Intermediate Products Research Articles

Host-Guest Approach to Promoting Photocatalysis Based on Consecutive Photo-Induced Electron-Transfer Processes via Efficient Förster Resonance Energy Transfer.

Supramolecular artificial light-harvesting system with highly efficient host-guest energy transfer pathway provides an ideal platform for optimizing the photochemistry process. The consecutive photo-induced electron transfer (conPET) process overcomes the energy limitation of visible-light photocatalysis, but is often compromised by mismatching between the absorption of ground state dye and its radical, weakening the efficiency of photoredox reaction. By encapsulating a conPET photocatalyst rhodamine 6G into metal-organic cage, the supramolecular approach was undertaken to tackle the intrinsic difficulty of matching the light absorption of photoexcitation between rhodamine 6G and its radical. The highly efficient Förster resonance energy transfer from the photoexcited cage to rhodamine 6G forced by host-guest encapsulation facilitates the conPET process for the single-wavelength light-driven activation of aryl halides by stabilizing and accelerating the production and accumulation of the rhodamine 6G radical intermediate. The tunable and flexible nature of the supramolecular host-guest complex renders the cage-based encapsulation strategy promising for the development of ideal photocatalysts toward the better utilization of solar energy.

Mechanistic study on 4, 4'-sulfonylbis removal with CO2/Ar gas-liquid DBD plasma

Abstract In this study, a single dielectric barrier discharge (DBD) coaxial reactor was used to degrade 4, 4'-sulfonylbis (TBBPS) in water using greenhouse gas (CO2) and argon as the carrier gases. The investigation focused on CO2 conversion, reactive species formation, gas-liquid mass transfer mechanism, and degradation mechanism of TBBPS during the discharge plasma process. With the decrease of CO2/Ar ratio in the process of plasma discharge, the emission spectrum intensity of Ar, CO2 and excited reactive species was enhanced. This increase promoted collision and dissociation of CO2, resulting in a series of chemical reactions that improved the production of reactive species such as ·OH, 1O2, H2O2 and O3. These reactive species initiated a sequence of reactions with TBBPS. Results indicated that at a gas flow rate of 240 mL/min with a CO2/Ar ratio of 1:5, both the highest CO2 conversion rate (17.76%) and TBBPS degradation rate (94.24%) were achieved. The degradation mechanism was elucidated by determining types and contents of reactive species present in treatment liquid along with analysis of intermediate products using liquid chromatography-mass spectrometry techniques. This research provides novel insights into carbon dioxide utilization and water pollution control through dielectric barrier discharge plasma technology.

Endothelial cell-derived extracellular vesicles modulate the therapeutic efficacy of mesenchymal stem cells through IDH2/TET pathway in ARDS

BackgroundAcute respiratory distress syndrome (ARDS) is a severe and fatal disease. Although mesenchymal stem cell (MSC)-based therapy has shown remarkable efficacy in treating ARDS in animal experiments, clinical outcomes have been unsatisfactory, which may be attributed to the influence of the lung microenvironment during MSC administration. Extracellular vesicles (EVs) derived from endothelial cells (EC-EVs) are important components of the lung microenvironment and play a crucial role in ARDS. However, the effect of EC-EVs on MSC therapy is still unclear. In this study, we established lipopolysaccharide (LPS) - induced acute lung injury model to evaluate the impact of EC-EVs on the reparative effects of bone marrow-derived MSC (BM-MSC) transplantation on lung injury and to unravel the underlying mechanisms.MethodsEVs were isolated from bronchoalveolar lavage fluid of mice with LPS - induced acute lung injury and patients with ARDS using ultracentrifugation. and the changes of EC-EVs were analysed using nanoflow cytometry analysis. In vitro assays were performed to establish the impact of EC-EVs on MSC functions, including cell viability and migration, while in vivo studies were performed to validate the therapeutic effect of EC-EVs on MSCs. RNA-Seq analysis, small interfering RNA (siRNA), and a recombinant lentivirus were used to investigate the underlying mechanisms.ResultsCompared with that in non-ARDS patients, the quantity of EC-EVs in the lung microenvironment was significantly greater in patients with ARDS. EVs derived from lipopolysaccharide-stimulated endothelial cells (LPS-EVs) significantly decreased the viability and migration of BM-MSCs. Furthermore, engrafting BM-MSCs pretreated with LPS-EVs promoted the release of inflammatory cytokines and increased pulmonary microvascular permeability, aggravating lung injury. Mechanistically, LPS-EVs reduced the expression level of isocitrate dehydrogenase 2 (IDH2), which catalyses the formation of α-ketoglutarate (α-KG), an intermediate product of the tricarboxylic acid (TCA) cycle, in BM-MSCs. α-KG is a cofactor for ten-eleven translocation (TET) enzymes, which catalyse DNA hydroxymethylation in BM-MSCs.ConclusionsThis study revealed that EC-EVs in the lung microenvironment during ARDS can affect the therapeutic efficacy of BM-MSCs through the IDH2/TET pathway, providing potential strategies for improving the therapeutic efficacy of MSC-based therapy in the clinic.

