Valence State Research Articles

Boosting Solar-Driven CO2 Conversion to Ethanol via Single-Atom Catalyst with Defected Low-Coordination Cu-N2 Motif.

In this paper,we report a high-performance carbon nitride supported Cu single-atom catalyst featuring defected low-coordination Cu-N2 motif (Cu-N2-V). Lead many recently reported photocatalysts and its Cu-N3 and Cu-N4 counterparts, Cu-N2-V exhibits superior photocatalytic activity for CO2 reduction to ethanol, delivering 69.8 μmol g-1 h-1 ethanol production rate, 97.8% electron-based ethanol selectivity, and a yield of ~10 times higher than Cu-N3 and Cu-N4. Revealed by the extensive experimental investigation combined with the DFT calculation, the superior photoactivity of Cu-N2-V stems from its unique defected Cu-N2 configuration. Firstly, Cu in Cu-N2-V exist in Cu+/Cu2+ dual valence states, although predominantly in Cu+. The Cu+ sites support CO2 activation and the Cu+/Cu2+ sites are conducive for strong *CO adsorption and subsequent *CO-*CO dimerization enabling C-C coupling. Secondly, the Cu sites in Cu-N2-V are rich in electrons and thus highly active. Together they dictate the rate-determining step on CO2 photoreduction to ethanol and lower the Gibbs free energy change. Furthermore, the defected configuration also promotes light adsorption and charge separation efficiency. Collectively, these make Cu-N2-V an effective and high-performance catalyst for solar-driven CO2 conversion to ethanol. This study also reveals the valence state change of Cu in Cu-N2-V during the CO2 photoreduction reaction.

Theoretical study on the hydrogen distribution and diffusion at the PuO2/α-Pu2O3 interface.

The interface is a region in the crystal that significantly changes various characteristics. There must be an interface between oxides of different valence states in the surface oxide layer of plutonium. In this work, a first principles approach based on DFT was used to study the hydrogen distribution and diffusion at the PuO2/α-Pu2O3 interface systematically. Our research reveals that at the interface, hydrogen can be captured by the O atoms of PuO2 and by the oxygen vacancies (OVs) of α-Pu2O3, and the capture of OVs is more energetically advantageous. On the PuO2 side, the cost of H atom diffusion towards the interface gradually increases. On the α-Pu2O3 side, the cost of H atoms diffusing inward from the interface gradually increases. OVs that already contain H atoms are more conducive to capturing H atoms. The formation of the interface has little effect on the hydrogen capture ability of O in PuO2, but it will reduce the capture ability of OVs in α-Pu2O3. Overall, the formation of interfaces has no disruptive impact on the behavior of hydrogen in the two plutonium oxides. This is closely related to the fact that α-Pu2O3 originates from PuO2 under anaerobic conditions. The difference in hydrogen behavior comes from the changes in the atomic environment and ion valence state caused by the OVs. This work supports further understanding of the behavior of hydrogen in plutonium oxides and provides a reference for further research on plutonium corrosion prevention.

Hydrogen generation by hydrolysis of alkaline NaBH4 solution doped with amorphous catalyst Co–Y2O3–B/CNTs

This investigation enhances the catalytic efficiency of Co–B/CNTs for hydrogen production via sodium borohydride hydrolysis by doping with 5%Y2O3. Such doping significantly boosts hydrogen evolution rates, with Co–Y2O3–B/CNTs achieving a production rate of 1083.43 ml g−1·min−1—surpassing Co–B/CNTs by 1.5 times and tripling that of Co–B catalysts. SEM and XRD analyses show Y2O3 doping reduces particle aggregation and maintains the catalyst's amorphous state, thereby increasing the active surface area. Furthermore, XPS analysis demonstrates that introducing yttrium into Co–B/CNTs catalysts improves their surface elemental composition and valence states. This improvement boosts catalyst performance and stability by enhancing electron transfer and particle size optimization. Optimal hydrolysis is achieved at an NaOH concentration of 2.5 mol/L, with higher concentrations diminishing hydrogen production due to increased viscosity from by-product formation. Additionally, Co–Y2O3–B/CNTs catalysts exhibit commendable durability, maintaining more than two-thirds of their initial activity after five reuse cycles, outperforming comparable catalysts to a moderate extent. These findings underscore the beneficial role of Y2O3 in the Co–B/CNTs framework, promoting Y2O3-doped catalysts for their enhanced efficiency, sustainability, and hydrogen production capabilities.

