Characterization of the degradation products of lignocellulosic biomass by using tandem mass spectrometry experiments, model compounds, and quantum chemical calculations.

Biomass-derived degraded lignin and cellulose serve as possible alternatives to fossil fuels for energy and chemical resources. Fast pyrolysis of lignocellulosic biomass generates bio-oil that needs further refinement. However, as pyrolysis causes massive degradation to lignin and cellulose, this process produces very complex mixtures. The same applies to degradation methods other than fast pyrolysis. The ability to identify the degradation products of lignocellulosic biomass is of great importance to be able to optimize methodologies for the conversion of these mixtures to transportation fuels and valuable chemicals. Studies utilizing tandem mass spectrometry have provided invaluable, molecular-level information regarding the identities of compounds in degraded biomass. This review focuses on the molecular-level characterization of fast pyrolysis and other degradation products of lignin and cellulose via tandem mass spectrometry based on collision-activated dissociation (CAD). Many studies discussed here used model compounds to better understand both the ionization chemistry of the degradation products of lignin and cellulose and their ions' CAD reactions in mass spectrometers to develop methods for the structural characterization of the degradation products of lignocellulosic biomass. Further, model compound studies were also carried out to delineate the mechanisms of the fast pyrolysis reactions of lignocellulosic biomass. The above knowledge was used to assign likely structures to many degradation products of lignocellulosic biomass.

Depleted carbon isotope compositions observed at Gale crater, Mars.

Obtaining carbon isotopic information for organic carbon from Martian sediments has long been a goal of planetary science, as it has the potential to elucidate the origin of such carbon and aspects of Martian carbon cycling. Carbon isotopic values (δ13CVPDB) of the methane released during pyrolysis of 24 powder samples at Gale crater, Mars, show a high degree of variation (-137 ± 8‰ to +22 ± 10‰) when measured by the tunable laser spectrometer portion of the Sample Analysis at Mars instrument suite during evolved gas analysis. Included in these data are 10 measured δ13C values less than -70‰ found for six different sampling locations, all potentially associated with a possible paleosurface. There are multiple plausible explanations for the anomalously depleted 13C observed in evolved methane, but no single explanation can be accepted without further research. Three possible explanations are the photolysis of biological methane released from the subsurface, photoreduction of atmospheric CO2, and deposition of cosmic dust during passage through a galactic molecular cloud. All three of these scenarios are unconventional, unlike processes common on Earth.

Effects of biochar types on seed germination, growth, chlorophyll contents, grain yield, sodium, and potassium uptake by wheat (Triticum aestivum L.) under salt stress.

Soil salinity is a significant challenge in agriculture, particularly in arid and semi-arid regions such as Pakistan, leading to soil degradation and reduced crop yields. The present study assessed the impact of different salinity levels (0, 25, and 50 mmol NaCl) and biochar treatments (control, wheat-straw biochar, rice-husk biochar, and sawdust biochar applied @ 1% w/w) on the germination and growth performance of wheat. Two experiments: a germination study and a pot experiment (grown up to maturity), were performed. The results showed that NaCl-stress negatively impacted the germination parameters, grain, and straw yield, and agronomic and soil parameters. Biochar treatments restored these parameters compared to control (no biochar), but the effects were inconsistent across NaCl levels. Among the different biochars, wheat-straw biochar performed better than rice-husk and sawdust-derived biochar regarding germination and agronomic parameters. Biochar application notably increased soil pHs and electrical conductivity (ECe). Imposing NaCl stress reduced K concentrations in the wheat shoot and grains with concomitant higher Na concentrations in both parts. Parameters like foliar chlorophyll content (a, b, and total), stomatal and sub-stomatal conductance, and transpiration rate were also positively influenced by biochar addition. The study confirmed that biochar, particularly wheat-straw biochar, effectively mitigated the adverse effects of soil salinity, enhancing both soil quality and wheat growth. The study highlighted that biochar application can minimize the negative effects of salinity stress on wheat. Specifically, the types and dosages of biochar have to be optimized for different salinity levels under field conditions.

