Absorption Spectroscopy Research Articles

Synthesis and characterization of titanium oxynitride catalyst via direct ammonia nitridation of titanium polyacrylate for oxygen reduction reaction

AbstractA titanium oxynitride catalyst for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells was synthesized through the direct ammonia nitridation of titanium complexes. Titanium polyacrylate was employed as the catalyst precursor, and the effect of the calcination temperature between 600 and 1000 °C on the catalyst structure was studied. The catalysts were characterized via X-ray diffraction, X-ray absorption spectroscopy, transmission electron microscopy, cyclic voltammetry, and powder electrical resistivity measurements. The formation of titanium oxynitride particles and deposited carbon was observed for all the samples; however, significant variations in the catalyst structure and catalytic activity were also observed. With an increase in the calcination temperature, nitridation of titanium oxynitride progressed, and the conductivity of the catalyst powder increased. The highest rest potential and ORR current density were achieved with calcination at 800 °C. Importantly, the results suggest that maintaining an optimal nitrogen doping level within the catalyst particles, along with ensuring the formation of electroconductive deposited carbon, is essential for achieving a high ORR current. This work introduces the direct ammonia nitridation of metal complexes as a promising process for designing metal oxynitride catalysts.

Excited State Dynamics of Geometrical Evolution of α-Substituted Dibenzoylmethanatoboron Difluoride Complex with Aggregation-Induced Emission Property.

Organic molecules with an aggregation-induced emission (AIE) property have been attracting much attention from the viewpoint of application to solid state emissive materials. For the AIE mechanism, quantum mechanical studies proposed the restriction of the intramolecular motion (RIM) model with the contribution of the conical intersection (CI) and deduced the importance of the restricted access to a conical intersection (RACI) in the potential energy surface (PES). Although these theoretical studies have contributed to the elucidation of AIE phenomena, direct detection of the reaction dynamics is indispensable to clarify the actual PES and the deactivation mechanism. Along this line, we investigated excited state dynamics of the AIE molecule with dibenzoylmethanatoboron difluoride complexes using time-resolved absorption spectroscopies in both visible and infrared (IR) regions. While the reference system of 1,3-bis(4-methoxyphenyl)methanatoboron difluoride (2aBF2) showed strong emission in solution, the methyl-substituted derivative at the α-position of the dioxaborine ring (2amBF2) led to the very weak fluorescence in solution but strong emission in the solid state. Time-resolved visible absorption measurements revealed a peak shift and broadening of the stimulated emission in the solution of 2amBF2, owing to the rapid change of the molecular geometry. With the temporal evolution of time-resolved IR absorption signals and density functional theory (DFT) calculation of these systems, it was deduced that 2amBF2 has two stable geometries, namely, planar and bending, in the S1 state and the bending geometry in the S1 state led to rapid conversion to the S0 state. These results support the RACI model in the aggregated states, leading to the AIE properties.

Fabrication of tannic acid-incorporated polyvinylpyrrolidone/polyvinyl alcohol composite hydrogel and its application as an adsorbent for copper ion removal.

An effective tannic acid-incorporated polyvinylpyrrolidone/polyvinyl alcohol composite hydrogel with high-potential sorption capacity was developed for the removal of copper from aqueous solution. The composite hydrogel exhibited pH-dependent swelling, in which swelling and shrinking occurred reversibly with adjustment of the pH of the medium. At pH 4, the maximal adsorption capacity for copper at 30°C was 297.0mg g-1, and the adsorbent dose was 4g L-1. The adsorption kinetics were best fitted with a pseudo-second order kinetic model. The adsorption behavior was well predicted by the Freundlish isotherm. The thermodynamics parameters indicated a spontaneous and exothermic reaction with an increase in the entropy of the system. The chemical changes in the film structure before and after adsorption treatment were characterized by Scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS). The FTIR, XPS and XAS results confirmed that Cu bound to the oxygens in the -OH, C = O and N-(C = O)- functional groups on the T-HD. XAS analysis revealed the chemical composition and molecular geometry of the adsorbed copper ions. The single-solute adsorption and coadsorption mechanisms, which provide insight into cobalt-copper, nickel-copper, or nickel-cobalt-copper complex solutions, were investigated. The composite hydrogel exhibited excellent regeneration ability in EDTA solution. Notably, the adsorbent retained an adsorption efficiency exceeding 87% even after five regeneration cycles. On the basis of both adsorbent characteristics and adsorption performance, it was determined that the composite hydrogel has the potential to be used as a platform for developing materials to treat wastewater containing high levels of metal contaminants such as those from the electroplating industry.