Thermal decomposition study of 4-methyloxybenzyl-glycoside by TG/DTA and on-line pyrolysis-photoionization mass spectrometry

A flavor precursor of 4-methyloxybenzyl-2, 3, 4, 6-tetra-O-acetyl-β-d-glucopyranoside (MBGL) was synthesized via a modified Koenigs–Knorr reaction. The thermal decomposition behaviour and pyrolysis intermediate products of the glycoside were studied by simultaneous thermogravimetric/differential thermal analysis (TG/DTA) and synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). TG/DTA results showed that the largest mass loss rate appeared at a Tp of 246.7 °C. PIMS was used to identify the pyrolysis products of MBGL at 300 °C, 500 °C and 700 °C, respectively. The experimental apparatus had some advantages in real-time analysis and fewer secondary reactions. Some important pyrolysis intermediates, such as the ions of the 4-methyloxybenzyl group at m/z 121 and the glycone moiety at m/z 347, were detected by PIMS. The results indicate that the MBGL was probably showed a different pyrolysis way compared with the other glycosides. This work reports a useful application of synchrotron VUV PIMS in a thermal decomposition study of glycoside flavor precursors.

Phenanthrene metabolism in Panicum miliaceum: anatomical adaptations, degradation pathway, and computational analysis of a dioxygenase enzyme.

Polycyclic aromatic compounds (PAHs) are persistent organic pollutants of environmental concern due to their potential impacts on food chain, with plants being particularly vulnerable. While plants can uptake, transport, and transform PAHs, the precise mechanisms underlying their localization and degradation are not fully understood. Here, a cultivation experiment conducted with Panicum miliaceum exposed different concentrations of phenanthrene (PHE). Intermediate PHE degradation compounds were identified via GC-MS analysis, leading to the proposal of a phytodegradation pathway featuring three significant benzene ring cleavage steps. Our results showed that P. miliaceum exhibited the ability to effectively degrade high levels of PHE, resulting in the production of various intermediate products through several chemical changes. Examination of the localization and anatomical characteristics revealed structural alterations linked to PHE stress, with an observed enhancement in PHE accumulation density in both roots and shoots as treatment levels increased. Following a 2-week aging period, a decrease in the amount of PHE accumulation was observed, along with a change in its localization. Bioinformatics analysis of the P. miliaceum 2-oxoglutarate-dependent dioxygenase (2-ODD) DAO-like protein revealed a 299 amino acid structure with two highly conserved domains, namely 2OG-FeII_Oxy and DIOX_N. Molecular docking analysis aligned with experimental results, strongly affirming the potential link and direct action of 2-ODD DAO-like protein with PHE. Our study highlights P. miliaceum capacity for PAHs degradation and elucidates the mechanisms behind enhanced degradation efficiency. By integrating experimental evidence with bioinformatics analysis, we offer valuable insights into the potential applications of plant-based remediation strategies for PAHs-contaminated environments.

