 Hz). Nevertheless, such response does not imply colossal polarizability processes, as its dielectric constant is not purely intrinsic, but is greatly enhanced by the activation of extrinsic dielectric effects close to room temperature associated to the diffusion of numerous guest molecules through the channels. If such extrinsic contributions are eliminated or reduced, the values of the dielectric constant turn to be much smaller, as observed in the closely related Co2(1,4-bdc-NH2)2(dabco)•[7/2DMF•1H2O], Co2(1,4-ndc)2(dabco) •[3DMF•2H2O] and Ni2(1,4-bdc)2(dabco)•[3DMF•1/2H2O] compounds. Therefore, we warn about the imperious necessity of distinguishing between intrinsic and extrinsic effects in electrically inhomogenous MOF materials that display a certain conductivity in order to adequately interpret their dielectric behaviorMinisterio de Economía y Competitividad; MAT2010-21342-C02-01Xunta de Galicia; PGIDIT10PXB103272P

Atypical magnetic behavior in the incommensurate [CH3NH3][Ni(HCOO)3][CH_3NH_3][Ni(HCOO)_3] hybrid perovskite

A plethora of temperature induced phase transitions have been observed in $[CH_3NH_3][M(HCOO)_3]$ compounds, where M is Co(II) or Ni(II). Among them, the nickel compound exhibits a combination of magnetic and nuclear incommensurabil-ity below N\'eel temperature. Despite the fact that the zero-field behavior has been previously addressed, here we study in depth the macroscopic magnetic behavior of this compound to unveil the origin of the atypical magnetic response found in it and in its parent family of formate perovskites. In particular, they show a puzzling magnetization reversal in the curves measured starting from low temperatures, after cooling under zero field. The first atypical phenomena is the im-possibility of reaching zero magnetization, even by nullifying the applied external field and even compensating it for the influence earth's magnetic field. Relatively large magnetic fields are needed to switch the magnetization from negative to positive values or vice versa, which is compatible with a soft-ferromagnetic system. The atypical path found in its first magnetization curve and hysteresis loop at low temperatures is the most noticeable feature. The magnetization curve switches from more than 1200 Oe from the first magnetization loop to the subsequent magnetization loops. A feature that cannot be explained using a model based on unbalanced pair of domains. As a result, we decipher this behavior in light of the incommensurate structure of this material. We propose, in particular, that the applied magnetic field induces a mag-netic phase transition from a magnetically incommensurate structure to a magnetically commensurate structure.Comment: 9 pages, 7 figures, 1 tabl

Atypical Magnetic Behavior in the Incommensurate (CH3NH3)[Ni(HCOO)3] Hybrid Perovskite

A plethora of temperature-induced phase transitions have been observed in (CH3NH3)[M(HCOO)3] compounds, where M is Co(II) or Ni(II). Among them, the nickel compound exhibits a combination of magnetic and nuclear incommensurability below Néel temperature. Despite the fact that the zero-field behavior has been previously addressed, here we study in depth the macroscopic magnetic behavior of this compound to unveil the origin of the atypical magnetic response found in it and in its parent family of formate perovskites. In particular, they show a puzzling magnetization reversal in the curves measured starting from low temperatures, after cooling under zero field. The first atypical phenomenon is the impossibility of reaching zero magnetization, even by nullifying the applied external field and even compensating it for the influence of the Earth’s magnetic field. Relatively large magnetic fields are needed to switch the magnetization from negative to positive values or vice versa, which is compatible with a soft ferromagnetic system. The atypical path found in its first magnetization curve and hysteresis loop at low temperatures is the most noticeable feature. The magnetization curve switches from more than 1200 Oe from the first magnetization loop to the subsequent magnetization loops. A feature that cannot be explained using a model based on unbalanced pair of domains. As a result, we decipher this behavior in light of the incommensurate structure of this material. We propose, in particular, that the applied magnetic field induces a magnetic phase transition from a magnetically incommensurate structure to a magnetically modulated collinear structureThe authors thank financial support from the Ministerio de Economía y Competitividad MINECO and EU-FEDER (projects MAT2017-86453-R and PDC 2021-121076-I00). The authors are grateful to Dra. Ana Arauzo at Servicio de Medidas Físicas of the Universidad de Zaragoza for heat capacity data. O.F. acknowledges the Spanish Ministry of Universities (UNI/551/2021) and the European Union through the Funds Next GenerationS

Coexistence of magnetic and electrical order in the new perovskite-like (C3N2H5)[Mn(HCOO)3] formate

