Sustainable design of photo-Fenton-like oxidation process in actual livestock wastewater through the highly dispersed FeCl3 anchoring on a g-C3N4 substrate.

Photocatalytic technology emerges as a promising solution for the sustainable treatment of contaminated wastewater. However, the practical implementation of designed photocatalysts often faces challenges due to the intricate 'high carbon footprint' process and limited outdoor laboratory investigations. Herein, a simple yet versatile impregnation approach is proposed to anchor highly dispersed FeCl3 on a g-C3N4 substrate (Fe-C3N4) with minimal energy consumption and post-processing. Fe-C3N4 enhances photocatalytic reactivity for antibiotic degradation via a synergistic photo-Fenton-like oxidation technique, efficiently removing antibiotic pollutants from actual livestock wastewater. The Fe-C3N4 catalyst exhibited consistent degradation performance over five cycles in laboratory conditions, maintaining a degradation efficiency exceeding 90 % for tetracycline hydrochloride (TCHCl). Furthermore, we engineered a straightforward Fe-C3N4Na2SiO3 reactor for treating livestock wastewater, achieving an 81.8 % removal of TCHCl in outdoor field tests conducted in the winter and summer in China. The Fe-C3N4 catalyst demonstrated high feasibility in treating antibiotic-contaminated livestock wastewater under year-round climatic conditions, leveraging synergistic effects. The stabilization of Fe-C3N4 for the degradation of antibiotic-containing wastewater under sunlight represents a significant advancement in the practical application of photocatalysts, marking a crucial milestone from experimental conception to implementation. Acute toxicity estimation suggested that intermediates/products generated exhibited lower toxicity compared to TCHCl, indicating their practical applicability. Density functional theory (DFT) analysis successfully predicted significant electron transfer between Fe-C3N4 and TCHCl, indicating efficient interfacial interactions on the TCHCl surface. To ensure the environmental sustainability of Fe-C3N4, a life cycle assessment (LCA) was conducted to compared this photocatalyst with other commonly used emerging photocatalysts. The results demonstrated that Fe-C3N4 exhibits a two orders of magnitude lower CO2 equivalent emission compared to the ZnO photocatalyst, indicating a cost-effective and efficient synergistic photo-Fenton-like catalytic approach. This low-cost photocatalyst, moving from the laboratory to real-world wastewater applications, provides a powerful and more sustainable solution for the efficient treatment of wastewater containing antibiotics from livestock farming.

A methodological review of compound-specific radiocarbon analysis for polycyclic aromatic hydrocarbons in environmental matrices.

Identifying the sources of polycyclic aromatic hydrocarbons (PAHs) in complex environmental matrices is essential for understanding the impact of combustion-related human activities on the environment. Since the turn of the century, advances in analytical capability and accuracy of accelerator mass spectrometry (AMS) have made it possible to accurately determine the source apportionment of PAHs based on their radiocarbon (14C) mass conservation. This also allows us to trace the environmental transport processes of PAHs from the perspective of molecular 14C. However, natural environmental matrices have very low concentrations of PAHs (ppb to ppm level). To meet the requirements of carbon weight for 14C measurement by AMS, trace PAHs in complex environmental matrices must be enriched thousands of times, and then higher purity individual PAH molecules should be obtained through a series of complex purification procedures. Therefore, the technical difficulty is the main challenge in expanding the application of compound-specific 14C analysis in environmental science. This article reviews the detailed pretreatment procedures for 14C measurement of specific PAHs, including sample enrichment, extraction and purification of aromatic components, preparation of compound-specific PAHs by preparative capillary gas chromatography, graphitization of samples with ultra-small carbon content, and relevant quality control and assurance procedures. This study aims to help environmental geoscientists understand the technical process of 14C analysis of PAHs and inspire new scientific questions related to environmental science. To our knowledge, this is the first comprehensive review of the technical method of compound-specific 14C analysis for PAHs.

Different crystalline manganese dioxide and biochar co-conditioning aerobic composting: Reduced ammonia volatilization and improved organic fertilizer quality.

Aerobic composting is a sustainable and effective waste disposal method. However, it can generate massive amounts of ammonia (NH3) via volatilization. Effectively reducing NH3 volatilization is vital for advancing aerobic composting and protecting the ecological environment. Herein, two crystal types of MnO2 (α-MnO2 and δ-MnO2) are combined with biochar (hydrochar (WHC) and pyrochar (WPC), respectively) and used as conditioners for the aerobic composting of chicken manure. Results reveal that α-MnO2 (34.6%) can more effectively reduce NH3 accumulation than δ-MnO2 (27.1%). Moreover, the combination of WHC and MnO2 better reduces NH3 volatilization (48.5-58.9%) than the combination of WPC and MnO2 (15.8-40.1%). The highest NH3 volatilization reduction effect (58.9%) is achieved using the combination of WHC and δ-MnO2. Because the added WHC and δ-MnO2 promote the humification of the compost, the humic acid to fulvic acid ratio (HA/FA ratio) dramatically increases. The combination of WHC and δ-MnO2 doubled the HA/FA ratio and resulted in a net economic benefit of 130.0 RMB/t. Therefore, WHC and δ-MnO2 co-conditioning can promote compost decomposition, improving the quality of organic fertilizers and substantially reducing NH3 volatilization.

