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The CaFe 0.1 Mn 0.9 O 3−δ0 oxide can reversibly release oxygen over a relatively wide range of temperatures and oxygen partial pressures and its favourable thermodynamic properties make it a promising candidate for thermochemical heat storage.
Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO 2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H 2 and CO) and Hythane (H 2 and CH 4 ) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. Finally, we show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C 2 H 4 have high profitability indices.
In the fast-evolving field of halide perovskite semiconductors, the 2D perovskites (A') 2 (A) n -1 M n X 3 n +1 [where A = Cs + , CH 3 NH 3 + , HC(NH 2 ) 2 + ; A' = ammonium cation acting as spacer; M = Ge 2+ , Sn 2+ , Pb 2+ ; and X = Cl - , Br - , I - ] have recently made a critical entry. The n value defines the thickness of the 2D layers, which controls the optical and electronic properties. The 2D perovskites have demonstrated preliminary optoelectronic device lifetime superior to their 3D counterparts. They have also attracted fundamental interest as solution-processed quantum wells with structural and physical properties tunable via chemical composition, notably by the n value defining the perovskite layer thickness. The higher members ( n > 5) have not been documented, and there are important scientific questions underlying fundamental limits for n . To develop and utilize these materials in technology, it is imperative to understand their thermodynamic stability, fundamental synthetic limitations, and the derived structure–function relationships. We report the effective synthesis of the highest iodide n -members yet, namely (CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 5 Pb 6 I 19 ( n = 6) and (CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 6 Pb 7 I 22 ( n = 7), and confirm the crystal structure with single-crystal X-ray diffraction, and provide indirect evidence for “(CH 3 (CH 2 ) 2 NH 3 ) 2 (CH 3 NH 3 ) 8 Pb 9 I 28 ” (“ n = 9”). Direct HCl solution calorimetric measurements show the compounds with n > 7 have unfavorable enthalpies of formation (Δ H f ), suggesting the formation of higher homologs to be challenging. Finally, we report preliminary n -dependent solar cell efficiency in the range of 9–12.6% in these higher n -members, highlighting the strong promise of these materials for high-performance devices.
Liquid polymorphism is an intriguing phenomenon which has been found in a few single-component systems, the most famous being water. By supercooling liquid Te to more than 130 K below its melting point and performing simultaneous small-angle and wide-angle X-ray scattering measurements, we observe clear maxima in its thermodynamic response functions around 615 K, suggesting the possible existence of liquid polymorphism. A close look at the underlying structural evolution shows the development of intermediate-range order upon cooling, most strongly around the thermodynamic maxima, which we attribute to bond-orientational ordering. The striking similarities between our results and those of water, despite the lack of hydrogen-bonding and tetrahedrality in tellurium, indicate that water-like anomalies may be a general phenomenon among liquid systems with competing bond- and density-ordering.
Hitting the limits on propene synthesis The greater abundance of propane from shale gas has spurred efforts to use it as a propylene feedstock. Direct dehydrogenation catalysts consisting of platinum–tin alloy nanoparticles supported on alumina often must run with hydrogen dilution to avoid carbon buildup and excess tin to avoid alloy segregation. Motagamwala et al. report that platinum–tin nanoparticles interact more weakly with a silica support and the metals thus do not segregate. The use of undiluted reactants allowed the reaction to run near the thermodynamically limit of about 67% conversion with a selectivity to propylene of more than 99%. This catalyst also does not build up carbon and could run up to 30 hours without deactivation. Science , abg7894, this issue p. 217
This dataset contains daily files with thermodynamic profiles retrieved with the optimal estimation physical retrieval TROPoe v0.19 (Turner and Löhnert 2014; Turner and Blumberg 2019; Turner and Löhnert 2021). The profiles are retrieved every 10 minutes from instantaneous observations from the NLR ASSIST II infrared spectrometer. Observations are noise-filtered but not averaged in time to minimize errors due to non-uniform clouds. Additional input data in TROPoe are cloud base height (CBH) from co-located scanning lidar. The full pipeline for running the retrieval is available at https://github.com/StefanoWind/TROPoe_processor. Met data was not ingested. In addition to these temporally resolved input data, TROPoe requires an a priori dataset (prior) that provides mean climatological estimates of thermodynamic profiles and specifies how temperature and humidity covary with height as an input (for details see, e.g., Djalalova et al. 2022). The prior is a key component of the retrieval and provides a constraint on the ill-posed inversion problem. A monthly prior was computed from operational radiosonde launches in Denver, CO.
