Lasers Research Articles

Efficient Preparation of S-Scheme Ag/AgBr/BiOBr Heterojunction Photocatalysts and Implications for Degradation of Carbendazim: Mechanism, Pathway, and Toxicology.

Carbendazim (CBZ), as a highly effective benzimidazole fungicide, has a good control effect on various crops caused by fungi. However, excessive use of CBZ in water, atmosphere, soil, and crops has serious effects. The efficient degradation of CBZ is an effective way to reduce its toxic effect. In this work, the type of S-scheme Ag/AgBr/BiOBr heterojunction photocatalyst was effectively prepared by a simple one-step solvothermal in situ method and first applied to the mineralization and degradation of CBZ. The effects of the molar ratio of AgBr to BiOBr, catalyst dosage, CBZ concentration, pH value of the original solution, and inorganic salt ions on the photocatalytic degradation performance of CBZ were comprehensively studied. The results showed that, under visible light irradiation, 0.9-Ag/AgBr/BiOBr (0.9-AAB) exhibited the best photocatalytic degradation performance (88.9%) against the concentration at 10 mg/L of CBZ in original solutions with pH of 10. However, the degradation effect was also good at pH 7. After 90 min, the degradation efficiency reached 86.0%, corresponding to a TOC removal efficiency of 84.0%. The results indicate that the main active species are 1O2 and •O2- free radicals according to the free radical quenching experiments and electron spin resonance spectra. Combined with the XPS characterization results, the electron transfer mechanism of the S-scheme heterojunction was deeply revealed. Additionally, the degradation pathway of CBZ was proposed through both the intermediate identification and the theoretical calculation derived from the DFT Fukui index. Finally, the toxicity of CBZ and the degradation intermediates were predicted based on the T.E.S.T.

Carbazolyl-Decorated Metal-Organic Framework with a High Fluorescent Quantum Yield for Detection and Photocatalytic Degradation of Organic Contaminants.

A carbazolyl-based fluorescent metal-organic framework with deep-blue light emission and a high quantum yield (88%) has been screened out by changing the ratio of mixed ligands, named Cz-MOF-2, which was constructed by ZrO4(OH)4 clusters, 3-(9-ethyl-9H-carbazol-3-yl)-4-methylthieno[2,3-b]thiophene-2,5-dicarboxylate (H2ECMTDC) and 3,4-dimethyl-dihydrothieno[2,3-b]thiophene-2,5-dicarboxylate (H2DMTDC). Cz-MOF-2 has excellent sensitivity in fluorescent sensing of 2,6-dichloro-4-nitroaniline (DCN), nitrofurazone (NZF), and nitrofurantoin (NFT) with detection limits of 3.37 × 10-7, 1.64 × 10-5, and 1.76 × 10-5 M, respectively. The quenching mechanisms involving electron transfer and competitive absorption were comprehensively elucidated through DFT calculations and UV absorption experiments. Cz-MOF-2 has been fabricated into a rapidly regenerated composite membrane with PVDF as a visualized fluorescent sensor for DCN. Furthermore, the carbazolyl groups covalently modified in the framework endowed Cz-MOF-2 with a suitable band gap (2.58 eV) for photocatalytic degradation of organic contaminants. It demonstrated superior photocatalytic efficiency compared to UiO-66 and NH2-UiO-66 in the degradation of tetracycline (TC), and the removal efficiency was up to 85% (20 mg of catalyst, 50 mL, 20 mg/L TC solution and 180 min) under simulated sunlight irradiation using a 300 W Xe lamp. Photoelectrochemical tests demonstrate that Cz-MOF-2 exhibits high photocurrent density and low charge transfer resistance, which provide evidence for the efficient charge separation capability. Radical trapping experiments and ESR detection have substantiated that ·O2- and h+ are the primary active species involved in this photocatalytic reaction. This work highlights the potential of MOFs in the targeted design and development of fluorescent sensors and photocatalysts for environmental detection and remediation.

Establishing robust ZnO-sodium alginate nanocomposite for dye wastewater treatment: characterization, RSM methodology, and mechanism evaluation.