The Electrode/Electrolyte Interface Study during the Electrochemical CO2 Reduction in Acidic Electrolytes

AbstractElectrochemical CO2 Reduction (CO2R) in acidic electrolytes has gained significant attention owing to higher carbon efficiency and stability than in alkaline counterparts. However, the proton source and the role of alkali cations for CO2R are still under debate. By using rotating ring disk electrode and surface‐enhanced infrared absorption spectroscopy, we find that a neutral/alkaline environment at the interface is necessary for CO2R even in acidic electrolytes. We also confirm that water molecules, rather than protons serve as the proton source for CO2R. Alkali cations in the outer Helmholtz plane activate H2O and promote the desorption of adsorbed carbon monoxide. Additionally, the solvated CO2, or CO2(aq), is the actual reactant for CO2R. This study provides a deeper understanding of the electrode/electrolyte interface during CO2R in acidic electrolytes and sheds light on further performance improvement of this system.

Association of whole blood essential metals with neurodevelopment among preschool children.

Essential metals may play roles in neurodevelopment. The aim was to evaluate the associations of magnesium (Mg), iron (Fe), copper (Cu), and zinc (Zn) levels with neurodevelopment among preschool children. The medical records of eligible children enrolled between January 2019 and July 2022 were retrospectively reviewed for required information. The quantitative measurement of metals was conducted using atomic absorption spectroscopy, while screening of neurodevelopment was performed using the Ages and Stages Questionnaire. Modified Poisson regression and Bayesian kernel machine regression (BKMR) analyses were used to evaluate the prevalence ratio (PR) of their independent and joint associations. 662 (14.8%) children were found to have possible neurodevelopmental delays. Modified Poisson regression showed that Mg, Cu, and Zn levels were independently and negatively associated with the risk of neurodevelopmental delay. The PRs (95% CIs) for per log2 increment of the above metals were 0.35 (0.19-0.62), 0.57 (0.42-0.77), and 0.63 (0.42-0.96). These negative associations were more pronounced in the gross motor and personal-social domains while considering the concrete five domains. BKMR showed a negative association of metal mixture with the risk of neurodevelopmental delay. Mg, Cu, and Zn were inversely associated with neurodevelopmental delay. Sufficient essential metal levels are important for neurodevelopment. Essential metals play a key role in neurodevelopment. The association of essential metal mixture with neurodevelopment is relatively scarce. Preschool children with possible neurodevelopmental delay are found to have lower Mg, Cu, and Zn levels than their counterparts. Single Mg, Cu, Zn levels, and elevated essential metal mixture are negatively associated with the risk of possible neurodevelopmental delay.

Hiding in plain sight: The prevalence and impact of trions and Fermi polarons in transient absorption spectroscopy experiments of 2D semiconductors.

Transient absorption (TA) spectroscopy is one of the most popular experimental methods to measure the excited state lifetimes and charge carrier recombination mechanisms in two dimensional (2D) semiconductors. This fundamental information is essential for designing and optimizing the next generation of ultrathin and lightweight 2D semiconductor-based optoelectronic devices. However, the interpretation of TA spectroscopy data varies across the community. The community lacks a unifying physical explanation for how and why experimental variables such as incident light intensity, sample-substrate interactions, and/or applied bias affect TA spectral data. This Perspective (1) compares the physical chemistry TA literature to nanomaterial physics literature from a historical perspective, (2) reviews multiple physical explanations that the TA community developed to explain spectral features and experimental trends, (3) provides a unifying explanation for how and why trions-and, more generally, Fermi polarons-contribute to TA spectra, and (4) quantifies the extent to which various physical interpretations and data analysis procedures yield different timescales and mechanisms for the same set of experimental results. We highlight the importance of considering trions/Fermi polarons in TA measurements and their implications for advancing our understanding of 2D material properties.

