Electron Spin Research Articles

Solar‐Assisted CO2 Methanation via Photocatalytic Sabatier Reaction by Calcined Titanium‐based Organic Framework Supported RuOx Nanoparticles

AbstractCO2 reduction by sunlight under mild reaction conditions is a research area of increasing interest expected to favor decarbonization and produce fuels and chemicals in the circular economy. We hereby report on the development of a series of titanium oxide‐based solids produced by calcination of MIL‐125(Ti)‐NH2 decorated with RuOx nanoparticles (1 wt %) material at temperatures from 350 to 650 °C and used as photocatalysts for CO2 methanation under simulated sunlight irradiation (45 mW/cm2) at <200 °C and 1.5 atm total pressure. The material synthesized at 350 °C produced the highest photoactivity of the series (4.73 mmol g−1 CH4 at 22 h and an apparent quantum yield at 400, 500 and 750 nm of 0.76, 0.65 and 0.54 %, respectively), comparing favorably with the activities of other MOF‐based materials reported so far. Insights into the material's photocatalytic performance and a study of the possible reaction pathways during CO2 methanation were obtained by electrochemical impedance, electron spin resonance, photoluminescence and in situ FT‐IR spectroscopies together with transient photocurrent and hydrogen temperature programed desorption measurements. The study showed the possibility of using MOF‐based materials as precursors to develop metal oxide photocatalysts with enhanced activities for solar‐driven gaseous CO2 photomethanation.

Single-Shot Readout and Weak Measurement of a Tin-Vacancy Qubit in Diamond

The negatively charged tin-vacancy center in diamond (SnV−) is an emerging platform for building the next generation of long-distance quantum networks. This is due to the SnV−’s favorable optical and spin properties including bright emission, insensitivity to electronic noise, and long spin coherence times at temperatures above 1 K. Here, we demonstrate measurement of a single SnV− electronic spin with a single-shot readout fidelity of 87.4%, which can be further improved to 98.5% by conditioning on multiple readouts. In the process, we develop understanding of the relationship between strain, magnetic field, spin readout, and microwave spin control. We show that high-fidelity readout is compatible with rapid microwave spin control, demonstrating a favorable parameter regime for use of the SnV− center as a high-quality spin-photon interface. Finally, we use weak quantum measurement to study measurement-induced dephasing; this illuminates the fundamental interplay between measurement and decoherence in quantum mechanics, and provides a universal method to characterize the efficiency of color-center spin readout. Taken together, these results overcome an important hurdle in the development of the SnV−-based quantum technologies and, in the process, develop techniques and understanding broadly applicable to the study of solid-state quantum emitters. Published by the American Physical Society 2024

Dynamic basis of lipopolysaccharide export by LptB2FGC

Lipopolysaccharides (LPS) confer resistance against harsh conditions, including antibiotics, in Gram-negative bacteria. The lipopolysaccharide transport (Lpt) complex, consisting of seven proteins (A-G), exports LPS across the cellular envelope. LptB2FG forms an ATP-binding cassette transporter that transfers LPS to LptC. How LptB2FG couples ATP binding and hydrolysis with LPS transport to LptC remains unclear. We observed the conformational heterogeneity of LptB2FG and LptB2FGC in micelles and/or proteoliposomes using pulsed dipolar electron spin resonance spectroscopy. Additionally, we monitored LPS binding and release using laser-induced liquid bead ion desorption mass spectrometry. The β-jellyroll domain of LptF stably interacts with the LptG and LptC β-jellyrolls in both the apo and vanadate-trapped states. ATP binding at the cytoplasmic side is allosterically coupled to the selective opening of the periplasmic LptF β-jellyroll domain. In LptB2FG, ATP binding closes the nucleotide binding domains, causing a collapse of the first lateral gate as observed in structures. However, the second lateral gate, which forms the putative entry site for LPS, exhibits a heterogeneous conformation. LptC binding limits the flexibility of this gate to two conformations, likely representing the helix of LptC as either released from or inserted into the transmembrane domains. Our results reveal the regulation of the LPS entry gate through the dynamic behavior of the LptC transmembrane helix, while its β-jellyroll domain is anchored in the periplasm. This, combined with long-range ATP-dependent allosteric gating of the LptF β-jellyroll domain, may ensure efficient and unidirectional transport of LPS across the periplasm.

