A new method for the rapid identification of external water types in rainwater pipeline networks using UV-Vis absorption spectroscopy.

Ultraviolet-visible (UV-Vis) absorption spectroscopy, due to its high sensitivity and capability for real-time online monitoring, is one of the most promising tools for the rapid identification of external water in rainwater pipe networks. However, difficulties in obtaining actual samples lead to insufficient real samples, and the complex composition of wastewater can affect the accurate traceability analysis of external water in rainwater pipe networks. In this study, a new method for identifying external water in rainwater pipe networks with a small number of samples is proposed. In this method, the Generative Adversarial Network (GAN) algorithm was initially used to generate spectral data from the absorption spectra of water samples; subsequently, the multiplicative scatter correction (MSC) algorithm was applied to process the UV-Vis absorption spectra of different types of water samples; following this, the Variational Mode Decomposition (VMD) algorithm was employed to decompose and recombine the spectra after MSC; and finally, the long short-term memory (LSTM) algorithm was used to establish the identification model between the recombined spectra and the water source types, and to determine the optimal number of decomposed spectra K. The research results show that when the number of decomposed spectra K is 5, the identification accuracy for different sources of domestic sewage, surface water, and industrial wastewater is the highest, with an overall accuracy of 98.81%. Additionally, the performance of this method was validated by mixed water samples (combinations of rainwater and domestic sewage, rainwater and surface water, and rainwater and industrial wastewater). The results indicate that the accuracy of the proposed method in identifying the source of external water in rainwater reaches 98.99%, with detection time within 10 s. Therefore, the proposed method can become a potential approach for rapid identification and traceability analysis of external water in rainwater pipe networks.

A nonparametric point-by-point method to measure time-dependent frequency in wavelength modulation spectroscopy.

A nonparametric point-by-point (NPP) method is presented for high-accuracy measurement of the time-dependent frequency (laser frequency) in tunable laser absorption spectroscopy, crucial for ensuring ultimate measurement accuracy. In wavelength modulation spectroscopy in particular, the parametric methods in current use for time-dependent frequency measurement are insufficiently accurate and are difficult to apply to complex modulation scenarios. Based on a multi-scale viewpoint, point-by-point measurement of the frequency is realized by linear superposition of the frequency information mapped from the interferometric signal on a unit scale and on a local scale. Validation experiments indicate that the measurement accuracy of the proposed NPP method is three times that of the existing parametric methods, while effectively immunizing against non-ideal tuning effects. Additionally, the NPP method is suitable for use with arbitrarily complex modulations such as square wave modulation, for which parametric methods are inapplicable.

Uranium Repartitioning during Microbial Driven Reductive Transformation of U(VI)-Sorbed Schwertmannite and Jarosite.

This study exposes U(VI)-sorbed schwertmannite and jarosite to biotic reductive incubations under field-relevant conditions and examines the changes in aqueous and solid-phase speciation of U, Fe, and S as well as associated microbial communities over 180 days. The chemical, X-ray absorption spectroscopy, X-ray diffraction, and microscopic data demonstrated that the U(VI)-sorbed schwertmannite underwent a rapid reductive dissolution and solid-phase transformation to goethite, during which the surface-sorbed U(VI) was partly reduced and mostly repartitioned to monomeric U(VI)/U(IV) complexes by carboxyl and phosphoryl ligands on biomass or organic substances. Furthermore, the microbial data suggest that these processes were likely driven by the consecutive developments of fermentative and sulfate- and iron- reducing microbial communities. In contrast, the U(VI)-sorbed jarosite only stimulated the growth of some fermentative communities and underwent very limited reductive dissolution and thus, remaining in its initial state with no detectable mineralogical transformation and solid-phase U reduction/repartitioning. Accordingly, these two biotic incubations did not induce increased risk of U reliberation to the aqueous phase. These findings have important implications for understanding the interactions of schwertmannite/jarosite with microbial communities and colinked behavior and fate of U following the establishment of reducing conditions in various acidic and U-rich settings.

Thermochemical Transformation of Calcium during Biomass Burning and the Effects on Postfire Aqueous Dissolution of Macronutrients.