Surface acidic sites strengthened core-shell HC@MnO2 for enhanced gaseous ammonia adsorption.

As a common gaseous pollutant in atmospheric environment, ammonia (NH3) not only contributes to the formation of haze, but also disturb the nitrogen balance in ecosystem through atmospheric nitrogen deposition. Therefore, the control of NH3 emission has important environmental significance. Adsorption is the most commonly used technology for NH3 purification in practice, and efficient adsorbents are the key to adsorption method. Herein, a core-shell structured HC@MnO2 adsorbent was constructed by in-situ growth of layered δ-MnO2 on hydrochar (HC) surface, and its surface acidic sites were further strengthened. The enhancement of surface acidic sites significantly improved the adsorption performance of HC@MnO2 for NH3, reaching 34.49 mg NH3/g, which was superior to commercial carbon-based materials (whose adsorption capacity was 8.47 times that of Coal-based activated carbon, 14.25 times that of Coconut shell activated carbon, and 12.77 times that of Bamboo charcoal). Moreover, the operating parameters and adsorption kinetics were detailly investigated. The adsorption of HC@MnO2 on NH3 was in accordance with pseudo-second-order adsorption kinetics model. Large surface area of core-shell structure and abundant surface acidic sites of δ-MnO2 are the decisive reasons for the excellent adsorption performance of HC@MnO2. Importantly, the enhancement of surface stronger Brønsted acidic sites is the key to improve NH3 adsorption performance of HC@MnO2. Finally, the thermal regeneration and recycling performance of HC@MnO2-H were also investigated. This study provides a suggestive for further research on low-cost composite materials with excellent NH3 adsorption performance.

Engineering Manganese Defects in Mn3O4 for Catalytic Oxidation of Carcinogenic Formaldehyde.

Formaldehyde (HCHO) is a priority pollutant in the indoor environment, which is irritative and carcinogenic to humans. The non-noble metal oxides have a wide application prospect in the decomposition of HCHO. Defects in metal oxides have been widely accepted as active sites in heterogeneous catalysis. Compared with the extensive study of oxygen defects, the effect of cation defects has not been clearly addressed. Herein, Mn defect-rich Mn3O4 was synthesized by pyrolysis of Ce-doped MnCO3. It is found for the first time that the content of Mn defects in Mn3O4 can be adjusted by introducing Ce. The introduction of Ce resulted in the higher contents of Mn defects, which significantly enhances the HCHO decomposition. Moreover, Mn defect can effectively narrow the half-metallic gap of Mn3O4, regulate the electronic structure and coordination environment of surrounding oxygen, and further improve the activity and mobility of neighboring oxygen atoms. Importantly, Mn defects are not only beneficial to the generation of neighboring oxygen vacancy but also conducive to enhancing the activation ability of oxygen vacancy for O2. The advantages resulting from Mn defects significantly enhance the HCHO decomposition. This research proposes a strategy to adjust cation defects and deepens the comprehension of the function of cation defects.

Photoinduced Simultaneous Thermal and Photocatalytic Activities of MnO2 Revealed by Femtosecond Transient Absorption Spectroscopy.

Solar light-induced catalysis has recently received great interest in efficiently and economically degrading volatile organic compounds, which deteriorate indoor and outdoor air quality. However, a few studies explored its essential photophysical and photochemical processes. Herein, the femtosecond transient absorption spectroscopy was used to investigate the decay of photogenerated holes in MnO2 with different Mn vacancies. About 67-93% of photogenerated holes recombined within a very short time (<130 ps), resulting in enhanced thermal catalytic activity of MnO2. Besides, really a small portion of photogenerated holes remained unchanged in the detection time period (1400 ps). ESR tests further confirm that photocatalytic pathway plays a significant role in degrading VOCs besides the thermal catalytic pathway when MnO2 is under illumination of UV-visible light. The introduction of an appropriate content of Mn vacancy did prolong the lifetime of photogenerated carriers. This work clarifies the mechanism of photoirradiation in improving the catalytic activity of MnO2 and the effect of manganese defects on the catalytic reaction.

Harvesting the vibration energy of α-MnO2 nanostructures for complete catalytic oxidation of carcinogenic airborne formaldehyde at ambient temperature.