In today's world, water is a highly valued resource, and enhancing the quality of this natural endowment is a significant concern and a worldwide endeavor. This study sought to purify real wastewater and water tainted with methylene blue (MB) by immobilizing ZnO nanoparticles onto an alginate matrix using a straightforward approach and a three-dimensional structure. After analyzing the impact of , it was determined that 93.84% of MB was successfully removed (time = 120 min, dye concentration = 15 mg/L, catalyst amount = 2.5 g). The effects of inorganic ions and water types were investigated to simulate real wastewater conditions, and the catalyst performed satisfactorily. Alginate played a significant role in selectively removing dye, and the catalyst effectively removed 80.36% of MB and, in contrast, 20% of methyl orange (MO). The practical application of the catalyst was evaluated in textile wastewater treatment, and the catalyst showed satisfactory performance. An average 2.49% reduction in dye removal was observed after five stages of using the catalyst, demonstrating the beads' excellent stability. The composites were subjected to free radical trapping experiments to ascertain the active species. According to the results, and acted as the main reaction species in the degradation of MB. At the end, the synergistic mechanism of adsorption and degradation in MB removal was presented.

Gamma-ray shielding effectiveness, optical, mechanical, dielectric properties of nanofiller-reinforced PVA/PVP polymeric blend nanocomposites

The aqueous solution cast method was used to create the biodegradable polymer nanocomposite (PNC) films from a blend of poly (vinyl alcohol) PVA and poly (vinyl pyrrolidone) PVP (70/30 wt %) and Fe2O3 nanoparticles (NPs). These PNC films were characterized using X-ray diffraction, scanning electron microscopy SEM, Fourier transform infrared spectroscopy FTIR, and ultraviolet-visible spectroscopy. XRD and FTIR results indicate that Fe+ 3 NPs interact with the host polymer. Optical, electrical, mechanical, and radiation shielding measurements were performed on the PNC films. From the optical measurements, the indirect optical band gap drops from 4.86 eV for the pure blend to 4.26 eV at the greatest NPs concentration. Optical limiting characterization shows that the output power of He-Ne and solid-state green laser beams is reduced from 22.98 to 3.6 mW and 6.59 to 1.4 mW, respectively, when the Fe2O3 NPs content in the blend matrix is increased to 6 wt %. The NGCal software was utilized to calculate nuclear radiation shielding properties. The findings demonstrated that when the concentration of Fe2O3 rose, the PNC films half-value layer and mean free path decreased. Mechanical measurements demonstrate that increasing the Fe2O3 content significantly improves nanocomposite films’ yield and tensile strength. Tensile strength is measured at 27.03 MPa for the composite film containing 6 wt % Fe2O3, which is significantly higher than the 8.66 MPa of the pure (PVA-PVP) film. Compared to the other samples under examination, the 6 wt % Fe2O3 sample yielded the best results (based on the analyzed optical, electrical, mechanical, and radiation shielding properties).

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro‐Reforming Coupled with Hydrogen Production

Alkaline methanol‐water electrolysis system is regarded as an appealing strategy for electro‐reforming methanol into formate and producing hydrogen with low energy‐consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH‐, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm‐2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm‐2 for hydrogen evolution reaction (HER). Furthermore, membrane‐free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long‐term stability and FEs at high current density of 300 mA cm‐2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

Enhanced Adsorption Kinetics and Capacity of a Stable CeF3@Ni3N Heterostructure for Methanol Electro-Reforming Coupled with Hydrogen Production.