Agricultural waste-based modified biochars differentially affected the soil properties, growth, and nutrient accumulation by maize (Zea mays L.) plants.

Biochar (BC) is an organic compound formed by the pyrolysis of organic wastes. Application of BCs as soil amendments has many benefits including carbon sequestration, enhanced soil fertility and sustainable agriculture production. In the present study, we acidified the different BCs prepared from rice straw, rice husk, wheat straw, cotton stalk, poultry manure, sugarcane press mud and vegetable waste; following which, we applied them in a series of pot experiments. Comparisons were made between acidified and non- acidified BCs for their effects on seed germination, soil properties (EC, pH) nutrient contents (P, K, Na) and organic matter. The treatments comprised of a control, and all above-described BCs (acidified as well as non-acidified) applied to soil at the rate of 1% (w/w). The maize crop was selected as a test crop. The results showed that acidified poultry manure BC significantly improved germination percentage, shoot length, and biomass of maize seedlings as compared to other BCs and their respective control plants. However, acidified BCs caused a significant decrease in nutrient contents (P, K, Na) of soil,maize seedlings, and the soil organic matter contents as compared to non- acidified BCs. But when compared with control treatments, all BCs treatments (acidified and non-acidified) delivered higher levels of nutrients and organic matter contents. It was concluded that none of the BCs (acidified and non-acidified) had caused negative effect on soil conditions and growth of maize. In addition, the acidification of BC prior to its application to alkaline soils might had altered soil chemistry and delivered better maize growth. Moving forward, more research is needed to understand the long-term effects of modified BCs on nutrient dynamics in different soils. In addition, the possible effects of BC application timings, application rates, particle size, and crop species have to be evaluated systemtically.

Hierarchical Hollow Carbon Particles with Encapsulation of Carbon Nanotubes for High Performance Supercapacitors.

A novel and sustainable carbon-based material, referred to as hollow porous carbon particles encapsulating multi-wall carbon nanotubes (MWCNTs) (CNTs@HPC), is synthesized for use in supercapacitors. The synthesis process involves utilizing LTA zeolite as a rigid template and dopamine hydrochloride (DA) as the carbon source, along with catalytic decomposition of methane (CDM) to simultaneously produce MWCNTs and COx -free H2 . The findings reveal a distinctive hierarchical porous structure, comprising macropores, mesopores, and micropores, resulting in a total specific surface area (SSA) of 913 m2  g-1 . The optimal CNTs@HPC demonstrates a specific capacitance of 306 F g-1 at a current density of 1 A g-1 . Moreover, this material demonstrates an electric double-layer capacitor (EDLC) that surpasses conventional capabilities by exhibiting additional pseudocapacitance characteristics. These properties are attributed to redox reactions facilitated by the increased charge density resulting from the attraction of ions to nickel oxides, which is made possible by the material's enhanced hydrophilicity. The heightened hydrophilicity can be attributed to the presence of residual silicon-aluminum elements in CNTs@HPC, a direct outcome of the unique synthesis approach involving nickel phyllosilicate in CDM. As a result of this synthesis strategy, the material possesses excellent conductivity, enabling rapid transportation of electrolyte ions and delivering outstanding capacitive performance.

Bimetal Oxides Anchored on Carbon Nanotubes/Nanosheets as High-Efficiency and Durable Bifunctional Oxygen Catalyst for Advanced Zn-Air Battery: Experiments and DFT Calculations.

To meet increasing requirement for innovative energy storage and conversion technology, it is urgent to prepare effective, affordable, and long-term stable oxygen electrocatalysts to replace precious metal-based counterparts. Herein, a two-step pyrolysis strategy is developed for controlled synthesis of Fe2O3 and Mn3O4 anchored on carbon nanotubes/nanosheets (Fe2O3-Mn3O4-CNTs/NSs). The typical catalyst has a high half-wave potential (E1/2 = 0.87 V) for oxygen reduction reaction (ORR), accompanied with a smaller overpotential (η10 = 290 mV) for oxygen evolution reaction (OER), showing substantial improvement in the ORR and OER performances. As well, density functional theory calculations are performed to illustrate the catalytic mechanism, where the in situ generated Fe2O3 directly correlates to the reduced energy barrier, rather than Mn3O4. The Fe2O3-Mn3O4-CNTs/NSs-based Zn-air battery exhibits a high-power density (153 mW cm-2) and satisfyingly long durability (1650 charge/discharge cycles/550 h). This work provides a new reference for preparation of highly reversible oxygen conversion catalysts.