Feasibility research of perovskite‐type PrAlO3+δ as high‐temperature infrared radiation coating

AbstractThermal radiation coating with low thermal conductivity and high infrared emissivity are desirable. In this work, a novel rare‐earth aluminate (PrAlO3+δ with rhombohedral structure) was synthesized via solid‐state reaction method, and the corresponding coating was fabricated using atmospheric plasma spraying (APS). The study encompassed an investigation into the phase structure, high‐temperature phase stability, thermo‐mechanical characteristics, and infrared properties. The results illustrate that as‐deposited coating contained amorphous phase, but recrystallized coating presented phase stability up to 1600°C. Furthermore, the recrystallized coating exhibited low thermal conductivity of 1.35 W/m K at 900°C as well as an average coefficient of thermal expansion of 10.36 × 10−6/K. Also, the coating exhibited high infrared emissivity related to high valance state (Pr4+) and oxygen vacancies. And the average infrared emissivity within 2–14 µm was 0.822 at 1300°C and presented slight decrease with the increase of temperature (the average infrared emissivity of 0.795 at 1800°C).

Fluorinated silane self-assembled monolayer modification of V2O5 for enhanced hole injection and device efficiency

This study introduces a new approach to enhance hole injection in organic light-emitting diodes (OLEDs) by modifying the energy band alignment. This enhancement is achieved by incorporating gap states near the Fermi level through the application of a 1H,1H,2H,2H-perfluorooctyltriethoxysilane self-assembled monolayer (F8SAM) coating on V2O5. Compared to thermally evaporated V2O5, the F8SAM coating induces greater oxygen deficiency, reducing the V2O5 (V5+) content from 84.2 % to 76.9 % and increasing the VO2 (V4+) content from 15.7 % to 23.0 %. This modification causes both the highest occupied molecular orbital and gap state levels to move closer to the Fermi level, facilitated by increased oxygen vacancies, high carrier concentration, and delocalized free electrons. The alteration in the gap state provides a more accessible pathway for efficient hole injection, as confirmed in optoelectronic green light devices, which demonstrate a wavelength of 530 ± 5 nm. Significantly, devices incorporating a double-layer hole-injection layer exhibit a 5-fold increase in maximum luminance, a 1.6-fold increase in current efficiency, and a 1.7-fold increase in power efficiency compared to devices with an unmodified V2O5 film. The enhanced performance is attributed to the well-aligned F8SAM on V2O5, which increases the density of hole states and thereby improves device performance. This study demonstrates a practical method for modulating the cation valence state of V2O5, offering a pathway toward improved hole injection and, consequently, more efficient and functional OLED devices.

Effects of doping with selected rare-earth elements (Eu3+, Dy3+, Eu3+/Dy3+) on the structural characteristics as well as electrical and luminescent properties of K0.5Na0.5NbO3

The effects of adding Eu3+, Dy3+, and Eu3+/Dy3+ rare-earth elements on the microstructural, optical and electrical properties of lead-free piezoelectric materials based on K0.5Na0.5NbO3 (KNN) were investigated. A series of fine powders were synthesized via a modified Pechini route utilizing citric acid. Relatively large amounts of rare-earth elements were successfully incorporated into the crystal lattice of KNN. A combination of X-ray diffraction, X-ray absorption spectroscopy, energy-dispersive X-ray and scanning electron microscopy were used to characterize the structure and chemical composition of the powders and sinters. XRD patterns indicated the formation of a single-phase orthorhombic structure in the co-doped sinter. X-ray absorption spectroscopy revealed the nominal 3+ valence states of Eu and Dy in KNN ceramic sinters. The Mott model and group symmetry theory were used to discuss the characteristics of Raman spectra obtained for the EuDy:KNN ceramics. The ceramics exhibited good dielectric permittivity (ε≃1300) and low dielectric loss (tan δ=0.03) in the temperature range of 170–240°C. The electrical properties of the ceramics showed that the basic mechanism of conduction and relaxation was thermal activation, and that small polaron hopping was responsible for charge carrying. The Eu3+ and Dy3+ ions displayed characteristic red and orange emissions in sinters when excited with light in the wide ultraviolet spectra range (380–420 nm).

Synthesis of β,β-Dithioketones by Merging C-C and C-S Bond Cleavage in [1 + 1 + 1 + 1 + 1 + 1] Annulation.