Alkaline methanol-water electrolysis system is regarded as an appealing strategy for electro-reforming methanol into formate and producing hydrogen with low energy-consumption compared with alkaline water electrolysis. However, stability and selectivity under high current densities for practical application remain challenging. Herein, a CeF3@Ni3N nanosheets array anchored on carbon cloth (CeF3@Ni3N/CC) was fabricated. The gradual extrusion of F species from Ni(OH)2 lattices can stabilize hierarchical structure and construct abundant heterostructure interfaces. Moreover, CeF3 can modulate electron distribution of Ni3N, thus simultaneously enhancing the surface adsorption kinetics and capability of methanol and OH-, which is conducive to enhanced methanol oxidation reaction (MOR) activity and selectivity. Therefore, bifunctional CeF3@Ni3N/CC exhibits low potential of 1.43 V at 500 mA cm-2, along with high stability over 72 h and high faradaic efficiency (FEs) in MOR, as well as an overpotential of 76 mV to achieve 50 mA cm-2 for hydrogen evolution reaction (HER). Furthermore, membrane-free CeF3@Ni3N/CC||CeF3@Ni3N/CC cell for MOR||HER delivers high electrocatalytic activity, long-term stability and FEs at high current density of 300 mA cm-2. This study highlights the importance of optimizing surface adsorption behavior of active species, as well as rational design of highly efficient heterostructure electrocatalysts for methanol upgrading coupled with hydrogen production.

Access to Alkenyl Cyclobutanols by Ni-Catalyzed Regio- and Enantio-Selective syn-Hydrometalative 4-exo-trig Cyclization of Alkynones.

Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel-catalyzed asymmetric syn-hydrometalative 4-exo-trig cyclization of 1,4-alkynones to synthesize alkenyl cyclobutanols with a tetrasubstituted stereocenter. This strategy features a broad substrate scope, delivering a variety of trifluoromethyl-containing rigid (spiro)carbocycle skeletons in good yields with high enantioselectivities (up to 84 % yield and 98.5 : 1.5 er). The synthetic utility is demonstrated through stereospecific transformations into fused spiro molecules. Experimental and computational mechanistic studies indicate that the reaction is initiated by an active Ni-H species, with carbonyl-directed hydrometalation as the key for regioselective control. This catalytic method provides a general solution for regioselective hydrofunctionalization of alkynes and represents an efficient reaction pattern for assembling highly strained enantioenriched bioisosteres.

Insights into the Synergistic Catalytic Effect of TiO2 Supported V-W Oxides for Selective C-H Bond Oxidation of Cyclohexane to KA Oil.

It is urgent to develop an efficient and stable non-noble metal catalyst for selective C-H bond oxidation of cyclohexane. Herein, a series of V-W oxides supported on TiO2 catalysts (V-W/TiO2) were fabricated. The V-W/TiO2 catalysts exhibited much higher catalytic activity for the selective oxidation of cyclohexane to KA oil, compared to that of V/TiO2 and W/TiO2 catalysts. The good distribution of active metals and the synergistic effect were responsible for the enhanced catalytic activity. H2-TPR results disclosed that the presence of V in V-W/TiO2 affected the reducibility of W6+ species, and XPS verified that an electronic interaction was formed between them. Such results led to good catalytic reusability of V-W/TiO2 catalyst during the reactions, and no obvious activity loss was found after six runs. The reaction mechanism was investigated, and the results verified that hydroxyl radicals generated from H2O2 homolysis were the main active oxidative species. Theoretical study revealed that V dopant could regulate electronic structure of adjacent O atom, facilitating the adsorption of cyclohexane, and lower energy was needed for the rate-limiting step over V-W/TiO2 during the whole oxidation reaction. This work developed an efficient V-W/TiO2 catalyst for the selective oxidation of cyclohexane via a synergistic effect.

Active Sites for CO2 Hydrogenation to Methanol: Mechanistic Insights and Reaction Control.

Catalytic CO2 conversion to methanol is a promising way to extenuate the adverse effects of CO2 emission, global warming and energy shortage. Understanding the fundamental features of CO2 activation and hydrogenation at the molecular level is essential for carbon utilization and sustainable chemical production in the current climate crisis. This review explores the recent advances in understanding the design of catalysts with desired active sites, including single-atom, dual-atom, interface, defects/vacancies and promoters/dopants. We focused on the design of various catalytic systems to enhance their catalytic performances by stabilizing active metal in a catalyst, identifying the unique structure of active species, and engineering coordination environments of active sites. Mechanistic insights provided by advanced operando and in situ spectroscopies were also discussed. Moreover, the review highlights the key factors affecting active sites and reaction mechanisms, such as local environments, oxidation states, and metal-support interactions. By integrating recent advancements and relating knowledge gaps, this review aims to endow an inclusive overview of the field and guide future research toward more efficient and selective catalysts for CO2 hydrogenation to methanol.