This is the accepted manuscript of the following article: Pato-Doldán, B., Gómez-Aguirre, L., Bermúdez-García, J., Sánchez-Andújar, M., Fondado, A., & Mira, J. et al. (2013). Coexistence of magnetic and electrical order in the new perovskite-like (C3N2H5)[Mn(HCOO)3] formate. RSC Advances, 3(44), 22404. doi: 10.1039/c3ra43165gIn this work we further the structural characterization of the recently discovered (C3N2H5)[Mn(HCOO)3] metal–organic framework with perovskite-like structure, and we present its magnetic and dielectric properties up to 350 K. At low temperature, the C3N2H5+ imidazolium cations, that sit oblique within the cavities of the [Mn(HCOO)3]− framework structure, show a cooperative order resulting in an antiparallel arrangement of their electrical dipole moments. Very interestingly, it is only above 220 K that thermal energy seems to be able to break this antiferroelectric order, resulting in a linear increase of its dielectric constant with temperature. In addition, this Mn(II) compound is antiferromagnetic below TN = 9 K, with a slightly non-collinear arrangement of its magnetic moments, yielding to a weak ferromagnetism. Therefore, this is a new multiferroic material which exhibits coexistence of magnetic and electric orderingThe authors are grateful for financial support from Ministerio de Economía y Competitividad MINECO (Spain) under project FEDER MAT2010-21342-C02-01 and from Xunta de Galicia under project PGIDIT10PXB103272PR. B.P.-D. also wants to thank MICINN for a FPI fellowshipS

Magnetic transitions and isotropic versus anisotropic magnetic behaviour of [CH3NH3][M(HCOO)3] M = Mn2+, Co2+, Ni2+, Cu2+ metal–organic perovskites

Here we present an in-depth study of the magnetic properties of a family of metal–organic perovskites ABX3, [CH3NH3][M(HCOO)3] in which A = CH3NH3+ is the methylammonium cation, B = M is a divalent metal cation (Mn2+, Co2+, Ni2+ or Cu2+), and X is the formate anion (HCOO−). The magnetic properties have been measured on powdered samples and along the different orientations of mm-sized single crystals. They display spin-canted weak ferromagnetism with Néel temperatures of 8.0 K (Mn2+), 15.7 K (Co2+) and 34 K (Ni2+), which are inversely proportional to the ionic radii of the metal cations. The Cu2+ member displays low-dimensional magnetism as a result of orbital ordering of the Cu2+ d orbitals originating from a Jahn–Teller distortion. Pulsed-field magnetization experiments (fields of up to 60 T at temperatures down to 0.6 K) show that Mn2+, Co2+ and Ni2+ formates display cation-characteristic spin flop transitions. A saturation magnetization value of 5 μB (at 12.5 T) was observed for Mn2+, meanwhile the Co2+ formate shows an orientation dependent quasi saturation (5.1 μB at 21 T along [101] vs. 5.8 μB at 26 T along [010]). The different isotropic/anisotropic behaviour can be explained by the orbital contribution to the magnetic responseThe Spanish authors are grateful for financial support from Ministerio de Economía y Competitividad (MINECO) (Spain) and EU under the project ENE2014-56237-C4-4-R, and Xunta de Galicia under the project GRC2014/042. L. C. G.-A. acknowledges UDC for a predoctoral fellowship and Fundación Barrié for the research stay grant at LANL. Work at LANL, A. P. H. and B. P.-D.'s visit to LANL were funded by the Laboratory Directed Research and Development program at LANL. The NHMFL pulsed-field facility is funded by the U.S. National Science Foundation through Cooperative Grant No. DMR-1157490, the State of Florida, and the U.S. Department of EnergyS

Geometric Frustration on the Trillium Lattice in a Magnetic Metal-Organic Framework

In the dense metal-organic framework Na[Mn(HCOO)3], Mn2+ ions (S = $5\over2$) occupy the nodes of a ‘trillium’ net. We show that the system is strongly magnetically frustrated: the Neel transition is suppressed well ´ below the characteristic magnetic interaction strength; short-range magnetic order persists far above the Neel ´ temperature; and the magnetic susceptibility exhibits a pseudo-plateau at $1\over3$-saturation magnetisation. A simple model of nearest-neighbour Heisenberg antiferromagnetic and dipolar interactions accounts quantitatively for all observations, including an unusual 2-k magnetic ground-state. We show that the relative strength of dipolar interactions is crucial to selecting this particular ground-state. Geometric frustration within the classical spin liquid regime gives rise to a large magnetocaloric response at low applied fields that is degraded in powder samples as a consequence of the anisotropy of dipolar interactions

Búsqueda de nuevos materiales termoeléctricos, dieléctricos y multiferroicos basados en óxidos mixtos y en híbridos orgánicos-inorgánicos