Antitumoral action of carvedilol–a repositioning study of the drug incorporated into mesoporous silica MCM-41

We have studied repositioning of carvedilol (an antihypertensive drug) incorporated into MCM-41 mesoporous silica. The repositioning proposes a reduction in the slow pace of discovery of new drugs, as well as toxicological safety and a significant reduction in high research costs, making it an attractive strategy for researchers and large pharmaceutical companies. We obtained MCM-41 bytemplatesynthesis and functionalized it by post-synthesis grafting with aminopropyltriethoxysilane (APTES) only or with folic acid (FA), which gave MCM-41-APTES and MCM-41-APTES-FA, respectively. We characterized the materials by scanning and transmission electron microscopy, zeta potential (ZP) measurements, Fourier transform infrared absorption spectroscopy, x-ray diffractometry, nitrogen gas adsorption, and CHNS elemental analysis. We quantified the percentage of drug that was incorporated into the MCM-41 materials by thermogravimetric analysis and evaluated their cytotoxic activity in non-tumor human lung fibroblasts and the tumor human melanoma and human cervical adenocarcinoma cell lines by XTT salt reduction (2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-arboxanilide). The x-ray diffractograms of the MCM-41 materials displayed low-angle peaks in the 2θrange between 2° and 3°, and the materials presented type IV nitrogen adsorption isotherms and H2 hysteresis typical of the MCM-41hexagonal network. The infrared spectra, the charge changes revealed by ZP measurements, and the CHN ratios obtained from elemental analysis showed that MCM-41 was amino-functionalized, and that carvedilol was incorporated into it. MCM-41-APTES incorporated 23.80% carvedilol, whereas MCM-41 and MCM-41-APTES-FA incorporated 18.69% and 12.71% carvedilol, respectively. Incorporated carvedilol was less cytotoxic to tumor and non-tumor cells than the pure drug. Carvedilol repositioning proved favorable and encourages further studies aimed at reducing its cytotoxicity to non-tumor cells. Such studies may allow for larger carvedilol incorporation into drug carriers or motivate the search for a new drug nanocarrier to optimize the carvedilol antitumoral activity.

The global daily High Spatial–Temporal Coverage Merged tropospheric NO2 dataset (HSTCM-NO2) from 2007 to 2022 based on OMI and GOME-2

Abstract. Remote sensing based on satellites can provide long-term, consistent, and global coverage of NO2 (an important atmospheric air pollutant) as well as other trace gases. However, satellites often miss data due to factors including but not limited to clouds, surface features, and aerosols. Moreover, as one of the longest continuous observational platforms of NO2, the Ozone Monitoring Instrument (OMI) has suffered from missing data over certain rows since 2007, significantly reducing its spatial coverage. This work uses the OMI-based tropospheric NO2 (OMNO2) product as well as a NO2 product from the Global Ozone Monitoring Experiment-2 (GOME-2) in combination with machine learning (eXtreme Gradient Boosting – XGBoost) and spatial interpolation (data-interpolating empirical orthogonal function – DINEOF) methods to produce the 16-year global daily High Spatial–Temporal Coverage Merged tropospheric NO2 dataset (HSTCM-NO2; https://doi.org/10.5281/zenodo.10968462; Qin et al., 2024), which increases the average global spatial coverage of NO2 from 39.5 % to 99.1 %. The HSTCM-NO2 dataset is validated using upward-looking observations of NO2 (multi-axis differential optical absorption spectroscopy – MAX-DOAS), other satellites (the Tropospheric Monitoring Instrument – TROPOMI), and reanalysis products. The comparisons show that HSTCM-NO2 maintains a good correlation with the magnitudes of other observational datasets, except for under heavily polluted conditions (> 6 × 1015 molec.cm-2). This work also introduces a new validation technique to validate coherent spatial and temporal signals (empirical orthogonal function – EOF) and confirms that HSTCM-NO2 is not only consistent with the original OMNO2 data but in some parts of the world also effectively fills in missing gaps and yields a superior result when analyzing long-range atmospheric transport of NO2. The few differences are also reported to be related to areas in which the original OMNO2 signal was very low, which has been shown elsewhere but not from this perspective, further confirming that applying a minimum cutoff to retrieved NO2 data is essential. The reconstructed data product can effectively extend the utilization value of the original OMNO2 data, and the data quality of HSTCM-NO2 can meet the needs of scientific research.