Detecting water-soaked disorder and reddish-pulp disorder in peach fruit using bio-speckle

This study addresses the challenges in nondestructive identifying diseases, particularly water-soaked and reddish-pulp disorders, in peaches during storage and transport. Existing technologies have struggled to detect these diseases during this period, leading to potential food loss and consumer distrust. Biospeckle has emerged as a promising discriminator of the internal state of the fruit by utilizing laser-induced scattered light patterns. Pigment interference is minimized by employing lasers with wavelengths of 532 and 650 nm. This study focuses on the ability of biospeckle to distinguish between healthy and diseased fruit based on characteristic values, specifically the Fujii index and cumulative amplitude (Cum. amp.) at 2–3, 3–4, 4–5, and 6–7 Hz. The t-test results demonstrated significant differences in these values, particularly for water-soaked and reddish-pulp disorders. Biospeckle outperforms other non-destructive methods by identifying the symptoms pre-storage. These results indicate that Cum. amp. at 3–4, 4–5, and 6–7 Hz may be more useful in identifying water-soaked fruit than the Fujii index and Cum. amp. at 2–3 Hz. Red lasers are more effective in detecting reddish-pulp disorders than green lasers, which are hindered by pigment absorption. This finding highlights the potential of biospeckle in precise symptom identification, which is crucial for ensuring food quality and consumer confidence.

Anchoring Perovskite-Like Bi4Ti3O12 and Plasmonic Bi on Defect-Rich Yellow TiO2-x for Enhanced Catalytic Activity toward Degradation of Pollutants upon Visible Light.

The efficiency of heterogeneous photocatalytic processes is currently limited due to the fast recombination of photocarriers, poor light absorption, and inefficient surface catalytic characteristics. In this study, defect-rich yellow TiO2-x nanoparticles (abbreviated as D-TiO2) with high surface area and significant absorption in the visible range were integrated with perovskite-like Bi4Ti3O12 to synthesize binary D-TiO2/Bi4Ti3O12 nanocomposites. To overcome the problem of insufficient activity, we integrated the optimized D-TiO2/Bi4Ti3O12 nanocomposite with plasmonic Bi nanoparticles. Significantly, the optimized D-TiO2/Bi4Ti3O12/Bi-2 nanocomposite efficiently removed tetracycline (TC) in 50 min through production of •OH, h+, and •O2- species, whose removal rate promoted 10.6, 3.18, 5.01, and 1.84 compared with the white TiO2 (abbreviated as W-TiO2), D-TiO2, Bi4Ti3O12, and D-TiO2/Bi4Ti3O12 (20%) photocatalysts, respectively. The outstanding performance of the D-TiO2/Bi4Ti3O12/Bi photocatalyst was attributed to its quantum dot size, low resistance for charge migration, increased surface area, oxygen vacancies in D-TiO2, and developed n-n heterojunction among D-TiO2 and Bi4Ti3O12, which accelerated charge transfer and promoted the generation of active species. Furthermore, the stability tests showed that the TC degradation efficiency still reached 96% after four recycles, indicating the remarkable stability of the photocatalyst. Eventually, the biocompatible nature of the treated solution over the optimized photocatalyst was also revealed from an investigation of the growth of lentil seeds.

Reducing Dead Species by Electrochemically‐Densified Cathode‐Interface‐Reaction Layer towards High‐Rate‐Endurable Zn||I‐Br Batteries