Vibration is one of the most prevalent energy sources in natural environment, which can also be harvested and utilized to drive chemical reaction. Herein, mechanical vibration is used for enhancing the catalytic decomposition of formaldehyde at ambient temperature with the assistance of four well-defined morphologies α-MnO2 (nanowire, nanotube, nanorod and nanoflower). In particular, α-MnO2 nanowire exhibits the best catalytic activity, which can completely mineralize formaldehyde into carbon dioxide at ambient temperature by harvesting the vibration energy. To the best of our knowledge, this may be the first report that α-MnO2, as a non-noble metal catalyst, can completely decompose formaldehyde to carbon dioxide at ambient temperature. The characterization results show that α-MnO2 nanowire has a much higher oxygen vacancy concentration than other three catalysts. In addition, thermal effect generated from friction between nanoparticles induced by ultrasonic vibration may enhance its catalytic activity. More importantly, it is the vibration that effectively promotes the activation of O2 adsorbed on the surface oxygen vacancy to produce more , thus increasing the catalytic decomposition performance. The strategy presented herein demonstrates a new approach for efficient use of mechanical vibration to improve catalytic activity of traditional catalysts.

Scalable synthesis of water-dispersible 2D manganese dioxide monosheets.

2D nanomaterials with atomic thickness usually exhibit high specific surface areas and atom exposure rates, which are suitable for surface reaction related applications. In this study, we selected the oxalate ions as the structure-inducing agent to synthesize δ-MnO2 ultrathin nanosheets (~4.5 nm) via a facile hydrothermal method. Subsequently, an efficient exfoliation method to prepare single-layer MnO2 nanosheets (~0.9 nm) with the major exposed {0 0 1} facets was successfully developed. We found that the oxalate ions play a major role in the growth and formation of δ-MnO2 ultrathin nanosheets, and the formation process of the ultrathin structure was also investigated. The resulting single-layer MnO2 nanosheets (monosheets) with exposed {0 0 1} facets showed much higher catalytic performance for carcinogenic airborne formaldehyde, better than few-layer ultrathin nanosheets and nanoflowers with exposed {1 0 0} facets. The reasons for the high catalytic activity of MnO2 monosheets can be attributed to its higher surface areas and oxygen vacancy concentration. Moreover, the density-functional-theory (DFT) theoretical calculations showed that the oxygen vacancy in single-layer {0 0 1} facets exhibited the strongest adsorption/activation ability to O2 and H2O, which was very favorable for catalytic oxidation of formaldehyde. The synthesis strategy of ultrathin nanosheets described in this article may serve as reference and guidance for the preparation of other 2D ultrathin nanomaterials.

Degradation of TAIC by water falling film dielectric barrier discharge--influence of radical scavengers.

This work describes the application of plasma generated by water falling film dielectric barrier discharge for the degradation of triallyl isocyanurate (TAIC). The results indicated that TAIC solution of 1000mg/L was effectively removed within 60min treatment at 120W output power. Six intermediates were identified and a possible evolution of the TAIC degradation process was continuously proposed basing on the results of mass spectrum analysis. The effects of metal ions and radical scavengers were investigated. Results showed that whatever hydrogen radical scavengers (carbon tetrachloride, perfluorooctane) or hydroxyl radical scavengers (iso-propyl alcohol, tert-butyl alcohol) all could further enhance the degradation processes, and both kings of radical scavengers could promote the generation of H2O2. In the present study, we employed a novel method by introducing the mixed additives of Fe(2+) and radical scavengers into the plasma. It was found that the reaction rate constant and energy efficiency were improved by 309.2% and 387.8%, respectively. Among the mixed additives, Fe(2+) could promote the decomposition and increase the oxidizing power of H2O2, which is generated from the plasma discharge and greatly enhanced by the radical scavengers.

Dielectric barrier discharge induced degradation of diclofenac in aqueous solution.

A dielectric barrier discharge (DBD) reactor as one of the advanced oxidation processes was applied to the degradation of diclofenac in aqueous solution. The various parameters that affect the degradation of diclofenac and the proposed evolutionary process were investigated. The results indicated that the inner concentrations of 10 mg/L diclofenac can be all removed within 10 min under conditions of 50 W and pH value of 6.15. The existence of Fe(2+) in the liquid phase can promote the degradation of diclofenac. But it was rather ineffective in mineralization, because the intermediates containing the aromatic rings were recalcitrant to be degraded. Five intermediates were identified by liquid chromatography-mass spectrometry (LC-MS), the OH · radical and O(3) were the major reactive species, and played an important role in the degradation of diclofenac. The toxicity of diclofenac degraded by DBD was assessed and the results indicated the efficiency of the DBD in the detoxification of the diclofenac solution.