Effect of sintering under CO+N2/H2 and CO2+air atmospheres on the physicochemical features of a commercial nano-YSZ

Given the need to process anodes and composites based on nano-YSZ in reducing or in air containing additional CO2 atmospheres for the fabrication of solid oxide fuel cells (SOFCs), and solid oxide electrolysis cells (SOECs), we have studied the effect of the exposure to CO+N2/H2 or CO2+air mixtures during sintering of YSZ green pellets, prepared from commercial nanopowders, on their structure, microstructure, chemical composition and their electrical properties. The reduced sample shows Raman bands at 1298 and 1605 cm−1 that are assigned to the D and G bands of carbon, respectively. The bands intensity ratio ID/IG indicates a larger content of disordered carbon. X-ray photoelectron spectroscopy (XPS) shows that C is present in the reduced samples as reduced carbon. However, the samples sintered in CO2+air present C as carbonate-type. Impedance spectroscopy reveals that the highest total conductivity is for the reduced samples in the whole range of studied temperatures. In addition, sintering in CO2+air causes a detrimental effect on the grain boundary conductivity and therefore, on the total electrical conductivity of YSZ. It can be due to the presence of impurities such as carbonates and oxidised or even, polymerised carbonaceous species located at those areas.España Ministerio de Ciencia e Innovación and cofinanced with FEDER Funds under the Grant PID2019-104118RB-C2

NMR and Raman Scattering Studies of Temperature- and Pressure-Driven Phase Transitions in CH3NH2NH2PbCl3 Perovskite

Three-dimensional methylhydrazinium (CH3NH2NH2+, MHy+) lead halides, related to the famous methylammonium (CH3NH3+, MA+) and formamidinium (CH(NH2)2+, FA) perovskites, are attractive optoelectronic materials crystallizing in polar structures. In this work, temperature-dependent 1H and 207Pb magic-angle spinning (MAS) NMR, Raman as well as high-pressure Raman studies of CH3NH2NH2PbCl3 (MHyPbCl3) are reported. Raman spectroscopy reveals many similarities between phonon properties of MHy lead halides and the MA and FA analogues. In particular, these families of compounds show an increase in wavenumber of cage modes when large I- ions are replaced by smaller Br- and then Cl- ones. They also show strong sensitivity of the CH3 torsional mode on size of the cavity occupied by MHy+ cation that decreases with decreasing size of the halide anion. The cage modes of MHyPbCl3 are, however, observed at significantly lower wavenumbers than similar modes of MAPbCl3 and FAPbCl3, indicating higher softness of MHyPbCl3. Temperature-dependent Raman and NMR studies demonstrate that the MHy+ cations in MHyPbCl3 are significantly less affected by the temperature-induced phase transition than the Pb-Cl framework. This suggests a displacive type of the phase transition dominated by tilting and deformation of the PbCl6 octahedra. Analysis of the 207Pb MAS NMR spectra reveals the presence of two differently distorted PbCl6 octahedra and diminishing (increasing) distortion of the less (more) distorted octahedra in the high-temperature phase. Pressure-dependent Raman studies reveal the presence of a single first-order pressure-induced phase transition between 0.72 and 1.27 GPa. Analysis of the spectra indicates that the driving forces for the pressure-induced phase transition in MHyPbCl3 are tilting and distortion of the PbCl6 octahedra accompanied by reorientation of MHy+ cations. Raman spectra do not show evidence of any additional phase transition or amorphization up to 6.95 GPa

Electron paramagnetic resonance study of ferroelectric phase transition and dynamic effects in a Mn²⁺ doped [NH₄][Zn(HCOO)₃] hybrid formate framework

We present an X- and Q-band continuous wave (CW) and pulse electron paramagnetic resonance (EPR) study of a manganese doped [NH4][Zn(HCOO)3] hybrid framework, which exhibits a ferroelectric structural phase transition at 190 K. The CW EPR spectra obtained at different temperatures exhibit clear changes at the phase transition temperature. This suggests a successful substitution of the Zn2+ ions by the paramagnetic Mn2+ centers, which is further confirmed by the pulse EPR and 1H ENDOR experiments. Spectral simulations of the CW EPR spectra are used to obtain the temperature dependence of the Mn2+ zero-field splitting, which indicates a gradual deformation of the MnO6 octahedra indicating a continuous character of the transition. The determined data allow us to extract the critical exponent of the order parameter (β = 0.12), which suggests a quasi two-dimensional ordering in [NH4][Zn(HCOO)3]. The experimental EPR results are supported by the density functional theory calculations of the zero-field splitting parameters. Relaxation time measurements of the Mn2+ centers indicate that the longitudinal relaxation is mainly driven by the optical phonons, which correspond to the vibrations of the metal–oxygen octahedra. The temperature behavior of the transverse relaxation indicates a dynamic process in the ordered ferroelectric phase