Dynamic basis of lipopolysaccharide export by LptB2FGC.

Lipopolysaccharides (LPS) confer resistance against harsh conditions, including antibiotics, in Gram-negative bacteria. The lipopolysaccharide transport (Lpt) complex, consisting of seven proteins (A-G), exports LPS across the cellular envelope. LptB2FG forms an ATP-binding cassette transporter that transfers LPS to LptC. How LptB2FG couples ATP binding and hydrolysis with LPS transport to LptC remains unclear. We observed the conformational heterogeneity of LptB2FG and LptB2FGC in micelles and/or proteoliposomes using pulsed dipolar electron spin resonance spectroscopy. Additionally, we monitored LPS binding and release using laser-induced liquid bead ion desorption mass spectrometry. The β-jellyroll domain of LptF stably interacts with the LptG and LptC β-jellyrolls in both the apo and vanadate-trapped states. ATP binding at the cytoplasmic side is allosterically coupled to the selective opening of the periplasmic LptF β-jellyroll domain. In LptB2FG, ATP binding closes the nucleotide binding domains, causing a collapse of the first lateral gate as observed in structures. However, the second lateral gate, which forms the putative entry site for LPS, exhibits a heterogeneous conformation. LptC binding limits the flexibility of this gate to two conformations, likely representing the helix of LptC as either released from or inserted into the transmembrane domains. Our results reveal the regulation of the LPS entry gate through the dynamic behavior of the LptC transmembrane helix, while its β-jellyroll domain is anchored in the periplasm. This, combined with long-range ATP-dependent allosteric gating of the LptF β-jellyroll domain, may ensure efficient and unidirectional transport of LPS across the periplasm.

Rational Doping Strategy to Build the First Solution‐Processed p‐n Homojunction Architecture toward Silicon Quantum Dot Photodetectors

Semiconductor p‐n homojunction is a requisite building block of operating transistors and diodes which make up the modern electronic circuits and optoelectronic applications. However, it has been so far limited to bulk form of single crystals such as silicon (Si) or gallium arsenide. Herein, a brand‐new method of constructing p‐n homojunction architectures that breaks through the limitation is presented. Colloidal inks of p‐type and n‐type Si quantum dots (QDs) are synthesized by thermal disproportionation of (HSiO1.5)n doped with boron or phosphorus, followed by surface ligand engineering. Analysis combining UV photoelectron spectroscopy, electron spin resonance, and current–voltage characteristics confirms that an orthogonal solvent trick makes clean interfaces between n‐type and p‐type SiQD layers without disruption on film formation. The forward and reverse current–voltage characteristics of the diode, along with various spectroscopic characterizations, demonstrate the formation of the first p‐n homojunction of SiQDs. The self‐powered photodiode provides a tunable response specific to the wavelength.

High magnetic susceptibility-based vanadate tellurite glasses for magneto-optical device applications

Tellurite glasses modified with V2O5, Fe2O3, and Na2O (TVFN), along with Sm3+-doped Gd2O3 and Sb2O3 based tellurite (TVGSNSm) glasses evaluated for various properties. The thermal stability of these glasses, with a critical value of 105 °C advantageous to luminescence. Fourier transform infrared and micro-Raman bands were identified at 669, 745, 859, 943, and 1003 cm−1 in the deconvolution. Electron spin resonance revealed a signal at a magnetic field of 340.75 mT (g = 1.77). The magnetic hysteresis of TVFN glasses from a vibrating sample magnetometer which possess coercivity 62 mT and remanence 1.5х10−2 Am2/kg with a saturation magnetization 0.1975 A m2/kg and magnetic susceptibility as high as 0.1328. The magnetic nature confirmed by superconducting quantum interference device. Photoluminescence of Sm3+-doped TVGSNSm glasses excited by 408 nm showed 646 nm (red-orange) dominated emission band over the 603 nm band. These findings underscore the potential of TVFN glasses for applications in magneto-optical devices.