Bio-electrochemical degradation of carbamazepine (CBZ): A comprehensive study on effectiveness, degradation pathway, and toxicological assessment

Recent attention on the detrimental effects of pharmaceutically active compounds (PhACs) in natural water has spurred researchers to develop advanced wastewater treatment methods. Carbamazepine (CBZ), a widely recognized anticonvulsant, has often been a primary focus in numerous studies due to its prevalence and resistance to breaking down. This study aims to explore the effectiveness of a bio-electrochemical system in breaking down CBZ in polluted water and to assess the potential harmful effects of the treated wastewater. The results revealed bio-electro degradation process demonstrated a collaborative effect, achieving the highest CBZ degradation compared to electrodegradation and biodegradation techniques. Notably, a maximum CBZ degradation efficiency of 92.01% was attained using the bio-electrochemical system under specific conditions: Initial CBZ concentration of 60 mg/L, pH level at 7, 0.5% (v/v) inoculum dose, and an applied potential of 10 mV. The degradation pathway established by identifying intermediate products via High-Performance Liquid Chromatography-Mass Spectrometry, revealed the complete breakdown of CBZ without any toxic intermediates or end products. This finding was further validated through in vitro and in vivo toxicity assays, confirming the absence of harmful remnants after the degradation process.

LaCoO3@Fe3O4 as peroxymonosulfate activator derived from spent lithium battery cathode materials for degradation of sulfamethoxazole in water

To reduce the various hazards of SMX to aquatic ecosystems, in this study, magnetically separable LaCoO3@Fe3O4 catalysts for the degradation of sulfamethoxazole (SMX) in water by activated peroxymonosulfate (PMS) were successfully prepared by using cobalt oxalate recovered from spent batteries using sol–gel, hydrothermal, and high-temperature calcination methods. The main factors influencing the reaction and the effect of coexisting ions on the degradation efficiency of SMX were investigated. The results showed that under optimal conditions ([SMX] = 30 mg, [LaCoO3@Fe3O4] = 10 mg/L, [PMS] = 30 mg/L, pH (initial) = 7.02), the LaCoO3@Fe3O4/PMS system degraded SMX up to 93 % in 15 min. The degradation of SMX in the LaCoO3@Fe3O4/PMS system was shown to be achieved by a combination of radical (SO4•-/•OH/•O2–) and non-radical (1O2) pathways by quenching experiments and electron paramagnetic resonance spectroscopy (EPR) analysis. Then, three possible degradation pathways were proposed using LC-MS, and Ecological Constitutive Relationship (ECOSAR) analysis showed that the toxicity of the intermediate products was all lower than that of SMX, indicating that the system is feasible for SMX degradation. This study provides a new idea for activating PMS for the degradation of antibiotics in water by preparing catalysts using precious metals from recycled batteries.

Multi-omics analyses provide insights into the genomic basis of differentiation among four sweet osmanthus groups.

Sweet osmanthus (Osmanthus fragrans) is famous in China for its flowers and contains four groups: Albus, Luteus, Aurantiacus, and Asiaticus. Understanding the relationships among these groups and the genetic mechanisms of flower color and aroma biosynthesis are of tremendous interest. In this study, we sequenced representative varieties from two of the four sweet osmanthus groups. Multi-omic and phylogenetic analyses of varieties from each of the four groups showed that Asiaticus split first within the species, followed by Aurantiacus and the sister groups Albus and Luteus. We show that the difference in flower color between Aurantiacus and the other three groups was caused by a 4-bp deletion in the promoter region of carotenoid cleavage dioxygenase 4 (OfCCD4) that leads to expression decrease. In addition, we identified 44 gene pairs exhibiting significant structural differences between the multi-seasonal flowering variety 'Rixianggui' in the Asiaticus group and other autumn flowering varieties. Through correlation analysis between intermediate products of aromatic components and gene expression, we identified eight genes associated with the linalool, α- and β-ionone biosynthesis pathways. Overall, our study offers valuable genetic resources for sweet osmanthus, while also providing genetic clues for improving the flower color and multi-season flowering of osmanthus and other flowers.

Mo-BiVO4 Photocatalytically Modified Ceramic Ultrafiltration Membranes for Enhanced Water Treatment Efficiency.