Pd Single-Atom Loaded Ce-Zr Solid Solution Catalysts Prepared by Flame Spray Pyrolysis for Efficient CO Catalytic Oxidation.

Single-atom catalysts (SACs) exhibit remarkable catalytic activity at each metal site. However, conventionally synthesized single-atom catalysts often possess low metal loading, thereby constraining their overall catalytic performance. Here, a flame spray pyrolysis (FSP) method for the synthesis of a single-atom catalyst with a high loading capacity of up to 1.4 wt.% in practice is reported. CeZrO2 acts as a carrier and provides a large number of anchoring sites, which promotes the high-density generation of Pd, and the strong interaction between the metal and the support avoids atom aggregation. Pd-CeZrO2 series catalysts have excellent CO oxidation performance. When 0.97 wt.% Pd is added, the catalytic activity is the highest, and the temperature can be reduced to 120 °C. This work presented here demonstrates that FSP, as an inherently scalable technique, allows for elevating the single-atom loading to achieve an increase in its catalytic performance. The method presented here more options for the preparation of SACs.

Exploring Carbonization Temperature to Create Closed Pores for Hard Carbon as High-Performance Sodium-Ion Battery Anodes.

Biomass-derived porous carbon materials are meaningful to employ as a hard carbon precursor for anode materials of sodium-ion batteries (SIBs) from a sustainability perspective. Here, a straightforward approach is proposed to develop rich closed pores in pinenut-derived carbon, with the aim of improving Na+ plateau storage by adjusting the pyrolysis temperature. The optimized sample, namely the pinenut-derived carbon at 1300 °C, demonstrates remarkable reversible specific capacity of 278 mAh g-1, along with a high initial Coulomb efficiency of 85% and robust cycling stability (with a capacity retention of 89% after 800 cycles at 0.2 A g-1). In situ and ex situ analyses unveil that the developed closed pores play a significant role in enhancing the plateau capacity, providing compelling evidence for the "adsorption-filling" mechanism. Moreover, the corresponding full-cell achieves a high energy density of 245.7 Wh kg-1 (based on the total weight of both electrode active materials) and exhibits outstanding rate capability (191.4 mAh g-1 at 3 A g-1).

Boron-Nitrogen-Edged Biomass-Derived Carbon: A Multifunctional Approach for Colorimetric Detection of H2O2, Flame Retardancy, and Triboelectric Nanogenerator.

Enhancing the concentration and type of nitrogen (N) dopants within the Sp2-carbon domain of carbon recycled from biomass sources is an efficient approach to mimic CNT, GO, and rGO to activate oxidants such as H2O2, excluding toxic chemicals and limiting reaction steps. However, monitoring the kind and concentration of N species in the Sp2-C domain is unlikely with thermal treatments only. A high temperature for graphitization reduces N moieties, leading to low electron density. This inhibits H2O2 adsorption and activation on catalyst surfaces. In this study, coffee waste (CW) is converted into B, N-doped biochar (BXNbY) using boric acid-assisted pyrolysis (H3BO3 mass = X and carbonization temperature = Y) under N2 to overcome the challenge. The B dopant regulates the concentration and type of N, provides Lewis's acid sites, and converts graphitic-N to pyridine-N in BXNbY. The optimized B3Nb900 exhibits excellent colorimetric sensing performance toward H2O2 with a low detection limit (36.9 nM) and high selectivity in the presence of many interferences and milk samples due to high pyridinic-N and Sp2 domain sizes. Interestingly, B enhances other properties of N-containing CW-derived carbon and introduces self-extinguishing and tribopositive properties. Hence, BXNbY-coated polyurethane foam shows excellent flame retardancy and energy harvesting performance.