Fabrication of CoTiO3/MgIn2S4 S–scheme heterojunctions with efficient charge separation to enhance the photocatalytic activities of hydrogen generation and formaldehyde removal

The efficient separation of photoinduced charge carriers is a primary factor in the catalytic performance of photocatalysts. Constructing S-scheme heterojunctions is a prospective strategy to efficiently and spatially separate photoinduced charges while retaining strong oxidation and reduction capacities of the catalyst system. Herein, CoTiO3/MgIn2S4 (abbreviated x% CTO/MIS, where x% represents the mass ratio of CTO-to-MIS; x = 5, 10, 15, 20, and 25) heterojunctions were successfully synthesized using a hydrothermal method. These heterojunctions exhibited highly efficient and reusable visible-light photocatalytic properties for hydrogen (H2) generation and formaldehyde (HCHO) degradation. Notably, the 15 % CTO/MIS demonstrated an admirable H2 evolution activity of 631.77 μmol·g−1·h−1, with AQE = 2.25 % at λ = 420 nm, and an HCHO degradation rate of 67.18 %. The intermediate products generated during HCHO removal were identified applying in situ diffuse reflectance infrared Fourier transform spectroscopy. The exceptional catalytic performance of the synthesized materials was attributed to the boosted light absorption and utilization, rapidly separation, and transfer of photoproduced charge carriers, which resulted from the internal electric field of the S-scheme mechanism. Moreover, the S-scheme electron transfer pathway for the CTO/MIS catalyst system during the photocatalytic process was confirmed using electron spin resonance spectroscopy, free-radical capturing tests, density functional theory calculations, in situ X-ray photoelectron spectroscopy, and semiconductor energy band theory. The study offers an innovative perspective for establishing S-scheme heterojunctions with highly efficient and stable photocatalytic activity for H2 generation and HCHO removal.

Acridone Derivatives for Near-UV Radical Polymerization: One-Component Type II vs. Multicomponent Behaviors.

In this work, two novel acridone-based photoinitiators were designed and synthesized for the free radical polymerization of acrylates with a light-emitting diode emitting at 405 nm. These acridone derivatives were employed as mono-component Type II photoinitiators and as multicomponent photoinitiating systems in the presence of an iodonium salt or an amine synergist (EDB) in which they achieved excellent polymerization initiating abilities and high final conversions of the acrylate group. Photoinitiation mechanisms through which reactive species are produced were investigated employing different complementary techniques including steady-state photolysis, steady-state fluorescence, cyclic voltammetry, UV-visible absorption spectroscopy, and electron spin resonance spectroscopy. Finally, these molecules were also used in the direct laser writing process for the fabrication of 3D objects.

Three-dimensional porous SiC/BDD electrode with long-term robustness and enhanced electrochemical degradation performance for refractory organic pollutants

Boron-doped diamond (BDD) electrodes with a three-dimensional (3D) porous network structure can overcome the mass transfer limitations and increase substantially the utilization rate of active oxygen species. Nonetheless, the 3D porous network structure was invariably built using metallic substrates, which inherently have inferior stability because of their non-corrosion resistance and the severe thermal mismatch between BDD films and substrates. Herein, we reported, for the first time, the use of a commercially porous silicon carbide (SiC) as the substrate to construct a 3D SiC/BDD electrode to simultaneously alleviate the problematics of substrate corrosion and thermal mismatch. This novel electrode exhibited a long-term service lifetime of 800 h in 3 M H2SO4 under the current density of 50 mA cm−2, over 500 times longer than the conventional metallic substrate-based BDD electrodes. The optimum p-SiC/BDD electrode exhibited a high oxygen evolution potential of 2.04 V vs. SHE, a low charge transfer resistance of 18.4 Ω, a high mass transfer coefficient of 2.78 × 10−5 m s−1, and a thin diffusion layer thickness of 25.2 μm. The proposed electrode had a threefold larger pseudo-first-order reaction rate constant than a flat BDD electrode, although it consumed just a fourth of the latter’s electric energy. The superior performance was attributable to an increased mass transfer rate confirmed by computational fluid dynamics (CFD) simulations as well as a high yield of reactive oxygen species verified by electron spin resonance (ESR). Furthermore, the proposed SiC/BDD electrode could work effectively under different water matrices in the presence of diverse salt electrolytes, thus paving a new avenue for the structure design of robust non-active anode materials.