This study highlights the effectiveness of photocatalytically modified ceramic ultrafiltration (UF) membranes in alleviating two major drawbacks of membrane filtration technologies. These are the generation of a highly concentrated retentate effluent as a waste stream and the gradual degradation of the water flux through the membrane due to the accumulation of organic pollutants on its surface. The development of two types of novel tubular membranes, featuring photocatalytic Mo-BiVO4 inverse opal coatings, demonstrated a negligible impact on water permeance, ensuring consistent filtration and photocatalytic efficiency and suggesting the potential for maintaining membrane integrity and avoiding the formation of highly concentrated retentate effluents. Morphological analysis revealed well-defined coatings with ordered domains and interconnected macropores, confirming successful synthesis of Mo-BiVO4. Raman spectroscopy and optical studies further elucidated the composition and light absorption properties of the coatings, particularly within the visible region, which is vital for photocatalysis driven by vis-light. Evaluation of the tetracycline removal efficiency presented efficient adsorption onto membrane surfaces with enhanced photocatalytic activity observed under both UV and vis-light. Additionally, vis-light irradiation facilitated significant degradation, showcasing the versatility of the membranes. Total Organic Carbon (TOC) analysis corroborated complete solute elimination or photocatalytic degradation without the production of intermediates, highlighting the potential for complete pollutant removal. Overall, these findings emphasize the promising applications of Mo-BiVO4 photocatalytic membranes in sustainable water treatment and wastewater remediation processes, laying the groundwork for further optimization and scalability in practical water treatment systems.

Regulation of Tetramethylpyrazine Formation by the Phenolics-Fenton Coupled Redox Cycling System.

A novel technique for generating tetramethylpyrazine (TTMP) was proposed, carried out on a phenolics-Fenton coupled redox cycling system in an acetoin-ammonium acetate (AA-ACT) pattern reaction. The TTMP generation employing the Fenton system is a first-order reaction that significantly increased the reaction rate, especially in the early stages, distinguishing it from the original zero-order kinetics reaction pattern. Further, the Fenton reaction effectively promotes the TTMP generation at lower temperature, and epigallocatechin gallate (EGCG) could reset the Fenton reaction, accomplishing the redox cycle. We have discovered a novel class of intermediate products, N-substituted amides, which act as a "reservoir" and transform into amino acid, then undergo aromatization to generate TTMP. The results provide a useful supplement for intelligent synthesis route design, and a new approach for understanding the transformation pathways of pyrazines.

New Method for Photoactive Cement Preparation-Selected Mechanical Properties and Photocatalytic Activity of New Materials.

In this study, a new method of obtaining photoactive cements is presented. The goal was to obtain photoactive cements using a method that could reduce the production costs. In the study, an intermediate product from the production of titanium dioxide using the sulfate method, taken from the installation before the calcination process, was used to obtain photoactive cements. Laboratory conditions corresponding to introducing this amorphous TiO2 into cement clinker during its cooling were simulated. The study shows that the temperature from 300 to 800 °C and the time of amorphous TiO2 contact with the cement clinker within 30 min is sufficient to obtain a photoactive cement. The highest photocatalytic activity was obtained for the material with 5 wt.% TiO2 content, and the method used did not cause a significant decrease in the bending and compressive strength of the new photoactive cements. The obtained materials were characterized by determining the crystal size of the TiO2, the sulfur content and the photocatalytic activity during NO decomposition under UV radiation. The bending and compressive strength were measured. The influence of the addition of photocatalysts on the beginning and end of the setting time was also investigated.

Sustainable Sol‐Gel Approach for Visible Light‐Responsive Titanium Dioxide Nanoparticles in Efficient Diazinon Removal

AbstractThis study addresses water pollution challenges by employing photocatalysis as an effective solution. Titanium dioxide (TiO2) with unique characteristics is widely utilized in this approach. However, the design of nanosized TiO2 particles is crucial for enhancing photocatalytic performance during diazinon's photodegradation. As such, the TiO2 nanoparticles (NPs) were synthesized via the green sol‐gel method in this study, exhibit a mixed anatase‐brookite phase, a small particle size of 11.17 nm, and lower bandgap energy (3.00 eV) than pure anatase TiO2 of 3.20 eV, rendering them active under visible light. DFTB calculation was deployed to investigate the role of oxygen vacancies in reducing the bandgap energy. Experimentally measured (3.00 eV) and computationally (2.812 eV) determined bandgap energies align well. The TiO2 NPs demonstrate significant photocatalytic efficacy, degrading 73.3 % of diazinon within 210 min under sunlight, with a mineralization degree of 43.50 %, and 2‐isopropyl‐6‐methylpyrimidin‐4‐ol (IMP) was detected as the intermediate product. The photodegradation follows first‐order kinetics, and adsorption isotherm analysis fits the Langmuir model. ⋅O2− is identified as the predominant reactive oxygen species in the diazinon's photodegradation. Hence, the synthesized TiO2 NPs offer good reusability, maintaining a degradation efficiency of 67.4 % even after five cycles, showing good potential for wastewater treatment applications.