Spray Pyrolysis Regulated FeCo Alloy Anchoring on Nitrogen-Doped Carbon Hollow Spheres Boost the Performance of Zinc-Air Batteries.

Low-cost and high-efficiency non-precious metal-based oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional catalysts are the key to promoting the commercial application of metal-air batteries. Herein, a highly efficient catalyst of Fe0.18Co0.82 alloy anchoring on the nitrogen-doped porous carbon hollow sphere (FexCo1-x/N-C) is intelligently designed by spray pyrolysis (SP). The zinc in the SP-derived metal oxides and metal-organic framework volatilize at high temperature to construct a hierarchical porous structure with abundant defects and fully exposes the FeCo nanoparticles which uniformly anchor on the carbon substrate. In this structure, the coexistence of Fe0.18Co0.82 alloy and binary metal active sites (Fe-Nx/Co-Nx) guarantees the Fe0.2Co0.8/N-C catalyst exhibiting an excellent half-wave potential (E1/2 ═ 0.84 V) superior to 20% Pt/C for ORR and a suppressed overpotential (280 mV) than RuO2 for OER. Assembled rechargeable Zn-air battery (RZAB) demonstrates a promising specific capacity of 807.02 mAh g-1, peak power density of 159.08 mW cm-2 and durability without electrolyte circulation (550 h). This work proposes the design concept of utilizing an oxide core to in situ consume the porous carbon shell for anchoring metal active sites and construct defects, which benefits from spray pyrolysis in achieving precise control of the alloy structure and mass preparation.

The Micron-Droplet-Confined Continuous-Flow Synthesis of Freestanding High-Entropy-Alloy Nanoparticles by Flame Spray Pyrolysis.

Alloying multiple immiscible elements into a nanoparticle with single-phase solid solution structure (high-entropy-alloy nanoparticles, HEA-NPs) merits great potential. To date, various kinds of synthesis techniques of HEA-NPs are developed; however, a continuous-flow synthesis of freestanding HEA-NPs remains a challenge. Here a micron-droplet-confined strategy by flame spray pyrolysis (FSP) to achieve the continuous-flow synthesis of freestanding HEA-NPs, is proposed. The continuous precursor solution undergoes gas shearing and micro-explosion to form nano droplets which act as the micron-droplet-confined reactors. The ultrafast evolution (<5 ms) from droplets to <10 nm nanoparticles of binary to septenary alloys is achieved through thermodynamic and kinetic control (high temperature and ultrafast colling). Among them, the AuPtPdRuIr HEA-NPs exhibit excellent electrocatalytic performance for alkaline hydrogen evolution reaction with 23 mV overpotential to achieve 10 mA cm-2, which is twofold better than that of the commercial Pt/C. It is anticipated that the continuous-flow synthesis by FSP can introduce a new way for the continuous synthesis of freestanding HEA-NP with a high productivity rate.

Constraining activity and growth substrate of fungal decomposers via assimilation patterns of inorganic carbon and water into lipid biomarkers.