Direct and indirect photodegradation mechanism of ractopamine in aquatic environment

As a kind of typical lean meat essences and veterinary drugs, ractopamine (RAC) has been frequently detected in agricultural sewage and livestock, posing potential risk to both aquatic ecosystems and human health. Despite its widespread occurrence, the environmental fate of RAC remains unclear. Here, the mechanisms underlying the direct and indirect photodegradation of RAC was investigated under UV light irradiation at wavelengths of 275 and 365 nm, respectively. The effect of pH, initial concentration, and co-existing ions were examined. For direct photodegradation, the quantum yield of RAC increased with increasing pH values. In solutions containing dissolved organic matter (DOM), indirect photodegradation of RAC intensified with increasing pH values, and the initial concentration of DOM accelerated the process. The presence of Cu2+ was found to inhibit both direct and indirect photodegradation of RAC. Electron spin resonance (ESR) spectrometry and quenching experiments revealed that direct photodegradation was primarily attributed to the decomposition of the triplet state of RAC. Both the triplet state of DOM (3DOM*) and singlet oxygen contributed to the indirect photodegradation of RAC. LC-MS/MS analysis indicated that oxidation of the phenol group and subsequent decarboxylation were the principal photodegradation processes. The energies of each state of RAC and the active sites of RAC molecules were computed using frontier molecular orbitals and Fukui indices based on density functional theory. Combining the analysis of photoproducts with energy calculation, pathways of the direct and indirect photodegradation of RAC were proposed. These findings unveiled the photochemical behaviors of RAC concerning the removal and attenuation in aquatic environment.

Electron Spin Dynamics of the Intersystem Crossing in Aminoanthraquinone Derivatives: The Spectral Telltale of Short Triplet Excited States.

We studied the excited state dynamics of two bis-amino substituted anthraquinone (AQ) derivatives, with absorption in the visible spectral region, which results from the attachment of a electron-donating group to the electron-deficient AQ chromophore. Femtosecond transient absorption spectra show that intersystem crossing (ISC) takes place in 190-320 ps, and nanosecond transient absorption spectra demonstrated an unusually short triplet state lifetime (2.06-5.43 μs) for the two AQ derivatives. Pulsed laser-excited time-resolved electron paramagnetic resonance (TREPR) spectra show an inversion of the electron spin polarization (ESP) phase pattern of the triplet state at a longer delay time after laser flash. Spectral simulations show faster decay of the Ty sublevel than the other two sublevels (τx = 15.0 μs, τy = 1.50 μs, τz = 15.0 μs); theoretical computation predicts initial overpopulation of the Ty sublevel, and rationalizes the short T1 state lifetime and the ESP inversion. Theoretical computations taking into account the electron-vibrational coupling, i.e., the Herzberg-Teller effect, successfully rationalize the TREPR experimental observations.

Effects of photodynamic therapy using bisdemethoxycurcumin combined with melatonin or acetyl-melatonin on C. Albicans

The current study aims to explore the efficacy of antifungal photodynamic therapy (PDT) on C. albicans biofilms by combining photosensitizers, bisdemethoxycurcumin (BDMC), and melatonin (MLT) or acetyl-melatonin (AcO-MLT). Additionally, the relationship between different types of reactive oxygen species and PDT’s antifungal efficacy was investigated. BDMC, MLT and AcO-MLT were applied, alone and in combination, to 48-hour C. albicans biofilm cultures (n = 6/group). Blue and red LED light (250 mW/cm2 with 37.5 J/cm2 for single or 75 J/cm2 for dual photosensitizer groups) were used to irradiate BDMC groups and MLT/AcO-MLT groups, respectively. For combination groups, blue LEDs and subsequently red LEDs were used. Drop plate assays were performed at 0, 1 and 6 h post-treatment. Colony forming units (CFUs) were then counted after 48 h. Hydroxyl radicals and singlet oxygen were measured using fluorescence spectroscopy and electron spin resonance (ESR) spectroscopy. Additionally, cell cytotoxicity was tested on human oral keratinocytes. Significant CFU reductions were observed with combinations 20 µM BDMC + 20 µM AcO-MLT and 60 µM BDMC + 20 µM MLT at 0 and 1 h post-treatment, respectively. Singlet oxygen production increased with the addition of MLT/AcO-MLT and had moderate-substantial correlations with inhibition at all times. Hydroxyl radical production was not significantly different from the control. Additionally, BDMC exhibited subtle cytotoxicity on human oral keratinocytes. PDT using BDMC + MLT or AcO-MLT, with blue and red LED light, effectively inhibits C. albicans biofilm through singlet oxygen generation. Melatonin acts as a photosensitizer in PDT to inhibit fungal infection.