Calcium is commonly the most abundant element in fire residues and its speciation largely determines the geochemical properties of fire residues and their effects on postfire soil chemistry. To explore the effects of biomass composition and fire conditions on ash Ca speciation, this study characterizes the speciation of Ca in charcoal and ash samples that were derived from different plant compartments and thermal conditions, using Ca K-edge X-ray absorption near edge spectroscopy. Results showed that biomass contains abundant organic Ca complexes, which were mineralized into fairchildite and calcite after heating at 450 to 600 °C and then CaO, as temperature increased to 750 °C. Apatite could be an abundant Ca species in fire residues if the Ca/P molar ratio of the biomass is small (<2). The mineralization of organic Ca to the identified Ca minerals during burning was negligibly affected by the oxygen level. Calcium speciation in prescribed fire residues resembled that of biomass ash burned at 550 °C with similar Ca/P molar ratios. Batch experiments showed that macronutrients (Ca, Mg, K, and P) were differentially released, as a result of different solubility of minerals in ashes and reprecipitation of minerals. The aqueous solubility of Ca, Mg, and P decreased as pH increased from 5 to 9, while K showed no pH dependency and was almost completely soluble. Results from this study improve our understanding of the chemistry of fire residues and their geochemical behaviors, which can help evaluate the impact of fire on postfire soil properties and macronutrient cycling.

Atomic Manipulation to Create High-Valent Fe4+ for Efficient and Ultrastable Oxygen Evolution at Industrial-Level Current Density.

Manipulating the electronic structure of a catalyst at the atomic level is an effective but challenging way to improve the catalytic performance. Here, by stretching the Fe-O bond in FeOOH with an inserted Mo atom, a Fe-O-Mo unit can be created, which will induce the formation of high-valent Fe4+ during the alkaline oxygen evolution reaction (OER). The highly active Fe4+ state has been clearly revealed by in situ X-ray absorption spectroscopy, which can both enhance the oxidation capability and lead to an efficient and stable adsorbate evolution mechanism (AEM) pathway for the OER. As a result, the obtained Fe-Mo-Ni3S2 catalyst exhibits both superior OER activity and outstanding stability, which can achieve an industrial-level current density of 1 A cm-2 at a low overpotential of 259 mV (at 60 °C) and can stably work at the large current for more than 2000 h. Moreover, by coupling with commercial Pt/C, the Fe-Mo-Ni3S2∥Pt/C system can be used in the anion exchange membrane cell to acquire 1 A cm-2 for overall water splitting at 1.68 V (2.03 V for 4 A cm-2), outperforming the benchmark RuO2∥Pt/C system. The efficient, low-cost, and ultrastable OER catalyst enabled by manipulating the atomic structure may provide potential opportunities for future practical water splitting.

The AUREX cell: a versatile operando electrochemical cell for studying catalytic materials using X-ray diffraction, total scattering and X-ray absorption spectroscopy under working conditions.

Understanding the structure-property relationship in electrocatalysts under working conditions is crucial for the rational design of novel and improved catalytic materials. This paper presents the Aarhus University reactor for electrochemical studies using X-rays (AUREX) operando electrocatalytic flow cell, designed as an easy-to-use versatile setup with a minimal background contribution and a uniform flow field to limit concentration polarization and handle gas formation. The cell has been employed to measure operando total scattering, diffraction and absorption spectroscopy as well as simultaneous combinations thereof on a commercial silver electrocatalyst for proof of concept. This combination of operando techniques allows for monitoring of the short-, medium- and long-range structure under working conditions, including an applied potential, liquid electrolyte and local reaction environment. The structural transformations of the Ag electrocatalyst are monitored with non-negative matrix factorization, linear combination analysis, the Pearson correlation coefficient matrix, and refinements in both real and reciprocal space. Upon application of an oxidative potential in an Ar-saturated aqueous 0.1 M KHCO3/K2CO3 electrolyte, the face-centered cubic (f.c.c.) Ag gradually transforms first to a trigonal Ag2CO3 phase, followed by the formation of a monoclinic Ag2CO3 phase. A reducing potential immediately reverts the structure to the Ag (f.c.c.) phase. Following the electrochemical-reaction-induced phase transitions is of fundamental interest and necessary for understanding and improving the stability of electrocatalysts, and the operando cell proves a versatile setup for probing this. In addition, it is demonstrated that, when studying electrochemical reactions, a high energy or short exposure time is needed to circumvent beam-induced effects.

Wavelength modulation spectroscopy of nitric oxide using a quantum cascade laser in intermittent continuous wave operation.