An unconventional [1 + 1 + 1 + 1 + 1 + 1] annulation process was developed for the construction of β,β-dithioketones by merging C-C and C-S bond cleavage. In this reaction, rongalite concurrently served as triple C1 units, dual sulfur(II) synthons, and a reductant for the first time. Mechanism investigation indicated that the reaction involved the self-mediated valence state change of rongalite. By performing this step-economical method, the challenging construction of C5-substituted 1,3-dithiane can be achieved under mild and simple conditions.

Palladium enhanced electrochemical supercapacitive performance of chromium oxide thin films synthesized by sputtering process

Recently, the use of transition metal oxide electrodes for supercapacitor applications has increased due to the possibility of variable mixed valence states. The present study has established the use of Pd-Cr2O3 composite thin films as a working electrode for high-performance supercapacitors. The reactive dc magnetron co-sputtering method has been used for the fabrication of thin film of Cr2O3 and Pd-Cr2O3 on SS-304 substrate. X-ray diffraction and X-ray photoemission spectroscopy techniques were used to examine the surface chemistry and phase purity of chromium oxide and Pd-Cr2O3 composite thin films. The incorporation of Pd in Cr2O3 delivers a drastic change in the surface morphology. Due to the modified morphology and electronic properties, a noticeable improvement in the electrochemical properties of Pd-Cr2O3 electrode is observed. The obtained value of specific capacitance for this electrode is 401 Fg−1 at 0.1 mAcm−2 scan rate and within the potential window range 0 to +1.2 V. This value of specific capacitance is almost twice in comparison to the Cr2O3 based electrode. The Pd-Cr2O3 composite thin film shows a good cycle retention capability of 8000 cycles with 87.5 % retention. The obtained value of energy density and power density for Pd-Cr2O3 electrode was 80.2 Whkg−1 and 3.23 kWkg−1, respectively at 0.1 mAcm−2. Consequently, this composite material electrode can be seen as a promising advancement for electrodes in supercapacitor devices.

High-Pressure Polymorphism in Silver Ferrite Delafossite, AgFeO2.

The delafossites are a class of layered metal oxides that are notable for being able to exhibit optical transparency alongside an in-plane electrical conductivity, making them promising platforms for the development of transparent conductive oxides. Pressure-induced polymorphism offers a direct method for altering the electrical and optical properties in this class, and although the copper delafossites have been studied extensively under pressure, the silver delafossites remain only partially studied. We report two new high-pressure polymorphs of silver ferrite delafossite, AgFeO2, that are stabilized above ∼6 and ∼14 GPa. In situ X-ray diffraction and vibrational spectroscopy measurements are used to examine the structural changes across the two phase transitions. The high-pressure structure between 6 and 14 GPa is assigned as a monoclinic C2/c structure that is analogous to the high-pressure phase reported for AgGaO2. Nuclear resonant forward scattering reveals no change in the spin state or valence state at the Fe3+ site up to 15.3(5) GPa.

Strategic Ni integration to study its impact on the photoluminescence and photocatalytic performances of SnO2 nanorod architecture

The sol-gel process was utilized to fabricate SnO2 nanoparticles, both in their pure form and with the addition of Ni dopants. The nanoparticles obtained were further examined to ascertain the characteristics associated with their structure, alterations in band gap, and photocatalytic performance. The insertion of nickel ions into tin sites hinders the formation of grain growth in tin oxide. The variation in the valence states and ionic radius of Sn4+ and Ni2+ ions, as revealed by X-ray diffraction (XRD) study, accounts for this disparity. FTIR measurements indicate the existence of stretching vibrations of metal-oxygen bonds that include Ni ions in the doped samples. The photoluminescence (PL) analysis reveals that the introduction of nickel doping alters the band structure of SnO2, leading to the creation of additional defect states, such as oxygen vacancies inside the crystal lattice. A study was undertaken to investigate the photocatalytic (PC) activity of SnO2 in the presence of Ni dopants. The results revealed a noticeable improvement in the efficiency of photodegradation. The degradation of Congo red (CR) dye using Ni–SnO2 nanocrystals achieves an efficiency of 94.88 % within a duration of 180 ​min. An analysis has been conducted on the impact of dye content, photocatalyst dosage, and pH on the degradation efficiency. As per the study, lower dose of Ni–SnO2 has shown better degradation efficiency in comparison to other studies. The improved performance of Ni–SnO2 can be ascribed to two main factors: the inhibition of carrier recombination due to the inclusion of defective states, and the production of hydroxyl radicals (OH•). The stability and reusability of these photocatalysts have been noted in their efficient application for environmental remediation.