Engineering hierarchical TiO2/ZnIn2S4 hybrid heterostructure with synergistic interfaces: A dual-functional S-scheme photocatalyst for efficient CO2 reduction and norfloxacin degradation

The development of multifunctional photocatalysts that can harness solar energy for both environmental remediation and energy generation is a considerable challenge in achieving sustainable development. This study introduces a dual-functional S-scheme hybrid catalyst comprising hierarchical 3D flower-like ZnIn2S4 (ZIS) microspheres embedded with TiO2 (TO) nanoparticles, synthesized via a facile in situ hydrothermal process. The unique structural and compositional synergy between ZIS and TO leverages their complementary photocatalytic properties, facilitating efficient solar energy utilization, increasing specific surface area, and enhancing CO2 adsorption capabilities. The S-scheme mechanism, confirmed by in situ-irradiated X-ray photoelectron spectroscopy and electron spin resonance spectroscopy, underlying this system promotes effective separation of photoexcited charge carriers while preserving the intrinsic strong reducibility of ZIS and high oxidizability of TO. These beneficial properties of the TO/ZIS hybrid provide a robust platform for CH4 production (75.6 μmol h−1 g−1) through selective (99.6 %) CO2 reduction over competing water reduction and achieve exceptional degradation and mineralization of the persistent antibiotic norfloxacin in water, addressing both energy and environmental challenges. Furthermore, the hybrid catalyst exhibits significant stability and recyclability, maintaining high catalytic performance across multiple cycles, thereby underscoring its practical viability. This work offers a promising blueprint for developing multifunctional photocatalysts capable of addressing critical global challenges, demonstrating the potential of hierarchical nanostructures and S-scheme charge transfer mechanisms.

Preliminary ESR dating results of fault barite shed new insights into the retrospective history of bedrock fault activities in basaltic regions

The chronology of fault activity in bedrock is critical to constraining and understanding periods of active faulting, assessing seismic hazards, and mitigating the effects of earthquakes. However, because of the lack of suitable materials for dating, the temporal reconstruction of faulting in bedrock remains highly challenging for geologists. In the present study, we determine for the first time the electron spin resonance (ESR) ages of fault barite (BaSO4), which is produced by episodes of intense faulting on basalt bedrock fault surfaces. Three barite samples were obtained from a basalt fault section (27°5′23″N, 100°25′45″E, 1.8 km above sea level) of the Lijiang–Xiaojinhe Fault (LXF), southeastern Tibetan Plateau, for ESR measurements. Similar to marine barite, the ESR spectrum of fault barite shows an electron-type center with g = 2.0037, 2.0034, and 2.0028 attributed to SO3−. The signal intensity systematically increased with increasing gamma-ray dose. Dose rates were calculated using a model based on the location and burial depth of the barite samples, as well as their surrounding bedrock. The three barite samples yield ESR ages of 131 ± 26, 503 ± 61, and 1416 ± 246 ka, respectively, which indicate that the LXF was active during the Early and Middle Pleistocene. The three ESR ages for fault barite from basalt extend the time range of activity of the LXF compared with previous carbonate ESR and radiocarbon dating results. Consequently, we propose that ESR dating of barite is valuable for reconstructing the history of bedrock fault activity. However, given that this investigation represents a preliminary application of the fault-barite ESR method, further study is needed to confirm its usefulness and the accuracy and precision of dating results.

A Paired-Ion Framework Composed of Vanadyl Porphyrin Molecular Qubits Extends Spin Coherence Times.