Operating quantum cascade lasers (QCLs) in intermittent continuous wave (iCW) shows the merit of a broader frequency tuning range and lower heat dissipation compared to the continuous wave (CW) operation. We demonstrate for the first time wavelength modulation spectroscopy (WMS) of a QCL in iCW operation for sensitive gas detection. A strong absorption line of nitric oxide (NO) at 5.18 µm is exploited by a QCL in iCW mode, which periodically switches off the QCL between individual laser scans. The generated thermal chirp dominates the laser frequency tuning, resulting in a broader spectral coverage of more than 2 cm-1 at a scanning rate of 1 kHz. In addition, a high-frequency dither (50 kHz) is supposed onto this iCW injection current to introduce the harmonic signals that arise from gas absorption. At the WMS-iCW operation of the QCL, we have obtained a minimum detection limit of 4.5 ppb at an averaging time of 80 s, which is improved significantly compared to 130 ppb achieved by direct absorption spectroscopy at the same averaging time using the identical optical setup, without external forced air- or water-cooling. Our method provides a promising method for sensor miniaturization and field application.

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

Electrochemical 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.

Solvent Polarity Dependent Ultrafast Relaxation Kinetics of ADS800AT Dye.

This work investigated the photoexcitation and relaxation kinetics of the ADS800AT dye dissolved in different solvents using transient absorption spectroscopy (TAS) with a white-light continuum probe. The dye was dissolved in various solvents, including dichloromethane (DCM), 1,2-dichlorobenzene (DCB), ethanol, and methanol, to study their impact on the dye's characteristics. The linear absorption peak varied from 835 to 809 nm, depending on the polarity of the solvent, and the pump wavelength for TAS was chosen accordingly. We observed ground-state bleaching and excited-state absorption after exciting the dye with the pump pulse. Global analysis was performed using Glotaran software to fit exponential decay curve models, allowing us to determine the relaxation time of the excited molecule. The relaxation time varied from 198 ps to 508 ps across the different solvents, decreasing as the polarity of the solvent increased. Additionally, we could experimentally correlate the dye molecule's nonlinear properties with the solvent's polarity.

Data on vermicompost effect on the uptake of cadmium from soil by the roots of radish (Raphanus sativus).

Cadmium is a common environmental heavy metal that is very toxic and carcinogenic for human and other flora and fauna. Therefore, this study is aimed to evaluate the fisibility of vermicompost fertilizer for cadmium uptake from soil by the root of radish (Raphanus sativus). For the purpose of the study, four different ratios of one case control, 1 per 1, 1 per 4, 2 per 4, 3 per 4 vermicompost fertilizer per soil with 0, 50000 and 100000 µg/L cadmium concentrations was evaluated. Cadmium in the samples was measured using an Atomic Absorption Spectroscopy (AAS). The results showed that the minimum uptake of cadmium by the plant was observed for 3 per 4 ratio of fertilizer per soil. In addition, results revealed that highest growth rate of Raphanus sativus roots occurred in maximum ratio of fertilizer per soil usage (3 per 4). This study showed that vermicompost as a organic fertilizer has a good ability to adsorb cadmium metal from soil. Therfore, vermicompost application can be considered as an inexpensive natural adsorbent in arable land contaminated with cadmium.•Heavy metals are very toxic and carcinogenic to human and animals.•Adding organic fertilizer to the soil increases the absorption of heavy metal (cadmium) in the soil and prevents it from entering the food chain.•The relationship between the concentration of cadmium absorbed by the tuber of radish plant and the percentage of vermicompost added to the soil is presented.

Charge Carrier Dynamics in Bandgap Modulated Covellite-CuS Nanostructures.

Copper Sulfide (CuS) semiconductors have garnered interest, but the effect of transition metal doping on charge carrier kinetics and bandgap remains unclear. In this study, the interactions between dopant atoms (Nickel, Cobalt, and Manganese) and the CuS lattice using spectroscopy and electrochemical analysis are explored. The findings show that sp-d exchange interactions between band electrons and the dopant ions, which replace Cu2+, are key to altering the material's properties. Specifically, these interactions result in a reduced bandgap by shifting the conduction and valence band edges and increasing carrier concentration. It is observed that undoped CuS nanoflowers exhibit a carrier lifetime of 2.16 ns, whereas Mn-doped CuS shows an extended lifetime of 2.62 ns. This increase is attributed to longer carrier scattering times (84 ± 5 fs for Mn-CuS compared to 53 ± 14 fs for CuS) and slower trapping (∼1.5 ps) with prolonged de-trapping (∼100 ps) rates. These dopant-induced energy levels enhance mobility and carrier lifetime by reducing recombination rates. This study highlights the potential of doped CuS as cathode materials for sodium-ion batteries and emphasizes the applicability of metal sulfides in energy solutions.