Spectroscopic investigations on trivalent ruthenium ions in ruthenium perovskite oxide thin films

The d5 electron configurations under the crystal field, spin–orbit coupling, and Coulomb interaction give rise to a plethora of profound ground states. Ruthenium perovskite oxides exhibit a number of unconventional properties yet the Ru4+ state (4d4) is usually stable in these materials. In this regard, Ru3+ ions in perovskite materials are expected to be a mesmerizing playground of 4d5 electron configurations. Here, we report measurements of x-ray photoemission spectroscopy on recently synthesized perovskite ruthenium oxide thin films, LaRuO3 and NdRuO3, whose valence state of the ruthenium ions is trivalent. We discuss correlation and spin–orbit effects from the valence band spectra, in particular an additional peak structure around 3–5 eV, reminiscent of the so-called 3 eV peak observed in Sr2RuO4. Moreover, we find that the core-level spectra of these materials are quantitatively different from those in other ruthenates, which possess Ru4+ ions, e.g., SrRuO3. We therefore argue that the core level spectra of LaRuO3 and NdRuO3 are peculiar to the Ru3+ states.

Efficient ozone decomposition in high humidity environments using novel iron-doped OMS-2-loaded activated carbon material.

This study effectively addresses the rapid deactivation of manganese-based catalysts in humid environments during ozone decomposition by introducing iron-doped manganese oxide octahedral molecular sieve (Fe-OMS-2) catalysts supported on activated carbon (AC). By optimizing the doping ratio of Fe-OMS-2, the Fe-OMS-20.5/AC catalyst achieves nearly 100% ozone decomposition efficiency across a wide range of relative humidity levels (0 to 60%), even at elevated air flow rates of 800 L·g-1·h-1, outperforming standalone AC, Fe-OMS-2, or a simple mixture of OMS-2 and AC. The Fe-OMS-20.5/AC catalyst features a porous surface and a mesoporous structure, providing a substantial specific surface area that facilitates the uniform distribution of the Fe-OMS-2 active phase on the AC surface. The incorporation of Fe3+ ions enhances electron transfer between valence state transitions of Mn, thereby improving the catalyst's efficiency in ozone decomposition. Additionally, the AC component protects catalytic sites and enhances the catalyst's humidity resistance. In conclusion, this research presents a novel strategy for developing highly efficient and cost-effective ozone decomposition catalysts that enhance dehumidification, significantly contributing to industrial ozone treatment technologies and advancing environmental protection.

Triple-function Mn regulation of NiFe (oxy)hydroxide for oxygen evolution reaction

Transition metal (oxy)hydroxides are potential oxygen evolution reaction (OER) electrocatalysts; however, simultaneously modulating multiple factors to enhance their performance is a grand challenge. Here, we report an incorporating heteroatom strategy via one-step hydrothermal approach to adjust more than one factor of Mn-doped NiFe (oxy)hydroxide (Mn-NiFeOOH/LDH) heterojunction. Mn doping regulates heterojunction morphology (reducing nanoparticles and becoming thinner and denser nanosheets), Ni/Fe ratio and valence states (Ni2+, Ni3+, and Ni3+Δ) of Ni ions. The former could effectively increase surface active sites, and the latter two reduce the content of Fe in the Mnx-NiFeOOH/LDH heterojunction, enabling more Ni2+ convert to Ni3+/3+Δ that have higher intrinsic OER activity. As a result, the first-rank Mn-NiFeOOH/LDH with ultra-low overpotential of 185 mV@20 mA cm−2 and 296 mV@500 mA cm−2, and the improved OER performance are outdo to those of commercial RuO2 catalyst for OER. Moreover, the Mn-NiFeOOH/LDH affords the earliest initial potential (1.392 V vs. RHE), corresponds to a recorded low overpotential (162 mV). Based on the density functional theory (DFT), Mn dopants can alter intermediate adsorption energy and effectively decrease *OOH’s energy barrier. This research exhibits a feasible strategy to design low cost electrocatalysts and provide new possibilities for future industrialization.