Phytochemical screening, nutritional, antinutritional, antioxidant, GCMS and mineral analysis of Zanthoxylum rhetsa (Roxb.) DC: Insights from tribal consumption in Mizoram, Northeast India

The plant Zanthoxylum rhetsa Roxb, a member of the Rutaceae family, holds dual significance in certain communities, particularly in Mizoram, Northeast India, where it is valued for its medicinal properties and consumed as a vegetable. This study comprehensively analyzes the phytochemical, nutritional, antinutritional, and antioxidant properties and the mineral content of Z. rhetsa, a plant traditionally consumed by tribal communities in this region. Minerals such as aluminum, copper, iron, manganese, nickel, and zinc were measured using Atomic Absorption Spectroscopy (AAS). Gas Chromatography-Mass Spectrometry (GC-MS) analysis was conducted to determine the chemical composition of the samples. Phytochemical screening revealed the existence of several bioactive components, such as tannins and flavonoids, while nutritional studies validated the plant's abundance of key nutrients. Among the minerals, manganese was found in the highest concentration (481.356 mg/100 g of DW), while nickel was present in the lowest concentration (1.614 mg/100 g of DW). The total calorific content was ascertained to be 51.344 Kcal/100g, adequate for dietary requirements. Additionally, the total phenolic content measured was 8.28 mg/g in gallic acid equivalent, and the total flavonoid content was 43.04 mg/g in quercetin equivalents. The existence of antinutritional compounds in differing amounts necessitates meticulous evaluation, particularly with the intake of fruits that may possess elevated levels of these substances. This comprehensive assessment highlights the nutritional significance of Z. rhetsa in local diets, emphasizing its dual role as a source of beneficial nutrients and potential antinutritional factors.

Determination of Metal Cadmium (Cd), Copper (Cu), Iron (Fe) and Zinc (Zn) in Drinking Water from The Boring Well of Surbakti Village, Karo District by Atomic Absorption Spectrophotometry Method

Water is an essential requirement for human existence. In addition to traditional water usage, water is essential for enhancing the quality of human existence and facilitating industrial and technological endeavors. An investigation was conducted on the contents of Cadmium (Cd), Copper (Cu), Iron (Fe), and Zinc (Zn) in drinking water from drilled wells in Surbakti Village, Karo District, employing Atomic Absorption Spectrophotometry (AAS) techniques. Sampling occurred during weeks 1, 2, 3, 4, and 5 and was subsequently digested with concentrated nitric acid until a volume of 15 mL was attained. The metal concentrations of Cd, Cu, Fe, and Zn were quantified using Atomic Absorption Spectroscopy (AAS) using a calibration curve. The findings indicated a concentration of Cd at 0.0031 mg/L, Cu at 0.0470 mg/L, Fe at 0.2741 mg/L, and Zn at 0.2929 mg/L. In this instance, Cd produced a greater concentration of drinking water standards compared to Cu, Fe, and Zn. Nonetheless, it nonetheless met the drinking quality standards established by Regulation Minister of Health No. 492/Menkes/Per/VII/2010.

Programmed Charge Transfer in Conjugated Polymers with Pendant Benzothiadiazole Acceptor for Simultaneous Photocatalytic H2O2 Production and Organic Synthesis.

While being important candidate for heterogeneous photocatalyst, conjugated polymer typically exhibits random charge transfers between the alternating donor and acceptor units, which severely limits its catalytic efficiency. Herein, inspired by natural photosystem, the concept of guiding the charge migration to specific reaction sites is employed to significantly boost photocatalytic performance of linear conjugated polymers (LCPs) with pendant functional groups via creating programmed charge-transfer channels from the backbone to its pendant moiety. The pendant benzothiadiazole, as revealed in both in situ X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations, can act as electron "reservoir" that aggregates electrons at the active sites. Moreover, the presence of charge-transfer channels, evidenced by transient absorption spectroscopy (TAS), accelerates the electron transfer, preventing the recombination of electrons and holes. As a result, in this elaborately-designed architecture, the photogenerated electron can move smoothly towards the reduction sites, facilitating the reduction of O2 into H2O2, while remaining holes are directed to oxidation centers, simultaneously oxidizing furfuryl alcohol to furoic acid. The optimized photocatalyst LCP-BT demonstrates a competitive catalytic performance with H2O2 productivity of 868.3 μmol L-1 h-1 (9.8 times higher than conventional random charge-transfer polymer LCP-1) and furfuryl alcohol conversion over 95% after 6 h.