The effect of fluence rate and wavelength on the formation of protoporphyrin IX photoproducts.

Photodynamic diagnosis and therapy (PDD and PDT) are emerging techniques for diagnosing and treating tumors and malignant diseases. Photoproducts of protoporphyrin IX (PpIX) used in PDD and PDT may be used in the diagnosis and treatment, making a detailed analysis of the photoproduct formation under various treatment and diagnosis conditions important.Spectroscopic and mass spectrometric analysis of photoproduct formation from PpIX dissolved in dimethyl sulfoxide were performed under commonly used irradiation conditions for PDD and PDT, i.e., wavelengths of 405 and 635 nm and fluence rates of 10 and 100 mW/cm2. Irradiation resulted in the formation of hydroxyaldehyde photoproduct (photoprotoporphyrin; Ppp) and formyl photoproduct (product II; Pp II) existing in different quantities with the irradiation wavelength and fluence rate. Ppp was dominant under 635 nm irradiation of PpIX, with a fluorescence peak at 673 nm and a protonated monoisotopic peak at m/z 595.3. PpIX irradiation with 405 nm yielded more Pp II, with a fluorescence peak at 654 nm. A higher photoproduct formation was observed at a low fluence rate for irradiation with 635 nm, while irradiation with 405 nm indicated a higher photoproduct formation at a higher fluence rate.The photoproduct formation with the irradiation conditions can be exploited for dosimetry estimation and may be used as an additional photosensitizer to improve the diagnostics and treatment efficacies of PDD and PDT. Differences in environmental conditions of the present study from that of a biological environment may result in a variation in the photoproduct formation rate and may limit their clinical utilization in PDD and PDT. Thus, further investigation of photoproduct formation rates in more complex biological environments, including in vivo, is necessary. However, the results obtained in this study will serve as a basis for understanding reaction processes in such biological environments.

Distinguishing Organomagnesium Species in the Grignard Addition to Ketones with X-ray Spectroscopy.

The addition of Grignard reagents to ketones is a well-established textbook reaction. However, a comprehensive understanding of its mechanism has only recently begun to emerge. X-ray spectroscopy, because of its high selectivity and sensitivity, is the ideal tool for distinguishing between an ensemble of competing pathways. With this aim in mind, we investigated the concerted mechanism of the addition of methylmagnesium chloride (CH$_3$MgCl) to acetone in tetrahydrofuran by simulating the X-ray spectra of different molecules in solution. We used electronic structure methods to calculate the X-ray absorption spectra at the Mg K- and L$_1$-edges and the X-ray photoelectron spectra at the Mg K-edge for different organomagnesium species, which coexist in solution due to the Schlenk equilibrium. The simulated spectra show that individual species can be distinguished throughout the different stages of the reaction.Each species has a distinct spectral feature which can be used as a fingerprint in solution. The absorption and photoelectron spectra consistently show a blue shift as the reaction progressed from reagents to products.

Impact of air pollution and heavy metal exposure on sperm quality: A clinical prospective research study.

Exposure to air pollution poses significant risks to human health, including detrimental effects on the reproductive system, affecting both men and women. Our prospective clinical study aimed to assess the impact of prolonged air pollution exposure on sperm quality in male patients attending a fertility clinic. The current study was conducted at Sri Narayani Hospital and Research Centre in Vellore, Tamil Nadu, India, and the study examined sperm samples obtained from individuals with extended exposure to air pollution. Microscopic analysis, including scanning electron microscopy (SEM), was conducted to evaluate sperm morphology. At the same time, atomic absorption spectroscopy (AAS) determined the presence of heavy metals, including Zinc (Zn), Magnesium (Mg), Lead (Pb) and Cadmium (Cd), known to affect sperm production. Our findings revealed that long-term exposure to air pollution adversely affects sperm quality, manifesting in alterations during the spermatogenesis cycle, morphological abnormalities observed through SEM, and impaired sperm motility. Additionally, epidemiological evidence suggests that elevated levels of cadmium and lead in the environment induce oxidative stress, leading to sperm DNA damage and reduced sperm concentrations. These results underscore the urgent need for environmental interventions to mitigate air pollution and protect reproductive health.