First-principles study on the coexistence of different valence states of Zn vacancy, Cu1+/2+ doping, and Hi in ZnO magnetic switch

In this study, we used first principles to investigate the magnetic sources and switches of Zn34Cu1+HiO36(VZn0), Zn34Cu1+HiO36(VZn2−), Zn34Cu2+HiO36(VZn0), and Zn34Cu2+HiO36(VZn2−) systems. On the basis of formation energy, phonon spectrum, and temporal variation of energy, we concluded that the above systems were all in a stable state. The doped system can be magnetized by adjusting the valence state of Zn vacancy, and the Zn34Cu1+HiO36(VZn0) and Zn34Cu2+HiO36(VZn2−) systems demonstrated magnetism. We found that the Zn34Cu1+HiO36(VZn0) system acquired magnetism through (O.↓↑+VZn")x⇔(↑O.+VZn"+↑O.)x⇔(↑O.+VZn"+↓O.)x super- and double-exchange interactions, whereas the magnetism of the Zn34Cu2+HiO36(VZn2−) system originated mainly from the action of the O1−–VZn2−–Cu2+-bound magnetic polaron and double exchange. Our theory provides a new approach for the use of magnetic switches in magnetic semiconductors.

Precise determination of oxygen content in SmBa2Cu3O7-δ thin film samples using x-ray diffraction

Abstract The superconducting properties of SmBa2Cu3O7-δ (SmBCO) thin films are predominantly influenced by the oxygen deficiency δ. Yet, the established methods to determine δ such as iodometric titration or thermogravimetry cannot be applied to thin films due to their very small volume.
Therefore, an alternative way to determine δ for SmBCO thin film samples using X-ray diffraction (XRD) is presented. Main point of this analysis is the structural relationship between the a, b and c lattice parameters and δ. A linear relationship between c and δ is found in SmBCO powder samples for both the orthorhombic and tetragonal phases.
Furthermore, an attempt is made to quantify the chemical composition using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). This attempt was inconclusive because of drastically changing ion yields due to δ influencing the valence state of the analyzed ions.
The found crystal structural relationship gathered from the powder samples is applied to thin film samples. Thereby, it becomes clear that thermal strain is affecting the crystal structure of the thin films. A simple correction model is used to correct for thermal strain and a good match between powder, literature and thin film data is achieved and thus a non-destructive way for the determination of δ using XRD.


Formation of nanophase metallic iron through charge disproportionation of ferrous iron during micrometeoroid impact‐induced splash melting

AbstractCharge disproportionation of ferrous iron has been considered as one of the mechanisms for the formation of metallic iron on the lunar surface. However, the detailed mechanism of the disproportionation reaction on the Moon is yet to be elucidated. We provide direct evidence for the ferrous disproportionation reaction that produces nano phase metallic iron (npFe0) during a rapid cooling process after splash melting from a lunar sample returned by China's Chang'e‐5 mission. Space weathering processes have resulted in the formation of three distinct zones at the rim of a pyroxene fragment, as observed through transmission electron microscopy. These zones, made up of splashed melts, newly formed melts from the substrate, and the mineral, are distinguished as I, II, and III. Quantitative analyses of the iron valence state by electron energy loss spectroscopy show that disproportionation reactions occurred in zone II at a low temperature of <570°C during a rapid cooling process. The reaction led to the production of α‐structure npFe0 and Fe3+ reserve in the glass phase. The npFe0 produced by the disproportionation reaction has a larger grain size than those formed from solar wind irradiation, implying that micrometeoroid impacts mainly contribute to the darkening of visible and near‐infrared reflectance. These findings reveal a novel rim structure by repeated space weathering and a universal formation mechanism of npFe0 during micrometeoroid impacts, suggesting that the disproportionation reaction could be widespread on airless bodies with impact‐induced splash processes.

Cooperation between single atom catalyst and support to promote nitrogen electroreduction to ammonia: A theoretical insight

The co-catalysis between single atom catalyst (SAC) and its support has recently emerged as a promising strategy to synergistically boost the catalytic activity of some complex electrochemical reactions, encompassing multiple intermediates and pathways. Herein, we utilized defective BC3 monolayer-supported SACs as a prototype to investigate the cooperative effects of SACs and their support on the catalytic performance of the nitrogen reduction reaction (NRR) for ammonia (NH3) production. The results showed that these SACs can be firmly stabilized on these defective BC3 supports with high stability against aggregation. Furthermore, co-activation of the inert N2 reactant was observed in certain embedded SACs and their neighboring B atoms on certain BC3 sheets due to the noticeable charge transfer and significant N–N bond elongation. Our high-throughput screening revealed that the Mo/DVCC and W/DVCC exhibit superior NRR catalytic performance, characterized by a low limiting potential of −0.33 and −0.43 V, respectively, which can be further increased under acid conditions based on the constant potential method. Moreover, varying NRR catalytic activities can be attributed to the differences in the valence state of active sites. Remarkably, further microkinetic modeling analysis displayed that the turnover frequency of N2–to–NH3 conversion on Mo/DVCC is as large as 1.20 × 10−3 s−1 site−1 at 700 K and 100 bar, thus guaranteeing its ultra-fast reaction rate. Our results not only suggest promising advanced electrocatalysts for NRR but also offer an effective avenue to regulate the electrocatalytic performance via the co-catalytic metal–support interactions.