Interhalogen‐involved aqueous Zn||halogen batteries (AZHBs) are latent high‐energy systems for grid‐level energy storage, yet usually suffer from poor high‐rate endurability caused by the formation of “dead species”. Herein, via an electrochemically‐densified cathode‐interface‐reaction layer (CIRL), Zn||I‐Br batteries involving interhalogen reactions between the I2 cathode and Br‐ from the electrolytes are initially achieved with excellent high‐rate endurability. Different from that in diluted electrolytes, the CIRL formed in Br‐‐concentrated electrolyte is denser and water‐lean, which enables halogen species conversion with a more rapid charge transfer and lower activation energy. More importantly, the CIRL robustly affords a decent I2 conservation by accelerated conversion kinetics and limited species diffusion, thereby endowing the Zn||I‐Br batteries with an ultralong high‐rate lifespan. The electrochemical mechanism is sufficiently verified by multiple spectral characterizations. Consequently, Zn||I‐Br batteries in Br‐‐concentrated (20 m) electrolytes exhibit an overwhelming rate capability and lifespan to those in Br‐‐diluted (2 m) electrolytes. Typically, when cycled at a large current density of 10 A g‐1, an ultralong lifespan of over 25,000 cycles is achieved with a high retention of 98.3%. This study provides new insight into the CIRL‐dictated active species conservation for high‐rate endurable AZHBs, which could apply to other high‐energy interhalogen batteries.

Efficient activation of peracetic acid by defect-engineered MoO2−x: Oxygen vacancies and surface Mo(Ⅴ)-mediated electron transfer processes

The role of defect regulation of transition metal catalysts in peracetic acid (PAA) activation is equivocal. To reveal the corresponding mechanism, this work provides a high-efficiency and eco-friendly catalyst (MoO2−x) for PAA activation by introducing various degrees of oxygen vacancies on the MoO2 surface. Interestingly, 95.83 % of tetracycline (TC) is rapidly degraded by MoO2−x with rich oxygen vacancies within 20 min via PAA activation, which is superior over that of MoO2−x with poor oxygen vacancies and other typical oxidants (H2O2, SO32−, S2O82−, HSO5−, IO4−). In addition, the defect-regulated MoO2−x exhibits good de-biotoxicity towards TC. Moreover, MoO2−x shows satisfactory purification of various contaminants and actual pharma wastewater. Active species identification suggests that the electron transfer process triggered by the active complex (MoO2−x −PAA*) of PAA bonded on the MoO2−x surface plays the dominant role in TC degradation, while •OH plays a minor role. Mechanism analysis reveals that oxygen vacancies play an indispensable role in accelerating the adsorption and complexation of PAA as well as improving electrical conductivity. Active site analysis demonstrates that Mo(Ⅴ) on the MoO2−x surface acts as an electron shuttle and is the main PAA activation site. This work provides a new approach into the application of MoO2 in hospital wastewater purification via defect engineering.

Reducing Dead Species by Electrochemically-Densified Cathode-Interface-Reaction Layer towards High-Rate-Endurable Zn||I-Br Batteries.

Interhalogen-involved aqueous Zn||halogen batteries (AZHBs) are latent high-energy systems for grid-level energy storage, yet usually suffer from poor high-rate endurability caused by the formation of "dead species". Herein, via an electrochemically-densified cathode-interface-reaction layer (CIRL), Zn||I-Br batteries involving interhalogen reactions between the I2 cathode and Br- from the electrolytes are initially achieved with excellent high-rate endurability. Different from that in diluted electrolytes, the CIRL formed in Br--concentrated electrolyte is denser and water-lean, which enables halogen species conversion with a more rapid charge transfer and lower activation energy. More importantly, the CIRL robustly affords a decent I2 conservation by accelerated conversion kinetics and limited species diffusion, thereby endowing the Zn||I-Br batteries with an ultralong high-rate lifespan. The electrochemical mechanism is sufficiently verified by multiple spectral characterizations. Consequently, Zn||I-Br batteries in Br--concentrated (20 m) electrolytes exhibit an overwhelming rate capability and lifespan to those in Br--diluted (2 m) electrolytes. Typically, when cycled at a large current density of 10 A g-1, an ultralong lifespan of over 25,000 cycles is achieved with a high retention of 98.3%. This study provides new insight into the CIRL-dictated active species conservation for high-rate endurable AZHBs, which could apply to other high-energy interhalogen batteries.