Computational Study on the Octahedral Surfaces of Magnetite Nanoparticles and Their Solvent Interaction.

Magnetite nanoparticles (MNPs) play an important role in geological and environmental systems because of their redox reactivity and ability to sequester a wide range of metals and metalloids. X-ray absorption spectroscopy conducted at metal and metalloid edges has suggested that the magnetite {111} faces of octahedrally shaped nanoparticles play a dominant role in the redox and sorption processes of these elements. However, studies directly probing the magnetite surfaces, especially in their fully solvated state, are scarce. Therefore, we investigated the speciation and stability over a wide Eh/pH range of octahedrally shaped MNPs of 2 nm size by means of Kohn-Sham density functional theory with Hubbard correction (DFT+U). By altering the protonation state of the crystals, a redox-sensitive response of the octahedrally coordinated Fe could be achieved. Furthermore, the preferential H distribution could be identified, highlighting the difference between the edges, vertices, and facets of the nanocrystals. Subsequently, the interactions of the MNPs with a solvent of pure water or a 0.5 M NaCl solution were studied by classical molecular dynamics (MD) simulations. Finally, a comparison of the corresponding macroscopic magnetite (111) surface to the investigated MNPs was conducted.

Direct visualization of the charge transfer state dynamics in dilute-donor organic photovoltaic blends.

The interconversion dynamics between charge transfer state charges (CTCs) and separated charges (SCs) is still an unresolved issue in the field of organic photovoltaics. Here, a transient absorption spectroscopy (TAS) study of a thermally evaporated small-molecule:fullerene system (α6T:C60) in different morphologies (dilute intermixed and phase separated) is presented. Spectral decomposition reveals two charge species with distinct absorption characteristics and different dynamics. Using time-dependent density functional theory, these species are identified as CTCs and SCs, where the spectral differences arise from broken symmetry in the charge transfer state that turns forbidden transitions into allowed ones. Based on this assignment, a kinetic model is formulated allowing the characterization of the charge generation, separation, and recombination mechanisms. We find that SCs are either formed directly from excitons within a few picoseconds or more slowly (~30-80 ps) from reversible splitting of CTCs. These findings constitute the first unambiguous observation of spectrally resolved CTCs and SCs.

Synergistic Catalytic Sites in High-Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction.

The integration of multiple elements in a high-entropy state is crucial in the design of high-performance, durable electrocatalysts. High-entropy metal hydroxide organic frameworks (HE-MHOFs) are synthesized under mild solvothermal conditions. This novel crystalline metal-organic framework (MOF) features a random, homogeneous distribution of cations within high-entropy hydroxide layers. HE-MHOF exhibits excellent electrocatalytic performance for the oxygen evolution reaction (OER), reaching a current density of 100mA cm-2 at ≈1.64 VRHE, and demonstrates remarkable durability, maintaining a current density of 10mA cm-2 for over 100 h. Notably, HE-MHOF outperforms precious metal-based electrocatalysts despite containing only ≈60% OER active metals. Ab initio calculations and operando X-ray absorption spectroscopy (XAS) demonstrate that the high-entropy catalyst contains active sites that facilitate a multifaceted OER mechanism. This study highlights the benefits of high-entropy MOFs in developing noble metal-free electrocatalysts, reducing reliance on precious metals, lowering metal loading (especially for Ni, Co, and Mn), and ultimately reducing costs for sustainable water electrolysis technologies.

Increasing Precursor Reactivity Enables Continuous Tunability of Copper Nanocrystals from Single-Crystalline to Twinned and Stacking Fault-Lined.