Fe─S Bond-Mediated Efficient Electron Transfer in Quantum Dots/Metal-Organic Frameworks for Boosting Photoelectrocatalytic Nitrogen Fixation.

Effective electron supply to produce ammonia in photoelectrochemical nitrogen reduction reaction (PEC NRR) remains challenging due to the sluggish multiple proton-coupled electron transfer and unfavorable carrier recombination. Herein, InP quantum dots decorated with sulfur ligands (InP QDs-S2-) bound to MIL-100(Fe) as a benchmark catalyst for PEC NRR is reported. It is found that MIL-100(Fe) can combined with InP QDs-S2- via Fe─S bonds as bridge to facilitate the electron transfer by experimental results. The formation of Fe─S bonds can facilitate electron transfer from inorganic S2- ligands of InP QDs to the Fe metal sites of MIL-100(Fe) within 52 ps, ensuring a more efficient electron transfer and electron-hole separation confirmed by the time-resolved spectroscopy. More importantly, the process of photo-induced carrier transfer can be traced by in situ attenuated total reflection surface-enhanced infrared tests, certifying that the effective electron transfer can promote N≡N dissociation and N2 hydrogenation. As a result, InP QDs-S2-/MIL-100(Fe) exhibits prominent performance with an outstanding NH3 yield of 0.58 µmol cm-2 h-1 (3.09 times higher than that of MIL-100(Fe)). This work reveals an important ultrafast dynamic mechanism for PEC NRR in QDs modified metal-organic frameworks, providing a new guideline for the rational design of efficient MOFs photocathodes.

Physicochemical Characterization and Antimicrobial Properties of Lanthanide Nitrates in Dilute Aqueous Solutions.

This work presents the results of studying dilute aqueous solutions of commercial Ln(NO3)3 · xH2O salts with Ln = Ce-Lu using X-ray diffraction (XRD), IR spectroscopy, X-ray absorption spectroscopy (XAS: EXAFS/XANES), and pH measurements. As a reference point, XRD and XAS measurements for characterized Ln(NO3)3 · xH2O microcrystalline powder samples were performed. The local structure of Ln-nitrate complexes in 20 mM Ln(NO3)3 · xH2O aqueous solution was studied under total external reflection conditions and EXAFS geometry was applied to obtain high-quality EXAFS data for solutions with low concentrations of Ln3+ ions. Results obtained by EXAFS spectroscopy showed significant contraction of the first coordination sphere during the dissolution process for metal ions located in the middle of the lanthanide series. It was established that in Ln(NO3)3 · xH2O solutions with Ln = Ce, Sm, Gd, Yb (c = 134, 100, 50 and 20 mM) there are coordinated and, to a greater extent, non-coordinated nitrate groups with bidentate and predominantly monodentate bonds with Ln ions, the number of which increases upon transition from cerium to ytterbium. For the first time, the antibacterial and antifungal activity of Ln(NO3)3 · xH2O Ln = Ce, Sm, Gd, Tb, Yb solutions with different concentrations and pH was presented. Cross-relationships between the concentration of solutions and antimicrobial activity with the type of Ln = Ce, Sm, Gd, Tb, Yb were established, as well as the absence of biocidal properties of solutions with a concentration of 20 mM, except for Ln = Yb. The important role of experimental conditions in obtaining and interpreting the results was noted.

Uncovering an Interfacial Band Resulting from Orbital Hybridization in Nickelate Heterostructures.

The interaction of atomic orbitals at the interface of perovskite oxide heterostructures has been investigated for its profound impact on the band structures and electronic properties, giving rise to unique electronic states and a variety of tunable functionalities. In this study, we conducted an extensive investigation of the optical and electronic properties of epitaxial NdNiO3 synthesized on a series of single-crystal substrates. Unlike nanofilms synthesized on other substrates, NdNiO3 on SrTiO3 (NNO/STO) gives rise to a unique band structure featuring an additional unoccupied band situated above the Fermi level. Our comprehensive investigation, which incorporated a wide array of experimental techniques and density functional theory calculations, revealed that the emergence of the interfacial band structure is primarily driven by orbital hybridization between the Ti 3d orbitals of the STO substrate and the O 2p orbitals of the NNO thin film. Furthermore, exciton peaks have been detected in the optical spectra of the NNO/STO film, attributable to the pronounced electron-electron (e-e) and electron-hole (e-h) interactions propagating from the STO substrate into the NNO film. These findings underscore the substantial influence of interfacial orbital hybridization on the electronic structure of oxide thin films, thereby offering key insights into tuning their interfacial properties.