Distribution characteristics and photochemical effects of isoprene in a coastal city of southeast China

As forest coverage and urban greening increase in China, the impact of biogenic volatile organic compounds (BVOCs) on urban atmospheric environment cannot be neglected. As one of the most abundant and reactive BVOCs globally, isoprene plays a crucial role in atmospheric radical chemistry. However, the reports on quantifying the impact of isoprene on atmospheric photochemistry remain scarce. This study selected Xiamen, a typical coastal city in Fujian Province, as the research area. By employing field observation and Photochemical Box Model (PBM), the study investigated the distribution characteristics, pollution mechanisms, and impact on O3 of the atmospheric photochemical active species isoprene in coastal urban area. The study found that the average concentration of isoprene in summer was 4.7 times higher than that in autumn. Isoprene degradation primarily occurred through oxidation by OH· radicals, reaching 88 % and 86 % in summer and autumn, respectively. Based on scenario simulations using the PBM model, it was observed that isoprene photochemistry led to increased daytime concentrations of ROx radicals (summer: 24 %, autumn: 23 %), peroxyacetyl nitrate (PAN, 49 %, 44 %), and formaldehyde (HCHO, 37 %, 38 %). Additionally, isoprene photochemistry enhanced reaction rates of HO₂· + NO (summer: 21 %, autumn: 16 %) and RO₂· + NO (50 %, 52 %), ultimately resulting in a 19 % and 15 % increase in net O3 production rates in summer and autumn, respectively. This study provides scientific evidence for exploring the photochemical mechanisms and pollution control strategies of O3 in coastal atmospheric environments.

Visualizing the Structure and Dynamics of Transition Metal-Based Electrocatalysts Using Synchrotron X-Ray Absorption Spectroscopy.

As the global energy structure evolves and clean energy technologies advance, electrocatalysis has become a focal point as a critical conversion pathway in the new energy sector. Transitional metal electrocatalysts (TMEs) with their distinctive electronic structures and redox properties show great potential in electrocatalytic reactions. However, complex reaction mechanisms and kinetic limitations hinder the improvement of energy conversion efficiency, highlighting the necessity for comprehensive studies on structure and performance of electrocatalysts. X-ray Absorption Fine Structure (XAFS) spectra stand out as a robust tool for examining the electrocatalyst's structures and performance due to its atomic selectivity and sensitivity to local environments. This review delves into the application of XAFS technology in characterizing TMEs, providing in-depth analyses of X-ray Absorption Near-Edge Structure (XANES) spectra, and Extended XAFS (EXAFS) spectra in both R-space and k-space. These analyses reveal intrinsic structural information, electronic interactions, catalyst stability, and aggregation morphology. Furthermore, the paper examines advancements in in-situ XAFS techniques for real-time monitoring of active site changes, capturing critical intermediate and transitional states, and elucidating the evolution of active species during electrocatalytic reactions. These insights deepen our understanding on structure-activity relationship of electrocatalysts and offer valuable guidance for designing and developing highly active and stable electrocatalysts.

Green-Fueled synthesis of rGO/CuO for catalytic degradation of methyl violet dye

This study presents the green synthesis of copper oxide (CuO) through an eco-friendly solution combustion method, utilizing lemongrass as a natural fuel source. The rGO/CuO composite was prepared via a simple reflux process, emphasizing environmental sustainability. Comprehensive characterization of the synthesized CuO and rGO/CuO composites was conducted using techniques such as XRD, SEM, FTIR, PL, HR-TEM, EDX, and UV–Vis's spectroscopy. The photocatalytic efficiency of the rGO/CuO composite was tested for the degradation of Methyl Violet (MV) dye, achieving an impressive degradation rate of 98.87 ​% and following first-order kinetic behavior. The half-life (t₁/₂) of the reaction was calculated to be 18.17 ​min, with a rate constant (k) of 0.0398 ​min⁻1. Various parameters affecting photocatalytic performance, including pH, dye concentration, light source, and catalyst dosage, were systematically investigated. Scavenger experiments were conducted to determine the active species involved in the degradation process, and total organic carbon (TOC) removal was measured to assess mineralization efficiency. The catalyst's reusability was also evaluated, confirming its potential for long-term use in sustainable environmental remediation applications.