The Elimination of Levofloxacin from High-Salinity Wastewater via the Electrochlorination Process

The electrochlorination (E-Cl) process has attracted much attention as it is a highly efficient method for treating organic compounds in hypersaline wastewater. In this study, the E-Cl process was utilized for the removal of antibiotics. The optimal experimental conditions were determined to be a NaCl concentration of 100 mM, a current density of 1.5 mA/cm2, a pH of 7.0, and a plate spacing of 1 cm, with a levofloxacin (LEV) degradation efficiency reaching as high as 99% using this setup. The effects of the presence of other ions and humic acid on the E-Cl process were investigated, and it was found that the degradation of LEV was not significantly affected by the presence of coexisting substances. In addition, free chlorine was identified as the primary active species for the degradation of LEV by means of a quenching experiment. It was demonstrated by 3D EEM and TOC that LEV was not completely mineralized and that intermediate products may be present. In order to reveal the degradation pathways of LEV, its degradation products were also analyzed via LC-MS, and some possible pathways of LEV degradation in this system were proposed. The successful degradation of LEV demonstrated that the E-Cl process is an efficient and promising technique for the treatment of organic pollutants in high-salinity wastewater.

Process Intensification of the Continuous Synthesis of Bio-Derived Monomers for Sustainable Coatings Using a Taylor Vortex Flow Reactor.

We describe the optimization and scale-up of two consecutive reaction steps in the synthesis of bio-derived alkoxybutenolide monomers that have been reported as potential replacements for acrylate-based coatings (Sci. Adv.2020, 6, eabe0026). These monomers are synthesized by (i) oxidation of furfural with photogenerated singlet oxygen followed by (ii) thermal condensation of the desired 5-hydroxyfuranone intermediate product with an alcohol, a step which until now has involved a lengthy batch reaction. The two steps have been successfully telescoped into a single kilogram-scale process without any need to isolate the 5-hydroxyfuranone between the steps. Our process development involved FTIR reaction monitoring, FTIR data analysis via 2D visualization, and two different photoreactors: (i) a semicontinuous photoreactor based on a modified rotary evaporator, where FTIR and 2D correlation spectroscopy (2D-COS) revealed the loss of the methyl formate coproduct, and (ii) our fully continuous Taylor Vortex photoreactor, which enhanced the mass transfer and permitted the use of near-stoichiometric equivalents of O2. The use of in-line FTIR monitoring and modeling greatly accelerated process optimization in the Vortex reactor. This led to scale-up of the photo-oxidation in 85% yield with a projected productivity of 1.3 kg day-1 and a space-time yield of 0.06 mol day-1 mL-1. Higher productivities could be achieved while sacrificing yield (e.g., 4 kg day-1 at 40% yield). The use of superheated methanol at 200 °C in a pressurized thermal flow reactor accelerated the second step, the thermal condensation of 5-hydroxyfuranone, from a 20 h batch reflux reaction (0.5 L, 85 g) to a space time of <1 min in a reactor only 3 mL in volume operating with projected productivities of >700 g day-1. Proof of concept for telescoping the two steps was established with an overall two-step yield of 67%, producing a process with a projected productivity of 1.1 kg day-1 for the methoxybutenolide monomer without any purification of the 5-hydroxyfuranone intermediate.

Enhancement of microplastics degradation with MIL-101 modified BiOI photocatalyst under light and dark alternated system