Colloidal nanocrystals (NCs) are active materials in different applications, wherein their shape dictates their properties, such as optical or catalytic properties, and, thus, their performance. Hence, learning to tune the NC shape is an important goal in chemistry, with implications in other fields of research. A knowledge gap exists in the chemistry of non-noble metals, wherein design rules for shape control of NCs are still poorly defined compared to those of other classes of materials. Herein, we demonstrate that tuning the precursor reactivity is crucial to obtaining a continuous shape modulation from single-crystalline to twinned and stacking fault-lined Cu NCs. This tunability is unprecedented for non-noble metal NCs. We achieve this result by using diphenylphosphine in place of the most commonly used trioctylphosphine. Using in situ X-ray absorption spectroscopy, we show that the temperature modifies the reaction kinetics of an in situ-forming copper(I)bromide-diphenylphosphine complex during the synthesis of Cu NCs. We propose the presence of a P-H functionality in the phosphine to explain the higher reactivity of this precursor complex formed with diphenylphosphine compared to that formed with trioctylphosphine. This work inspires future studies on the role of phosphine ligands during the synthesis of Cu NCs to rationally target new morphologies, such as high-index faceted Cu NCs, and can be conceptually translated to other transition-metal NCs.

Achieving High Photocatalytic NOx Removal Activity Using a Bi/BiOBr/TiO2 Composite Photocatalyst.

Fossil fuel combustion generates nitrogen oxides (NO + NO2 = NOx), which pose threats to the environment and human health. Although commercial products containing titanium dioxide (TiO2) can remedy NOx pollution by photocatalysis, they only function in the ultraviolet (UV). On the other hand, bismuth oxybromide (BiOBr) is active in the visible. BiOBr is stable, affordable, and non-toxic, making it an appealing alternative. In addition, nanoparticulate Bi metal can further enhance visible light absorption through its surface plasmon properties and charge carrier lifetime by spatially separating charge. In this study, to enhance the visible-light activity of TiO2-based photocatalysts for NOx pollution, a composite of Bi-decorated BiOBr/TiO2 was synthesized using a solvothermal method across varying the Ti/Bi atomic ratio (0.2, 2.2, 4.4, and 6.6), and synthesis duration (6h, 12h, and 18h). The photocatalytic performance of the synthesised composites for NO gas removal was investigated using an adapted ISO method (22197-1:2016). Analysis showed that the preferential growth of the (010) crystal facet in BiOBr and the presence of Bi metal both play an important role in the superior photocatalytic activity seen in our Bi-decorated BiOBr/TiO2 composite. The composites were characterised using X-ray diffraction (XRD), attenuated total reflectance - Fourier transform infrared spectroscopy (ATR-FTIR), high-resolution scanning electron microscopy (HRSEM), UV-Vis diffuse reflectance (DRS) spectroscopy, transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Brunauer-Emmett-Teller (BET) analysis, thermogravimetric analysis (TGA), and diffuse reflectance transient absorption spectroscopy (DR-TAS). Our research shows that the Bi/BiOBr-TiO2 composite synthesised through the 12-hour solvothermal method with a Ti/Bi atomic ratio of 4.4 exhibits the highest photocatalytic performance towards both NO and NO2 oxidation; with 32.8% and 54.9% NO removal and 15.1% and 29.5% NO2 under visible and UV lamps, respectively.

Modulating RuO2 Electrocatalysis via Introducing Lanthanides for Enhanced Acidic Oxygen Evolution

AbstractThe low activity of ruthenium dioxide (RuO2) and the rapid dissolution of the ruthenium (Ru) site during acid oxygen evolution reaction (OER) at high current density restricts its application in proton exchange membrane (PEM) electrolyzers. In this work, a series of rare‐earth (RE) elements doped RuO2 nanorods is developed as high‐performance OER electrocatalysts. X‐ray absorption spectroscopy suggests that RE doping regulates the local coordination environment around Ru sites, lowers the valance of Ru, and shortens the Ru─O─Ru(M) bond length, which enhances structural stability. Among the RE‐RuO2 samples, Sm‐RuO2 exhibits remarkable performance with a low overpotential of 283 mV to reach 100 mA cm−2 and maintained stability for over 140 h at 10 mA cm−2. Moreover, the PEM electrolyzer using Sm‐RuO2 as the anode can be stably operated at 500 mA cm−2 for 15 h. Electrochemical analysis, X‐ray photoelectron spectroscopy, and in situ Raman spectroscopy show that Sm doping lowers the d‐band center, reduces the adsorption energy of O intermediates to enhance the OER activity, and restrains excessive oxidation of Ru sites while stabilizing lattice oxygen during the OER process, thereby enhancing OER stability. This work offers valuable insights into improving the stability of metal oxide catalysts in acidic electrolytes.