Molecular electron spin qubits arranged in precise arrays have great potential for use in quantum information science applications. Molecular qubits are synthetically versatile and can be placed in ordered arrangements upon incorporation into a new class of materials known as paired-ion frameworks (PIFs). A PIF composed of vanadyl porphyrin molecular qubits, VOTCPP-PIF-1, was synthesized as single crystals. Electron paramagnetic resonance spectroscopy was used to study their spin coherence at temperatures up to 293 K. A suspension of VOTCPP-PIF-1 at 5 K in dimethylformamide (DMF) had a spin-spin relaxation time (Tm) of 270 ns. In DMF-d7 and at 5 K, the coherence time of this material increased to 370 ns. This increase in Tm is attributed to the lower gyromagnetic ratio of 2H compared to 1H, which results in weaker electron-nuclear dipolar coupling that reduces the effect of nuclear spin flips on electron spin coherence. In toluene, crystals of VOTCPP-PIF-1 had a Tm of 31 ns at 293 K, demonstrating that PIFs are a promising platform for creating materials for quantum information science applications.

Walnut Shell Biomass Triggered Formation of Fe3C-Biochar Composite for Removal of Diclofenac by Activating Percarbonate

Percarbonate (SPC) as a promising substitute for liquid H2O2 has many advantages in the application of in situ chemical oxidation (ISCO). Developing efficient, cost effective and environmentally friendly catalysts for SPC activation plays the key role in promoting the development of SPC-based ISCO. Herein, the walnut shell biomass was combined with ferric nitrate for the catalytic synthesis of Fe3C@biochar composite (Fe3C@WSB), which demonstrated high efficiency in activating SPC for the removal of diclofenac (DCF). The Fe3C showed average crystallite size of 32.6 nm and the composite Fe3C@WSB demonstrated strong adsorptivity. The prepared Fe3C@WSB could activate both SPC and H2O2 with high efficiency at ca. pH 3 with extremely low leaching of iron, while in a weak acidic condition, higher efficiency of DCF removal was obtained in the Fe3C@WSB/SPC process than in the Fe3C@WSB/H2O2 process. Moreover, the Fe3C@WSB/SPC and Fe3C@WSB/H2O2 processes did not show significant differences when supplied with varying amounts of catalyst or oxidant, but the Fe3C@WSB/SPC process exhibited stronger capability in dealing with relatively highly concentrated DCF solution. Based on quenching experiments and electron spin resonance (ESR) analysis, heterogeneous activation of SPC was assumed as the dominant route for DCF degradation, and both the oxidation by radicals, including •OH, •O2− and CO3•−, combined with electron transfer pathway contributed to DCF degradation in the Fe3C@WSB/SPC process. The cycling experiment results also revealed the stability of Fe3C@WSB. This work may cast some light on the development of efficient catalysts for the activation of SPC.

Critical trigger of self-assembled bimetallic Fe/Mn-MOF with SnS2 heterojunctions by persulfate activation for efficient tetracyclines photodegradation

Developing advanced strategies, including exposing active site centers, regulating coordination environments, controlling crystallographic facets, optimizing electronic structures and constructing defects for enhancing photocatalytic performance is of great significance to improving the ecosystem. In this study, a novel self-assembled bimetallic Fe/Mn-MOF with SnS2 Z-scheme heterojunction photocatalyst was designed using a facile multistep solvothermal method. Benefiting from the interfacial heterojunction synergistic effect, the photocatalysts exhibited an outstanding catalytic performance. Nearly 91.4% efficiency of tetracyclines was degraded within 80 min through the assistance of a persulfate-based advanced oxidation process. DFT calculations utilizing the Fukui index identified the sites vulnerable to attack by the active species. As demonstrated by the trapping experiments and electron spin resonance (ESR), the involved oxygen-active species (•O2− and 1O2) facilitated the rapid degradation of tetracycline. The degradation pathways were further guided in the elucidation of the rationale mechanism and the toxicity of derived intermediates was revealed. This work opens a new strategy for the rational design of bimetallic photocatalysts, emphasizing interface-modulated heterojunctions for efficient solar energy conversion.