Fungi are among the few organisms on the planet that can metabolize recalcitrant carbon (C) but are also known to access recently produced plant photosynthate. Therefore, improved quantification of growth and substrate utilization by different fungal ecotypes will help to define the rates and controls of fungal production, the cycling of soil organic matter, and thus the C storage and CO2 buffering capacity in soil ecosystems. This pure-culture study of fungal isolates combined a dual stable isotope probing (SIP) approach, together with rapid analysis by tandem pyrolysis-gas chromatography-isotope ratio mass spectrometry to determine the patterns of water-derived hydrogen (H) and inorganic C assimilated into lipid biomarkers of heterotrophic fungi as a function of C substrate. The water H assimilation factor (αW) and the inorganic C assimilation into C18:2 fatty acid isolated from five fungal species growing on glucose was lower (0.62% ± 0.01% and 4.7% ± 1.6%, respectively) than for species grown on glutamic acid (0.90% ± 0.02% and 7.4% ± 3.7%, respectively). Furthermore, the assimilation ratio (RIC/αW) for growth on glucose and glutamic acid can distinguish between these two metabolic modes. This dual-SIP assay thus delivers estimates of fungal activity and may help to delineate the predominant substrates that are respired among a matrix of compounds found in natural environments.IMPORTANCEFungal decomposers play important roles in food webs and nutrient cycling because they can feed on both labile and more recalcitrant forms of carbon. This study developed and applied a dual stable isotope assay (13C-dissolved inorganic carbon/2H) to improve the investigation of fungal activity in the environment. By determining the incorporation patterns of hydrogen and carbon into fungal lipids, this assay delivers estimates of fungal activity and the different metabolic pathways that they employ in ecological and environmental systems.

Elevated atmospheric CO2 drives decreases in stable soil organic carbon in arid ecosystems: Evidence from a physical fractionation and organic compound analysis.

The increasing concentration of CO2 in the atmosphere is perturbing the global carbon (C) cycle, altering stocks of organic C, including soil organic matter (SOM). The effect of this disturbance on soils in arid ecosystems may differ from other ecosystems due to water limitation. In this study, we conducted a density fractionation on soils previously harvested from the Nevada Desert FACE Facility (NDFF) to understand how elevated atmospheric CO2 (eCO2 ) affects SOM stability. Soils from beneath the perennial shrub, Larrea tridentata, and from unvegetated interspace were subjected to a sodium polytungstate density fractionation to separate light, particulate organic matter (POM, <1.85 g/cm3 ) from heavier, mineral associated organic matter (MAOM, >1.85 g/cm3 ). These fractions were analyzed for organic C, total N, δ13 C and δ15 N, to understand the mechanisms behind changes. The heavy fraction was further analyzed by pyrolysis GC/MS to assess changes in organic compound composition. Elevated CO2 decreased POM-C and MAOM-C in soils beneath L. tridentata while interspace soils exhibited only a small increase in MAOM-N. Analysis of δ13 C revealed incorporation of new C into both POM and MAOM pools indicating eCO2 stimulated rapid turnover of both POM and MAOM. The largest losses of POM-C and MAOM-C observed under eCO2 occurred in soils 20-40 cm in depth, highlighting that belowground C inputs may be a significant driver of SOM decomposition in this ecosystem. Pyrolysis GC/MS analysis revealed a decrease in organic compound diversity in the MAOM fraction of L. tridentata soils, becoming more similar to interspace soils under eCO2 . These results provide further evidence that MAOM stability may be compromised under disturbance and that SOC stocks in arid ecosystems are vulnerable under continued climate change.

Sustainable management of tea wastes: resource recovery and conversion techniques.

As the demand for tea (Camellia sinensis) has grown across the world, the amount of biomass waste that has been produced during the harvesting process has also increased. Tea consumption was estimated at about 6.3 million tonnes in 2020 and is anticipated to reach 7.4 million tonnes by 2025. The generation of tea waste (TW) after use has also increased concurrently with rising tea consumption. TW includes clipped stems, wasted tea leaves, and buds. Many TW-derived products have proven benefits in various applications, including energy generation, energy storage, wastewater treatment, and pharmaceuticals. TW is widely used in environmental and energy-related applications. Energy recovery from low- and medium-calorific value fuels may be accomplished in a highly efficient manner using pyrolysis, anaerobic digestion, and gasification. TW-made biochar and activated carbon are also promising adsorbents for use in environmental applications. Another area where TW shows promise is in the synthesis of phytochemicals. This review offers an overview of the conversion procedures for TW into value-added products. Further, the improvements in their applications for energy generation, energy storage, removal of different contaminants, and extraction of phytochemicals have been reviewed. A comprehensive assessment of the sustainable use of TWs as environmentally acceptable renewable resources is compiled in this review.