[Resumen] Esta tesis doctoral tiene por objetivo el desarrollo de nuevos materiales, basados en óxidos mixtos o en híbridos orgánicos-inorgánicos, que presenten propiedades termoeléctricas, dieléctricas y magnéticas que permitan su uso en diversos dispositivos funcionales. En la primera parte describimos la preparación de los compuestos ACo2+xRu4-xO11 (A = Ba+2, Sr+2; 0=x=0.5), su estructura y sus propiedades termoeléctricas. Estos compuestos muestran valores de resistividad eléctrica en torno a los 10-5 Om, y su coeficiente Seebeck varía desde 1 µVK-1 (T = 100 K) a 20 VK-1 (T = 450 K). El compuesto BaCo2Ru4O11 presenta el mayor valor del factor de potencia a 300 K (0.20 µWK-2cm-1). En la segunda parte estudiamos la estructura y las propiedades dieléctricas y magnéticas de la familia de compuestos con fórmula [AminaH][M(HCOO)3]. De los resultados obtenidos, tenemos que destacar que describimos por primera vez la transición estructural y dieléctrica del compuesto [(CH3)2NH2][Mg(HCOO)3] (T ~ 270 K), muy próxima a temperatura ambiente, lo cual es muy interesante por sus posibles aplicaciones prácticas; profundizamos en el estudio de la relación entre la estructura y las propiedades dieléctricas y magnéticas de la familia de compuestos [(CH3)2NH2][M(HCOO)3 (M= Fe2+, Ni2+, Zn2+, Cu2+ y Cd2+); por último, preparamos por primera vez el compuesto (C3N2H5)[Mn(HCOO)3], en el que coexisten dipolos dieléctricos y magnéticos ordenados, y que por lo tanto es multiferroico.[Resumo] Esta tese doutoral ten por obxectivo o desenvolvemento de novos materiais, baseados en óxidos mixtos ou en híbridos orgánicos-inorgánicos, que presenten propiedades termoeléctricas, dieléctricas e magnéticas que permitan a súa utilización en diversos dispositivos funcionais. Na primeira parte describimos a preparación dos compostos ACo2+xRu4- xO11 (A = Ba+2, Sr+2; 0=x=0.5), a súa estrutura e as súas propiedades termoeléctricas. Estes compostos mostran valores de resistividade eléctrica en torno aos 10-5 Om, e o seu coeficiente Seebeck varía dende 1 µVK-1 (T = 100 K) ata 20 VK-1 (T = 450 K). O composto BaCo2Ru4O11 presenta o maior valor do factor de potencia a 300 K (0.20 µWK-2cm-1). Na segunda parte estudamos a estrutura e as propiedades dieléctricas e magnéticas da familia de compostos con fórmula [AminaH][M(HCOO)3]. Dos resultados obtidos temos que destacar que describimos por primeira vez a transición estrutural e dieléctrica do composto [(CH3)2NH2][Mg(HCOO)3] (T~270 K), moi próxima a temperatura ambiente, o cal é moi interesante polas súas posibles aplicacións prácticas; afondamos no estudo das propiedades dieléctricas e magnéticas da familia de compostos [(CH3)2NH2][M(HCOO)3], (M= Fe2+, Ni2+, Zn2+, Cu2+ y Cd2+); por último, preparamos o composto (C3N2H5)[Mn(HCOO)3] no que coexisten dipolos dieléctricos e magnéticos ordenados, e que polo tanto é multiferroico.[Abstract] This doctoral thesis has as objective the development of new materials, based on mixed oxides or in organic-inorganic hybrids, which show thermoelectric, dielectric and magnetic properties that allow their use in diverse functional devices. In its first part we describe the preparation of the compounds ACo2+xRu4-xO11 (A = Ba+2, Sr+2; 0=x=0.5), their structure and their thermoelectric properties. These compounds show an electrical resistivity around the 10-5 Om, and their Seebeck coefficient varies from 1 µVK-1 (T = 100 K) to 20 VK-1 (T = 450 K). The compound BaCo2Ru4O11 has the higher power factor at 300 K (0.20 µWK-2cm-1). In its second part we study the structure and the dielectric and magnetic properties of the family of compounds whose formula is [AmineH][M(HCOO)3]. We should highlight among the results obtained that we have described for the first time the structural and dielectric transition of the compound [(CH3)2NH2][Mg(HCOO)3] (T ~ 270 K), really close to room temperature, which is very interesting due to their feasible practical applications; we have deepened in the study of the relation between structure and dielectric and magnetic properties of the compounds [(CH3)2NH2][M(HCOO)3] (M= Fe2+, Ni2+, Zn2+, Cu2+ and Cd2+); finally, we have prepared for the first time the compound (C3N2H5)[Mn(HCOO)3], which shows coexistence of ordered electric and magnetic dipoles, and so it is multiferroic

Role of the metal cation in the dehydration of the microporous metal–organic frameworks CPO-27-M

The dehydration of the CPO-27-M (M-MOF-74, M = Zn, Co, Ni, Mg, Mn, Cu) metal-organic framework series has been investigated comprehensively using in situ variable temperature powder X-ray diffraction (VT-PXRD) and thermal analysis (TG) coupled with mass spectrometry (MS). Significant differences in the order of water desorption from different adsorption sites on heating are found with varying metal cation in the otherwise isostructural material. For all CPO-27-M (except M = Cu), water is bonded significantly more strongly to the accessible open metal sites, and these water molecules are only desorbed at higher temperatures than the other water molecules. CPO-27-Cu is an exception, where all water molecules desorb simultaneously and at much lower temperatures (below 340 K). MS and TG data show that all CPO-27-M start to release traces of CO2 already at 300–350 K, and thus long before bulk thermal decomposition is observed. Only for CPO-27-Co, the CO2 release is essentially constant on its baseline between 450 and 700 K, and it is the only CPO-27-M member that shows a stable plateau in the TG in this region. Additional rehydration studies on CPO-27-Co show that the MOF incorporates any water molecules present until the pores are fully loaded. CPO-27-Co consequently behaves as an efficient trap for any water present