Lithium aluminate has attracted researchers’ interests due to its wide applications. The structural, electronic, optical, lattice phonon thermodynamic, and thermo-conductive properties of ?-LiAlO2 with 6Li-isotope substitution are investigated by density functional theory and lattice phonon dynamics. The calculated results show that ?-LiAlO2 possesses a wide band-gap of 4.63 eV. The valence band is mainly formed by p orbitals of Li, O, and Al. The calculated lattice thermal conductivity of ?-LiAlO2 is found to be in good agreement over a wide range of temperatures with the available experimental data. The calculated dielectric matrix shows anisotropic behavior along z and x (or y) axes. Due to the wide band-gap, the optical conductivity of ?-LiAlO2 is mainly contributed from the electron hopping between valence-conduction bands. Substitution of 7Li with 6Li isotope in ?-LiAlO2 leads to observable differences in the lattice phonon frequencies at higher frequencies (>8THz) and to slight changes in corresponding thermal conductivity and the infrared and Raman spectra which are in good agreement with the measured data. The relevance of these properties for tritium production through 6Li absorbing neutron in nuclear reactors is discussed.
We show how equations of state generated by density functional theory methods can be augmented to match experimental data without distorting the correct behavior in the high- and low-density limits. The technique is thermodynamically consistent and relies on knowledge of the density and bulk modulus at a reference state and an estimation of the critical density of the liquid phase. We apply the method to four materials representing different classes of solids: carbon, molybdenum, lithium, and lithium fluoride. It is demonstrated that the corrected equations of state for both the liquid and solid phases show a significantly reduced dependence of the exchange-correlation functional used.
Approximate formulas for calculating thermodynamic characteristics and equilibrium constants of chemical reactions
The acid-catalyzed transformation of furfuryl alcohol (FA) monomer to oligomers has been studied in the liquid phase to investigate the reaction mechanisms and intermediate species by using a combination of quantitative reaction product measurements and density functional theory calculations. FA monomer was converted into oligomers with a broad range of carbon number: C9–C10, C14–C15, C19–C29, NC29. Based on the calculations, terminal CH2OH dimer formation is both kinetically and thermodynamically favored, consistent with the experimental results. The order for dimer production in the C9–C10 range follows terminal CH2OH N ether bridged–methylene bridged dimer N OH-carbon bridge.
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An important characteristic of RNA folding is the adoption of alternative configurations of similar stability, often referred to as misfolded configurations. These configurations are considered to compete with correctly folded configurations, although their rigorous thermodynamic and structural characterization remains elusive. Tetraloop motifs found in large ribozymes are ideal systems for an atomistically detailed computational quantification of folding free energy landscapes and the structural characterization of their constituent free energy basins, including nonnative states. In this work, we studied a group of closely related 10-mer tetraloops using a combined parallel tempering and metadynamics technique that allows a reliable sampling of the free energy landscapes, requiring only knowledge that the stem folds into a canonical A-RNA configuration. Here we isolated and analyzed unfolded, folded, and misfolded populations that correspond to different free energy basins. We identified a distinct misfolded state that has a stability very close to that of the correctly folded state. This misfolded state contains a predominant population that shares the same structural features across all tetraloops studied here and lacks the noncanonical A-G base pair in its loop portion. Further analysis performed with biased trajectories showed that although this competitive misfolded state is not an essential intermediate, it is visited in most of the transitions from unfolded to correctly folded states. Moreover, the tetraloops can transition from this misfolded state to the correctly folded state without requiring extensive unfolding.