Modifying d–p orbital hybridization of Ni/Fe[sbnd]O species by high-valence ruthenium doping to enhance oxygen evolution performance

The electron distribution of catalysts can be modulated by high-valence metal doping, thus enhancing the intrinsic activity. Herein, we adopt Ru modification to adjust the d–p orbital hybridization of Ni-Fe oxyhydroxides, significantly increasing the oxygen evolution reaction (OER) activity. The amorphous NiFe0.5Ru0.1OxHy catalyst synthesized by sol–gel method exhibits excellent OER activity, far superior to commercial RuO2. In situ Raman and XPS results confirm that the NiOOH/FeOOH active species gradually form with increasing applied voltage. Density functional theory (DFT) calculations reveal that high-valence Ru dopants can effectively regulate the hybridization of d–p orbital of Ni/FeO, significantly increase the electron density around Fermi level, promote charge transfer, make them have more anti-bonding orbitals, enhance the binding ability of active sites to intermediates, reduce the reaction energy barrier of the rate-determining step (H2O → *OH), and thus improve the OER activity. In addition, NiFeRuOxHy as a cathode catalyst in a rechargeable zinc-air battery shows an outstanding cycle life of 600 h. This study provides a promising hybrid orbital method for designing high-performance OER catalysts for water splitting and rechargeable zinc-air batteries.

Exploration on structure-activity relationship over substituted Co-doped spinel AlFe2O4 for enhanced CO2 hydrogenation into C2-C4 hydrocarbons

As the main greenhouse gas, CO2 has caused some serious environmental problems. Hence the abatement of CO2 allows of no delay. Among all strategies for CO2 reduction, CO2 hydrogenation reveals the great potential for industrial application, and becomes the efficient path to achieve target of “Carbon Neutral”. In this work, the Co-doped AlFe2O4 catalysts were firstly reported for CO2 hydrogenation test, and the enhancement of Co doping on activity was explored systematically via a series of conventional characterization methods. The Fischer-Tropsch synthesis-based CO2 hydrogenation was conducted over Co-doped AlFe2O4, thus the dissociation of CO2 and the carbon chain growth were both important. The observation of CoFe2O4 in the composites indicated the strong electronic interaction between Co and Fe species. This could strengthen the electrons transfer to generate more metallic Co and Fe species during H2 reduction, and then increased the Fe3C percentage during CO2 hydrogenation process. Moreover, the generated Co0 species could provide the additional adsorption sites for reactant gas. Therefore, the strategy of Co doping could strengthen the CO2 hydrogenation performance, reflected in the increase of CO2 conversion, the selectivity and space time yield of C2-C4 products. However, the formed “too stable” structure in the condition of the excessive Co doping prohibited the electrons transfer and the generation of Fe3C active species, thus existing an optimum Co doping amount.

Regulating Interface Dipole Interaction between Ethers and Active Species Toward Highly Stable Li-SPAN Batteries.

Sulfurized polyacrylonitrile (SPAN) is recognized as a promising organic cathode for long-lifespan lithium metal batteries. Nevertheless, the irreversible cleavage/formation of multiple sulfur-sulfur (S-S) bonds of SPAN within conventional ether-based electrolytes results in loss of active S species, severe capacity fading and shuttle effects. Herein, we propose a new electrolyte based on dipropyl ether (PE) solvent for Li-SPAN batteries. Benefiting from the particular chain-coordination structure and weak dipole interactions with Li+ and active species, the resulting electrolyte not only achieves low desolvation energy barrier and high Li+ transference number, but also displays stable electrolyte-electrode interface (EEI). Consequently, the full cells utilizing this electrolyte exhibit good cyclability, outstanding capacity retention and superior extreme-temperature (-50 °C to 50 °C) performance. Furthermore, the Ah-scale pouch cell with lean electrolyte (2.5 g Ah-1) achieves record cycle stability with 96.5 % capacity retention after 75 cycles, which deliver an initial specific energy density of 150 Wh kg-1 (based on the weight of the entire cell). Impressively, this strategy demonstrates universality in a series of organic electrodes employing with PE-based electrolytes. This work highlights the strategy for modulating the dipole interaction at EEI for long-lifespan Li-organic batteries at extreme conditions.