Chiral Nanostructured Ag Films for Multicarbon Products from CO2 Electroreduction.

The formation of multicarbon products from CO2 electroreduction is challenging on materials other than Cu-based catalysts. Ag has been known to be a typical metal catalyst, producing CO in CO2 electroreduction. The formation of C2+ products by Ag has never been reported because the carbon-carbon (C-C) coupling is an unfavorable process due to the high reaction barrier energy of *OCCO. Here, we propose that the chirality-induced spin polarization of chiral nanostructured Ag films (CNAFs) can promote the formation of triplet OCCO by regulating its parallel electron spin alignment, and the helical lattice distortion of nanostructures can decrease the reaction energy of *OCCO, which triggers C-C coupling and promotes subsequent *OCCO hydrogenation to facilitate the generation of C2+ products. The CNAFs with helically lattice-distorted nanoflakes were fabricated via electrodeposition using phenylalanine as the symmetry-breaking agent. C2+ products (C2H4, C2H6, C3H8, C2H5OH, and CH3COOH) with a Faradaic efficiency of ∼4.7% and a current density of ∼22 mA/cm2 were generated in KHCO3 electrolytes under 12.5 atm of CO2 (g). Our findings propose that the chiral nanostructured materials can regulate the multifunctionality of catalytic performance in the catalytic reactions with triplet intermediates and products.

A Spin‐Polarized Electron‐Induced MXene‐KBi0.9Co0.1Fe2O5 Photocatalyst for Enhanced Dye Degradation

In photocatalysts aimed to degrade environmental pollutants, photons are generally used as primary stimuli to generate electron–hole pairs to target the chemical bonds to disintegrate. Recently, electron spin has been reported as an essential degree of freedom to improve the performance of photocatalysts. In this work, spin‐polarized electrons and holes are introduced into a brownmillerite KBi0.9Co0.1Fe2O5 semiconductor and a two‐dimensional (2D) MXene composite system by application of an external magnetic field. The spin polarization properties are monitored by measuring the magnetoresistance effect of the MXene‐KBCFO device, which is related to the carrier transfer efficiency. Remarkably, the photocatalytic performance of MXene‐KBCFO is significantly enhanced by the simultaneous application of an external magnetic field and illumination due to the increased number of spin‐polarized photoexcited carriers caused by the synergy effect of the 2D MXene heterostructure together with the ferromagnetic spin ordering. This results in increased reaction hotspots, effective built‐in electric field, extended carrier lifetime, and reduced charge recombination owing to parallel alignment of electron spin orientation. The results show that the efficiency and stability of photocatalytic dye degradation can be effectively enhanced by manipulating the spin‐polarized electrons in the MXene‐based oxide‐perovskite heterostructure photocatalyst.

Study of Optoelectronic, Magnetic, and Thermoelectric Properties of Sr2XOsO6 (X = Y, Lu, Sc) Double Perovskites for Spintronic and Data Storage Devices

Advancement in electronic device miniaturization coupled with the precise control over their electromagnetic and transport properties, holds great promise for realizing practical quantum computing devices. Double perovskites, known for their stability, non-toxicity, and spin-polarized characteristics, are particularly appealing for spintronics applications. In this communication, we investigate the role of 6d-electrons of Os in regulating the magnetic properties in Sr2XOsO6 (X = Y, Lu, Sc) using theoretical methods with the WIEN2k code. The computed formation energies (-3.04, -2.91, and -2.82 eV) confirm the thermodynamic stability of these compositions. Analysis of the band structures and DOS exhibit ferromagnetic semiconducting character, elucidated through exchange constants and energies. This computation highlights the essential role of basic hybridization processes, crystal field effects, and exchange energy in generating ferromagnetic character driven by electronic spin. The analysis of optical behavior against photon energy (eV) reveals the maximum absorption in the UV region. Furthermore, the calculated values of σ/τ, ke/τ, S, χ, PF, and ZT in the temperature range of 200-800 K highlight the potential of these compounds for thermoelectric applications. This comprehensive analysis underscores the suitability of Sr2XOsO6 (X = Y, Lu, Sc) for advanced electronic and spintronic technologies.