The influence of sodium alginate on the structural and adsorption properties of resorcinol-formaldehyde resins and their porous carbon derivatives.

A series of carbon composites were synthesised by carbonisation of resorcinol-formaldehyde resin mixtures with the addition of different amounts of sodium alginate (SA) and compared with a composite prepared using Na2 CO3 as a catalyst for the polymerisation reaction. The effect of operating parameters such as SA concentration and polycondensation time on the structural and morphological properties of resorcinol-formaldehyde resins (RFR) and carbon-derived composites was investigated for further use as adsorbents. The synthesised composites were characterised by FTIR, SEM, Raman spectroscopy and N2 adsorption/desorption techniques. It was found that the morphology, specific surface area (SBET ~347-559 m2 /g), volume and particle size distribution (~0.5-4 µm) and porosity (Vpor =0.178-0.348 cm3 /g) of the composites were influenced by the concentration of SA and the synthesis technique and determined the adsorption properties of the materials. It was found that the surface of the filled chars was found to have an affinity for heavy metals and has the ability to form chemical bonds with cadmium ions. The maximum sorption capacities for Cd(II), i. e. 13.28 mg/g, were observed for the sample synthesised with the highest SA content. This confirms the statement that as-synthesised materials are promising adsorbents for environmental applications.

Effect of pyrolysis temperature and hydrothermal activation on structure, physicochemical, thermal and dye adsorption characteristics of the biocarbons.

In this study, the possibility of using sawdust from mixed woods to obtain biocarbons in the pyrolysis and steam activation using microwave radiation as an energy source was investigated. Biocarbons were characterized based on the results of N2 adsorption, thermogravimetric analysis (TGA), Fourier spectroscopy (ATR-FTIR), and Raman spectroscopy. Surface characterization was performed by Boehm titration and pHpzc determination. The adsorption capacity of methylene blue (MB) and methyl orange (MO) was studied. It was proved that the pyrolysis temperature and hydrothermal activation increased the biocarbons structural, surface and adsorption parameters of the obtained biocarbons. The amorphous materials of small specific surface area with a significant share of micropores were obtained. The steam activation resulted in significant development of the porous structure (to SBET =729.2 m2 /g and Vp =0.36 cm3 /g). The presence of functional groups, mainly phenolic ones, and pHpzc values indicating a potential for adsorption applications regarding MO and MB were found. The highest sorption capacity concerning MB (qe =122.8 mg/g) and MO (qe =99.1 mg/g) was observed for the steam-activated biocarbon BC-800MW . Using microwave energy hydrothermal activation proved very efficient, resulting in significant surface area and porosity development with a small loss of carbon matter.

Preparation of biochars by conventional pyrolysis of herbal waste and their potential application for adsorption and energy purposes.

The nettle, sage, mint and lemon balm herbs were used for biochars preparation. The physicochemical parameters of obtained materials were related to the lignocellulose composition of the precursors. It has been proved that the content of mineral substance has a significant influence on development of surface area, whereas the amount of hemicellulose affects the content of surface functional groups. It has been also shown that the obtained biochars are characterized by great energy parameters. The higher heating values (HHV) of the carbonaceous materials are comparable to the typical energy sources. The greatest HHV value (20.36 MJ/kg) was characteristic for the biochar obtained by pyrolysis of the lemon balm. In addition, the biochars were used for ionic polymers adsorption from one- and two-components solutions. Despite the adsorbed amounts of macromolecules are not great is has been proved that polyethylenimine and polyacrylic acid have positive influence on their mutual adsorption.

The effect of nitrogen source and levels on hybrid aspen tree physiology and wood formation.