The composite material combining BiOI with metal-organic frameworks, was developed as catalyst for microplastics degradation. The preparation was modified to achieve the optimal composite catalyst BiOI/MIL-101–40%. The composites exhibited a larger surface area, superior photo-activity, and a distinct heterojunction structure, which accelerated the separation of electrons and holes. Besides, the inclusion of Fe(II) within MIL-101 could construct a photo-Fenton reaction upon the addition of H2O2 in the solution. The carbonyl index of treated polyethylene microplastics increased by 0.127 after 6 h reaction, which was 5.3 and 3.7 times higher than monomer BiOI and MIL-101, respectively. Efficient electron-hole separation and Fe(III)/Fe(II) conversion improved the rate-limiting step of the Fenton process, leading to a synergistic effect between photocatalysis and Fenton reaction, significantly enhancing PE degradation efficiency. Electron spin resonance spectroscopy and selective radical quenching experiments were performed to detect the active components, and the main active species proved to be the hydroxyl radical and the hole. The band structure of the photocatalyst and intermediate products in the reaction solution were subsequently analyzed, leading to the inference of potential reaction mechanisms and pathways. The catalyst-built Fenton system demonstrated outstanding proficiency even under alternating light and dark conditions. The extracted microplastic samples also confirmed the feasibility of this system for complex samples. In conclusion, this study highlighted a green and efficient approach that may be used in future industrial applications to combat microplastic pollution.

Metal-modified CeO2 nanobelts for catalytic oxidation of ethyl acetate: Roles of surface lattice oxygen and hydrolysis behaviors

Based on the comparison of three counterparts [Mg-, Al- and Cu-modified CeO2 nanobelts], it is illustrated that the low-temperature hydrolysis of ethyl acetate (EA) rapidly occurs and the removal of absorbed hydrolyzates (mainly acetates) is considered the rate-determining step. As the temperature increases, the escape of surface lattice oxygen (Os-latt) breaks through the shield of hydrolyzates and promotes the deep oxidation of intermediate products. Additionally, the activated Os-latt also facilitates the C-O bond cleavage in EA by nucleophilic attack. Due to the Os-latt escape, surface metal ions achieve more unsaturated coordinations to absorb the CH3COO– species, leading to competitive adsorption between O2 and hydrolyzates. The Cu modification strengthens the coordination adsorption of CH3COO– species, and the Al modification exhibits a low Os-latt mobility. These factors all contribute to a strong adsorption or accumulation of surface hydrolyzates. Therefore, a favorable ester hydrolysis-oxidation process over CeO2-based catalysts depends not only on excellent Os-latt mobility but also the suitable adsorption capacity of hydrolyzates, such as Mg modification.

Ruthenium decorated nickel-iron layered double hydroxides (NiFe-LDH) for promoting peroxymonosulfate activation and atrazine degradation

With the extensive use of atrazine (ATZ), its potential hazards to ecological environment and human health have raised public concerns. This study reports the effective degradation of ATZ via advanced oxidation processes (AOPs) using peroxymonosulfate (PMS) activated by heterogeneous catalysts of Ru loaded NiFe-LDH blossom nanosheets (Ru/NiFe-LDH). During AOPs, the highly dispersed Ru sites as the main catalytic centers and the NiFe-LDH substrate synergistically stimulated PMS to efficiently produce reactive oxygen species to oxidize ATZ. Under optimal conditions, the degradation activity of ATZ by 5.8Ru/NiFe-LDH/PMS system reached 100% within 90 min. Additionally, it also exhibited good environmental applicability. Besides, electron paramagnetic resonance along with quenching experiments illustrated the production of 1O2, O2• −, •OH, SO4• − and surface-bond radicals during the degradation, where 1O2, •OH and surface-bond radicals were further identified as the dominant oxygen species for the oxidation. The ATZ degradation pathway was determined using the liquid chromatography-mass spectrometry to discern the intermediate products, e.g., dealkylation, alkylic-hydroxylation and dechlororination-hydroxylation processes. This work holds a potential application value for the removal of atrazine and other pollutants.

Decoupling and decomposition of emissions and economic growth in Guangdong: A perspective of embodied carbon flow

Decoupling the dependence on carbon emissions from achieving high-quality economic development is a paramount objective for China. However, the often-overlooked aspect is the carbon emissions generated through trade activities, which can lead to an overestimation of decoupling progress. Our study quantified and compared the decoupling status of production-based and consumption-based carbon emissions from economic growth in Guangdong from 2002 to 2017 from the perspective of inter-provincial embodied carbon flow, and further investigated its driving factors. The results reveal that consumption-based carbon emissions consistently surpass production-based emissions, although they exhibited a steady decline in recent years. As a significant contributor to embodied carbon emissions, Guangdong outsources a considerable portion of its emissions to less developed regions such as Liaoning and Guangxi by importing raw or intermediate products with lower value-added raw, while it exports service products to provinces like Beijing and Zhejiang. Decoupling analysis indicated that Guangdong is progressively moving towards an optimal state of "double decoupling", where both production and consumption-based carbon emissions are decreasing. This represents a departure from the previous scenario of "fake decoupling", characterized by a reduction in production-based carbon emissions but persistently high consumption-based emissions. Additionally, our structural decomposition analysis highlights the potential for reducing carbon emissions and enhancing decoupling by increasing the utilization of clean energy and optimizing the trade input structure. These findings underscore the importance of accounting for embodied carbon emissions in decoupling studies and offer valuable insights for achieving high-quality development.