100 µs Luminescence Lifetime Boosts the Excited State Reactivity of a Ruthenium(II)-Anthracene Complex in Photon Upconversion and Photocatalytic Polymerizations with Red Light.

The triplet excited state lifetime of a photosensitizer is an essential parameter for diffusion-controlled energy- and electron-transfer, which occurs usually in a competitive manner to the intrinsic decay of a triplet excited state. Here we show the decisive role of luminescence lifetime in the triplet excited state reactivity toward energy- and electron transfer. Anchoring two phenyl anthracene chromophores to a ruthenium(II) polypyridyl complex (RuII ref) leads to a RuII triad with a luminescence lifetime above 100 µs, which is more than 40 times longer than that of the prototypical complex. The obtained RuII triad sensitizes energy transfer to anthracene-based annihilators more efficiently than the RuII ref and enables red-to-blue photon upconversion with a pseudo anti-Stokes shift of 0.94 eV and a moderate upconversion efficiency near 1% in aerated solution. Particularly, the RuII triad allows rapid photoredox catalytic polymerizations of acrylate and acrylamide monomers under aerobic condition with red light, which are kinetically hindered for the RuII ref. Our work shows that excited state lifetime of a photosensitizer governs the dynamics of the excited state reactions, which seems an overlooked but important aspect for photochemistry.

Selective Catalytic Combustion of Hydrogen under Aerobic Conditions on Na2WO4/SiO2.

Na2WO4/SiO2, a material known to catalyze oxidative coupling of methane, is demonstrated to catalyze selective hydrogen combustion (SHC) with >97% selectivity in mixtures with several hydrocarbons (CH4, C2H-6, C2H4, C3H6, C6H6) in the presence of gas-phase dioxygen at 883-983 K. Hydrogen combustion rates exhibit a near-first-order dependence on H2 partial pressure and are zero-order in H2O and O2 partial pressures. Mechanistic studies using isotopically-labeled reagents demonstrate the kinetic relevance of H-H dissociation and absence of O-atom recombination. In situ X-ray diffraction and W LIII-edge X-ray absorption spectroscopy studies demonstrate, respectively, a loss of Na2WO4 crystallinity and lack of second-shell coordination with respect to W6+ cations below 923 K; benchmark experiments show that alkali cations must be present for the material to be selective for hydrogen combustion, but that materials containing Na alone have much lower combustion rates (per gram Na) than those containing Na and W. These data suggest a synergy between Na and W in a disordered phase during SHC catalysis. The Na2WO4/SiO2 SHC catalyst maintains stable combustion rates at temperatures ca. 100 K higher than redox-active SHC catalysts and could potentially enable enhanced olefin yields in tandem operation of reactors combining alkane dehydrogenation with SHC processes.

Ultrafast Hole Trapping in Te-MoTe2-MoSe2/ZnO S-Scheme Heterojunctions for Photochemical and Photo-/Electrochemical Hydrogen Production.

Te-MoTe2-MoSe2/ZnO S-scheme heterojunctions are engineered to ascertain the advanced redox ability in sustainable HER operations. Photo-physical studies have established the steady state transfer of photo-induced charge carriers whereas an improved transfer dynamics realized by state-of-art ultrafast transient absorption and irradiated-XPS analysis of optimized 5wt% Te-MoTe2-MoSe2/ZnO heterostructure. 2.5, 5, and 7.5wt% Te-MoTe2-MoSe2/ZnO photocatalysts (2.5MTMZ, 5MTMZ and 7.5MTMZ) exhibited 2.8, 3.3, and 3.1-fold higher HER performance than pristine ZnO with marvelous apparent quantum efficiency of 35.09%, 41.42% and 38.79% at HER rate of 4.45, 5.25, and 4.92 mmol/gcat/h, respectively. Electrochemical water splitting experiments manifest subdued 583 and 566 mV overpotential values of 2.5MTMZ and 5MTMZ heterostructures to achieve 10 mA cm-2 current density for HER, and 961 and 793 mV for OER, respectively. For optimized 5MTMZ photocatalyst, lifetime kinetic decay of interfacial charge transfer step is evaluated to be 138.67 ps as compared to 52.92 ps for bare ZnO.