Experimental study of low-temperature combustion performance in hydrogen/air mixtures over Pt–Cu/HZSM-5/cordierite bimetallic catalysts

Catalytic combustion provides a feasible technology to effectively avoid NOx formation due to the high temperature in the process of hydrogen combustion. Recently, the development of efficient and affordable catalysts has attracted extensive attention as the cost of noble metals remained high. In this study, a list of cordierite monolithic catalysts with low noble metal loading are prepared by introducing the appropriate amount of transition metals (Mn, Cu, Fe, Co, and Ce), and their catalytic performance are further investigated. On this basis, the study on catalytic stability and kinetic is carried out, and the synergistic interaction between the bimetals is revealed with comprehensive characterization methods. The results show that Cu could promote the reaction rate of the Pt-based catalyst which show the best catalytic performance with the Cu loading of 1 g/L. The ignition temperature T10 is 58.5 °C, and the burnout temperature T100 is 100 °C, with activation energy as low as 44.00 kJ/mol. The enhancement of the catalytic performance is attributed to the interaction between the bimetallic elements. On the one hand, the valence state of Cu and Pt is changed, and on the other hand the dispersion of Pt get improved, which contributed to the catalytic reaction rate.

Reaction mechanism and kinetics for Pt/C and Au/C catalyzed aqueous phase glycerol oxidation to various carboxylic acids

Fundamental understanding of heterogeneously catalytic aerobic oxidation of polyol is highly desirable for sustainable and efficient chemical synthesis. Herein, based on the purpose of exploring the selectivity of various carboxylic acids on Pt-Au catalysts with different ratios, we conducted a comprehensive investigation into the reaction pathways of glycerol oxidation over pristine Pt/C and Au/C catalysts via experiments, kinetics analysis and DFT calculations. Structural characterizations revealed that Pt/C exhibits a higher metallic state and more d electrons, thus tending to strongly adsorb OH– and promote oxygen activation. Conversely, the weak oxygen activation of Au/C could be attributed to fewer cationic high valence state and d electrons. Furthermore, the Langmuir-Hinshelwood kinetic model and DFT calculations indicate both catalysts exhibit obvious differences in product distribution. Specifically, Pt demonstrated higher selectivity towards lactic acid by facilitating dehydration of C-OH in glyceraldehyde and promoting timely desorption of lactic acid species. In contrast, Au displayed more glycolic acid products caused by strengthening oxidative cleavage of C-C bond in glyceric acid. Expanding to bimetallic catalysts, it was observed that catalysts with higher Au content exhibit enhanced selectivity towards the oxidation of glyceric acid to glycolic acid, while those with a higher Pt ratio demonstrate increased selectivity for the oxidation of glycerol to lactic acid. These findings provide valuable insights for guiding the design and optimization of this catalytic process to achieve targeted product generation.

Optoelectronic and transport properties of Lead-Free halide based Na2AgTlZ6 (Z = Cl, Br, I) double perovskites for energy harvesting applications

The bandgap engineering and deliberate band edge manipulation of perovskites make them potential candidates for the photovoltaic industry. Here we theoretically investigate the structure, density of states, and photovoltaic and thermoelectric characteristics of Na2AgTlZ6 (Z = Cl, Br, I) using WIEN2k code. The incorporation of Br and I at the Cl site caused the increase in lattice constant which leads to the decrease in bulk modulus and Debye temperature. The computed values of Poisson (<0.26) and Pugh (<1.75) ratio verified their brittle nature. The bandgap analysis reveals direct bandgap nature and bandgap value lie in the visible region for parent composition and infrared and far infrared when Cl is replaced with Br and I. The density of state plots uncovers the shifting of energy states in valence and conduction bands towards the Fermi level with the increasing number of electrons in the halogens. The increase in the value of dielectric constant, refractive index, and shifting of peaks towards lower energy value is witnessed with atomic number of halogen atoms. The viability of these compositions for thermoelectric devices is further confirmed when electrical conductivity and Seebeck coefficient dependent Figure of merit and power factor are evaluated in the temperature range of 200–800 K. In addition, the anisotropic nature of studied compositions is explored through the computation of the modulus of elasticity including Young’s modulus, Shear modulus in addition to compressibility, and Poisson’s ratio.