Fabrication of porous biochar supported Bi2MoO6 photocatalyst for efficient degradation of ciprofloxacin in seawater under visible light irradiation: Mechanistic investigation and intermediates analysis

Efficient separation of photocarriers is a critical approach for advancing high-performance photocatalyst systems to effectively remove environmental contaminants. In this investigation, a hydrothermal technique was employed to synthesize composites of Bi2MoO6 and porous biochar derived from banana peels (BPB). The samples underwent various characterization methods to assess their composition, morphology, and photoelectrochemical properties. The BPB/Bi2MoO6 composite exhibited a synergistic adsorption and photocatalytic impact in eliminating the antibiotic ciprofloxacin (CIP) from pure water and seawater. The optimized BPB/Bi2MoO6 sample displayed a significant degradation efficiency of 98.7 % for CIP after 90 min of visible-light exposure in pure water. In artificial seawater, the degradation efficiency for CIP remained high at 93.6 %, which was 12.2 times greater than that of pure Bi2MoO6. The study also explored the impact of various factors such as catalyst dosage, solution pH, and pollutant concentration on the photocatalytic performance of BPB/Bi2MoO6. Moreover, the catalyst exhibited enhanced efficiency in the adsorption-photocatalytic degradation of CIP within a continuous flow reaction system. The enhanced photocatalytic performance was attributed to the composite's exceptional adsorption capacity, enhanced response to visible light, and efficient separation of photoinduced electron-hole pairs. Furthermore, the BPB/Bi2MoO6 photocatalyst displayed good stability and recyclability over five consecutive photodegradation cycles. Radical trapping and electron spin resonance (ESR) experiments verified that the degradation of CIP was mainly driven by •OH and h+ radicals. A thorough investigation employing density functional theory (DFT), radical trapping and ESR tests, and liquid chromatography mass spectrometry (LC-MS) was conducted to elucidate the degradation mechanism and pathways. Furthermore, toxicity assessment software was utilized to illustrate the progressive reduction in toxicity of the intermediate products. In conclusion, this study provides valuable insights into the role of biochar in enhancing the photocatalytic degradation of pollutants and offers guidance for the future development of environmentally friendly photocatalysts.

Cascaded *CO-*COH Intermediates on a Nonmetallic Plasmonic Photocatalyst for CO2-to-C2H6 with 90.6% Selectivity.

Oxygen vacancies (OV) in nonmetallic plasmonic photocatalysts can decrease the energy barrier for CO2 reduction, boosting C1 intermediate production for potential C2 formation. However, their susceptibility to oxidation weakens C1 intermediate adsorption. Herein we proposed a "photoelectron injection" strategy to safeguard OV in W18O49 by creating a W18O49/ZIS (W/Z) plasmonic photocatalyst. Moreover, photoelectrons contribute to the local multi-electron environment of W18O49, enhancing the intrinsic excitation of its hot electrons with extended lifetimes, as confirmed by in-situ XPS and femtosecond transient absorption analysis. Density functional theory calculations revealed that W/Z with Ov enhances CO2 adsorption, activating *CO production, while reducing the energy barrier for *COH production (0.054 eV) and subsequent *CO-COH coupling (0.574 eV). Successive hydrogenation revealed that the free energy for *CH2CH2 hydrogenation (0.108 eV) was lower than that for *CH2CH2 desorption for C2H4 production (0.277 eV), favouring C2H6 production. Consequently, W/Z achieves an efficient C2H6 activity of 653.6 μmol g-1 h-1 under visible light, with an exceptionally high selectivity of 90.6%. This work offers a new strategy for the rational design of plasmonic photocatalysts with high selectivity for C2+ products.