Nitrogen can be taken up by trees in the form of nitrate, ammonium and amino acids, but the influence of the different forms on tree growth and development is poorly understood in angiosperm species like Populus. We studied the effects of both organic and inorganic forms of nitrogen on growth and wood formation of hybrid aspen trees in experimental conditions that allowed growth under four distinct steady-state nitrogen levels. Increased nitrogen availability had a positive influence on biomass accumulation and the radial dimensions of both xylem vessels and fibers, and a negative influence on wood density. An optimal level of nitrogen availability was identified where increases in biomass accumulation outweighed decreases in wood density. None of these responses depended on the source of nitrogen except for shoot biomass accumulation, which was stimulated more by treatments complemented with nitrate than by ammonium alone or the organic source arginine. The most striking difference between the nitrogen sources was the effect on lignin composition, whereby the abundance of H-type lignin increased only in the presence of nitrate. The differential effect of nitrate is possibly related to the well-known role of nitrate as a signaling compound. RNA-sequencing revealed that while the lignin-biosynthetic genes did not significantly (FDR <0.01) respond to added NO3 - , the expression of several laccases, catalysing lignin polymerization, was dependent on N-availability. These results reveal a unique role of nitrate in wood formation and contribute to the knowledge basis for decision-making in utilizing hybrid aspen as a bioresource.

Mechanistic Implications of the Varying Susceptibility of PAHs to Pyro-Catalytic Treatment as a Function of Their Ionization Potential and Hydrophobicity.

Transition metal catalysts in soil constituents (e.g., clays) can significantly decrease the pyrolytic treatment temperature and energy requirements for efficient removal of polycyclic aromatic hydrocarbons (PAHs) and, thus, lead to more sustainable remediation of contaminated soils. However, the catalytic mechanism and its rate-limiting steps are not fully understood. Here, we show that PAHs with lower ionization potential (IP) are more easily removed by pyro-catalytic treatment when deposited onto Fe-enriched bentonite (1.8% wt. ion-exchanged content). We used four PAHs with decreasing IP: naphthalene > pyrene > benz(a)anthracene > benzo(g,h,i)perylene. Density functional theory (DFT) calculations showed that lower IP results in stronger PAH adsorption to Fe(III) sites and easier transfer of π-bond electrons from the aromatic ring to Fe(III) at the onset of pyrolysis. We postulate that the formation of aromatic radicals via this direct electron transfer (DET) mechanism is the initiation step of a cascade of aromatic polymerization reactions that eventually convert PAHs to a non-toxic and fertility-preserving char, as we demonstrated earlier. However, IP is inversely correlated with PAH hydrophobicity (log Kow), which may limit access to the Fe(III) catalytic sites (and thus DET) if it increases PAH sorption to soil OM. Thus, ensuring adequate contact between sorbed PAHs and the catalytic reaction centers represents an engineering challenge to achieve faster remediation with a lower carbon footprint via pyro-catalytic treatment.

Recent Advancements in Pyrolysis of Halogen-Containing Plastics for Resource Recovery and Halogen Upcycling: A State-of-the-Art Review.

Plastic waste has emerged as a serious issue due to its impact on environmental degradation and resource scarcity. Plastic recycling, especially of halogen-containing plastics, presents challenges due to potential secondary pollution and lower-value implementations. Chemical recycling via pyrolysis is the most versatile and robust approach for combating plastic waste. In this Review, we present recent advancements in halogen-plastic pyrolysis for resource utilization and the potential pathways from "reducing to recycling to upcycling" halogens. We emphasize the advanced management of halogen-plastics through copyrolysis with solid wastes (waste polymers, biomass, coal, etc.), which is an efficient method for dealing with mixed wastes to obtain high-value products while reducing undesirable substances. Innovations in catalyst design and reaction configurations for catalytic pyrolysis are comprehensively evaluated. In particular, a tandem catalysis system is a promising route for halogen removal and selective conversion of targeted products. Furthermore, we propose novel insights regarding the utilization and upcycling of halogens from halogen-plastics. This includes the preparation of halogen-based sorbents for elemental mercury removal, the halogenation-vaporization process for metal recovery, and the development of halogen-doped functional materials for new materials and energy applications. The reutilization of halogens facilitates the upcycling of halogen-plastics, but many efforts are needed for mutually beneficial outcomes. Overall, future investigations in the development of copyrolysis and catalyst-driven technologies for upcycling halogen-plastics are highlighted.