Prolonging Charge Carrier lifetime via Intraband Defect Levels in S-scheme Heterojunctions for Artificial Photosynthesis.

S-scheme heterostructure photocatalysts, distinguished by unique charge-transfer pathways and exceptional catalytic redox capabilities, have found widespread applications in addressing challenging chemical processes, including the photocatalytic reduction of CO2 with a high reaction barrier. Nevertheless, the influence of intraband defect levels within S-scheme heterojunctions on charge separation, carrier lifetime, and surface catalytic reactions has, for the most part, been overlooked. Herein, we develop a tunable defect-level-assisted strategy to construct an electron reservoir, effectively prolonging the lifetime of charge carriers through the rapid capture and gradual release of photoelectrons within WO3-x/In2S3 S-scheme heterojunctions, as authenticated by femtosecond transient absorption spectroscopy and theoretical simulations. The surface photoredox mechanism, unraveled by Gibbs free energy calculations, demonstrates that oxygen-vacancy-induced defect states in WO3-x/In2S3 heterojunctions unlock the rate-determining H2O oxidation into free oxygen molecules by forming metastable oxygen intermediates, contributing to the facilitation of H2O photooxidation. This distinct role, combined with the extended carrier lifetime, results in boosted CO2 photoreduction with nearly 100% CO selectivity in the absence of any photosensitizer or scavenger. Our work sheds light on the role of controllable defect levels in governing charge transfer dynamics within S-scheme heterojunctions, thereby inspiring the development of more advanced photocatalysts for artificial photosynthesis.

Perfluorocarbons: a material platform for tunable nonlinear frequency conversion in liquid filled suspended core fibers

This study investigates supercontinuum generation in suspended core fibers filled with perfluorocarbons, highlighting their potential for ultrafast nonlinear frequency conversion. Spectroscopic absorption and refractive index dispersions are analyzed for three perfluorocarbons in the visible and near-infrared. Experiments show that the insertion of these liquids into suspended core fibers changes the dispersion landscape, enabling broadband soliton-based supercontinuum generation from 0.6 µm to 2.4 µm due to the creation of a confined domain of anomalous dispersion in the telecom range. In addition, temperature-dependent output spectrum modulation is demonstrated, highlighting the utility of the platform in photonic applications such as spectroscopy, sensing, and microscopy.

Reassessing the Photochemical Upcycling of Polystyrene Using Acridinium Salts.

Approaches aimed at deconstructing PS by photocatalytic means struggle to generate high-energy species capable of cleaving the C-H and C-C bonds of PS. We show herein that 9-mesityl-10-methylacridinium perchlorate (MA) is capable of upcycling various grades of PS susbstrates into benzoic acid (BAc) up to 40%, with small proportions of acetophenone and formic acid, under visible light (456 nm) or through solar radiation. Time-resolved emission and absorption spectroscopy evidence that a reaction with oxygen is the primary photochemical step in oxygen-saturated solutions, accounting for 77% of the photons absorbed vs. 1% for the direct reaction with PS. These results suggest a mechanism in which MA-mediated photocycling of PS to BAc occurs through the abstraction of benzylic H atoms by reactive oxygen species generated by energy or electron transfer from the excited state of MA. Addition of triplet O2 to these radicals, followed by intra- or inter-molecular hydrogen atom transfer (HAT), generates C- or O-centered radicals then undergoing β-scission or hydroperoxide fragmentation. The formation of intermediate oligomers functionalized by terminal carbonyl groups is demonstrated by both infrared analysis and mass spectrometry. These oligomers undergo further photoinduced conversion in the absence of MA, as evidenced by size exclusion chromatography analysis.