Self-assembly of 5,6-dihydroxyindole-2-carboxylic acid: Polymorphism of a eumelanin building block on Au(111)

Investigating two-dimensional (2D) self-assembled structures of biological monomers governed by intermolecular interactions is a prerequisite to understand the self-assembly of more complex biomolecular systems. 5,6-Dihydroxyindole carboxylic acid (DHICA) is one of the building blocks of eumelanin-an irregular heteropolymer and the most common form of melanin which has potential applications in organic electronics and bioelectronics. By means of scanning tunneling microscopy, density functional theory and Monte Carlo calculations, we investigate DHICA molecular configurations and interactions underlying the multiple 2D patterns formed on Au(111). While DHICA self-assembled molecular networks (SAMNs) are dominated by the hydrogen bonding of carboxylic acid dimers, a variety of 2D architectures are formed due to the multiple weak interactions of the catechol group. The hydroxyl group also allows for redox reactions, caused by oxidation via O 2 exposure, resulting in molecular rearrangement. The susceptibility of the molecules to oxidation is affected by their SAMNs architectures, giving insights on the reactivity of indoles as well as highlighting non-covalent assembly as an approach to guide selective oxidation reactions

Functional basis of electron transport within photosynthetic complex I

Photosynthesis and respiration rely upon a proton gradient to produce ATP. In photosynthesis, the Respiratory Complex I homologue, Photosynthetic Complex I (PS-CI) is proposed to couple ferredoxin oxidation and plastoquinone reduction to proton pumping across thylakoid membranes. However, little is known about the PS-CI molecular mechanism and attempts to understand its function have previously been frustrated by its large size and high lability. Here, we overcome these challenges by pushing the limits in sample size and spectroscopic sensitivity, to determine arguably the most important property of any electron transport enzyme – the reduction potentials of its cofactors, in this case the iron-sulphur clusters of PS-CI (N0, N1 and N2), and unambiguously assign them to the structure using double electron-electron resonance. We have thus determined the bioenergetics of the electron transfer relay and provide insight into the mechanism of PS-CI, laying the foundations for understanding of how this important bioenergetic complex functions

Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles

Functional basis of electron transport within photosynthetic complex I

Photosynthesis and respiration rely upon a proton gradient to produce ATP. In photosynthesis, the Respiratory Complex I homologue, Photosynthetic Complex I (PS-CI) is proposed to couple ferredoxin oxidation and plastoquinone reduction to proton pumping across thylakoid membranes. However, little is known about the PS-CI molecular mechanism and attempts to understand its function have previously been frustrated by its large size and high lability. Here, we overcome these challenges by pushing the limits in sample size and spectroscopic sensitivity, to determine arguably the most important property of any electron transport enzyme – the reduction potentials of its cofactors, in this case the iron-sulphur clusters of PS-CI (N0, N1 and N2), and unambiguously assign them to the structure using double electron-electron resonance. We have thus determined the bioenergetics of the electron transfer relay and provide insight into the mechanism of PS-CI, laying the foundations for understanding of how this important bioenergetic complex functions

Effect of sintering under CO+N2/H2 and CO2+air atmospheres on the physicochemical features of a commercial nano-YSZ

Given the need to process anodes and composites based on nano-YSZ in reducing or in air containing additional CO2 atmospheres for the fabrication of solid oxide fuel cells (SOFCs), and solid oxide electrolysis cells (SOECs), we have studied the effect of the exposure to CO+N2/H2 or CO2+air mixtures during sintering of YSZ green pellets, prepared from commercial nanopowders, on their structure, microstructure, chemical composition and their electrical properties. The reduced sample shows Raman bands at 1298 and 1605 cm−1 that are assigned to the D and G bands of carbon, respectively. The bands intensity ratio ID/IG indicates a larger content of disordered carbon. X-ray photoelectron spectroscopy (XPS) shows that C is present in the reduced samples as reduced carbon. However, the samples sintered in CO2+air present C as carbonate-type. Impedance spectroscopy reveals that the highest total conductivity is for the reduced samples in the whole range of studied temperatures. In addition, sintering in CO2+air causes a detrimental effect on the grain boundary conductivity and therefore, on the total electrical conductivity of YSZ. It can be due to the presence of impurities such as carbonates and oxidised or even, polymerised carbonaceous species located at those areas.This work was partially supported by the Science and Innovation Ministry (Government of Spain) and cofinanced with FEDER Funds under the Grant PID2019-104118RB-C21. The authors acknowledge to Dr. D.G. Calatayud for his help in the analysis of the distributions of the average of grain sizes for the sintered samples. In addition, the authors are also grateful to Mrs. C. Díaz-Dorado for her help in the preparation of FEG-SEM and TEM figures. We also acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).Peer reviewe

Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles