Where You Protonate Matters: Deciphering the Unimolecular Chemistry of Protonated Myrcene and Linalool.

The unimolecular reactions of protonated myrcene and linalool were investigated by collision-induced dissociation and density functional theory calculations. Experiments on a triple quadrupole mass spectrometer showed that protonated myrcene undergoes two major unimolecular reactions losing propene and isobutene, and two minor reactions of ethene and propane loss. In each case, the product ion consists of a substituted five-member ring. Protonation of myrcene was found to form four distinct protomers, three of which can be significantly populated in the ion source. The observed fragmentation reactions were calculated and found to depend on the starting protomer. Each pathway consisted of several hydrogen-migration and ring-forming/opening steps on the way to the observed products. Likewise, protonation of linalool also produces three distinct protomers, with the global minimum being formed by protonation of a central double bond. The major reaction is water loss to form protonated myrcene, but two minor channels were also observed resulting in loss of acetone and isobutene. The calculated minimum energy reaction pathways were found to be consistent with the relative abundances of the ions in the experimental breakdown diagrams.

Switching CO2 Electroreduction Pathways between Ethylene and Ethanol via Tuning Microenvironment of the Coating on Copper Nanofibers.

Engineering the microenvironment of electrode surface is one of the effective means to tune the reaction pathways in CO2RR. In this work, we prepared copper nanofibers with conductive polypyrrole coating by polymerization of pyrrole using polyvinyl pyrrolidone (PVP) as template. As a result, the obtained copper nanofibers Cu/Cu2+1O/SHNC, exhibited a superhydrophobic surface, which demonstrated very high selectivity for ethanol with a Faraday efficiency (FE) of 66.5 % at -1.1 V vs reversible hydrogen electrode (RHE) in flow cell. However, the catalyst Cu/Cu2+1O/NC, which was prepared under the same conditions but without PVP, possessed a hydrophobic surface and exhibited high selectivity towards ethylene at the given potentials. The mechanism for switch of reaction pathways from ethylene to ethanol in CO2RR was studied. Incorporating pyrrolidone groups into the polymer coating results in the formation of a superhydrophobic surface. This surface weakens the hydrogen bonding interaction between interfacial water molecules and facilitates the transfer of CO2, thereby enhancing the local CO2/H2O ratio. The high coverage of *CO promotes the coupling of *CO and *CHO to form C2 intermediates, and reduces the reaction energy for the formation of *CHCHOH (ethanol path) at the interface. This ensures that the reaction pathway is directed towards ethanol.

Ranitidine degradation in layered double hydroxide activated peroxymonosulfate system: impact of transition metal composition and reaction mechanisms.

Ranitidine, a competitive inhibitor of histamine H2 receptors, has been identified as an emerging micropollutant in water and wastewater, raising concerns about its potential impact on the environment and human health. This study aims to address this issue by developing an effective removal strategy using two types of layered double hydroxide (LDH) catalysts (i.e., CoFeLDH and CoCuLDH). Characterization results show that CoFeLDH catalyst has superior catalytic properties due to its stronger chemical bond compared to CoCuLDH. The degradation experiment shows that 100% degradation of ranitidine could be achieved within 20 min using 25 mg/L of CoFeLDH and 20 mg/L of peroxymonosulfate (PMS). On the other hand, CoCuLDH was less effective, achieving only 70% degradation after 60 min at a similar dosage. The degradation rate constant of CoFeLDH was 10 times higher than the rate constant of CoCuLDH at different pH range. Positive zeta potential of CoFeLDH made it superior over CoCuLDH regarding catalytic oxidation of PMS. The catalytic degradation mechanism shows that sulfate radicals played a more dominant role than hydroxyl radicals in the case of LDH catalysts. Also, CoFeLDH demonstrated a stronger radical pathway than CoCuLDH. XPS analysis of CoFeLDH revealed the cation percentages at different phases and proved the claim of being reusable even after 8 cycles. Overall, the findings suggest that CoFeLDH/PMS system proves to be a suitable choice for attaining high degradation efficiency and good stability in the remediation of ranitidine in wastewater.

The generation of sulfate species on Ir-based catalysts for boosting NO reduction with CO under the coexistence of O2 and SO2 atmosphere.

Generally, sulfur poisoning is considered to be one of the main factors contributing to the deactivation of selective catalytic reduction of NOx by CO (CO-SCR) catalysts, while the promotional effect of SO2 on NO reduction over Ir/SiO2 is observed which is an interesting scientific phenomenon. After the introduction of 20 ppm SO2, NOx conversion increased from âˆ¼ 40 % to âˆ¼ 90 % at 275 °C, and N2 selectivity increased from âˆ¼ 80 % to 100 % at 200 âˆ¼ 300 °C. Furthermore, the promoting effect could remain unchanged after 24 h of continuous reaction. However, the temperature point for achieving complete conversion of CO increased from 225 °C to 275 °C after the introduction of SO2. Experimental characterization and theoretical calculation jointly proved that the inhibition of CO oxidation by the generation of sulfate was the main reason for promoting NO reduction. Under the coexistence of O2 and SO2, SO2 was firstly oxidized to SO3 on the iridium surface and generated sulfate species on surface hydroxyl groups of SiO2. Some active sites for O2 adsorption were covered by the generated surface sulfate, and adsorbed CO was hard to react with adsorbed O2, resulting in Langmuir-Hinshelwood (L-H) reaction pathways for CO oxidation being inhibited. Therefore, unoxidized CO reacted with NO adsorbed species and generated N2O to generate N2 and CO2, improving NO reduction. This new insight has implications for understanding the promotional effect of SO2 on NO reduction with CO in the presence of O2.

Effects of photochemical aging on the molecular composition of organic aerosols derived from agricultural biomass burning in whole combustion process.

Biomass burning organic aerosols (BBOA) are key components of atmospheric particulate matter, yet the effects of aging process on their chemical composition and related properties remain poorly understood. In this study, fresh smoke emissions from the combustion of three types of agricultural biomass residues (rice, maize, and wheat straws) were photochemically aged in an oxidation flow reactor. The changes in BBOA composition were characterized by offline analysis using ultrahigh performance liquid chromatography coupled with Orbitrap mass spectrometry. The BBOA molecular composition varied dramatically with biomass type and aging process. Fresh and aged BBOA were predominated by CHO and nitrogen-containing CHON, CHN, and CHONS species, while with very few CHOS and other non­oxygen species. The signal peak area variations revealed that individual molecular species underwent dynamic changes, with 77-81 % of fresh species decreased or even disappeared and 33-46 % of aged species being newly formed. A notable increase was observed in the number and peak area of CxHyO≥6 compounds in aged BBOA, suggesting that photochemical process served as an important source of highly oxygenated species. Heterocyclic CxHyN2 compounds mostly dominated in fresh CHN species, whereas CxHyN1 were more abundant in aged ones. Fragmentation and homologs oxidation by addition of oxygen-containing functional groups were important pathways for the BBOA aging. The changes in BBOA composition with aging would have large impacts on particle optical properties and toxicity. This study highlights the significance of photochemical aging process in altering chemical composition and related properties of BBOA.

Quantum chemical pathways for the formation of 2,3,7,8-tetrachloro dibenzo-p-dioxin (TCDD) from 2,4,5-trichlorophenol: a mechanistic and thermo-kinetic study.

CONTEXT: Dioxins, specifically 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TCDD), are highly toxic dioxins known for their severe health impacts and persistent environmental pollutants. This study focuses on understanding the formation pathways of TCDD from its precursor molecule 2,4,5-trichlorophenol (2,4,5-TCP). In our exploration of reaction pathways from 2,4,5-trichlorophenol (TCP), we delve into three reaction mechanisms: free-radical, direct condensation, and anionic. Our findings highlight the significance of the radical mechanism, particularly propagated by H radicals, with a notable increase in dioxin formation around 900 K. These results are consistent with experimental observations indicating an increase in the conversion of trichlorophenol from 600 to 900 K in the non-catalytic gas phase reaction. Thermodynamic parameters (∆H, ∆S, and ∆G), reaction barriers, and rate constants (k) were calculated across a temperature range of 300-1200 K to support the findings and provide insights into the optimal temperature range for controlling dioxins during the incineration process. METHOD: In this study, quantum chemical calculations were conducted using density functional theory (DFT) with the B3LYP functional and the 6-311 + + G(d,p) basis set in Gaussian 16 software. Stationary points, including transition states (TS), were confirmed with frequency calculations. Intrinsic reaction coordinate (IRC) calculations ensured minimum energy paths between TS and products, visualized in GaussView 6.0 Program. Single-point energy calculations utilized a more precise basis set, 6-311 + + G(3df,2p), for enhanced energy accuracy, incorporating zero-point vibrational energy (ZPE) and other energy corrections. These calculations were repeated over a temperature range of 298.15-1200 K at 1 atm pressure. Finally, rate constant (k) expressions associated with TCDD formation were determined using transition state theory (TST).

Altering the CO2 Electroreduction Pathways Towards C1 or C2+ Products via Engineering the Strength of Interfacial Cu-O Bond.

Copper (Cu)-based catalysts have established their unique capability for yielding wide value-added products from CO2. Herein, we demonstrate that the pathways of the electrocatalytic CO2 reduction reaction (CO2RR) can be rationally altered toward C1 or C2+ products by simply optimizing the coordination of Cu with O-containing organic species (squaric acid (H2C4O4) and cyclohexanehexaone (C6O6)). It is revealed that the strength of Cu-O bonds can significantly affect the morphologies and electronic structures of derived Cu catalysts, resulting in the distinct behaviors during CO2RR. Specifically, the C6O6-Cu catalysts made up from organized nanodomains shows a dominant C1 pathway with a total Faradaic efficiency (FE) of 63.7 % at -0.6 V (versus reversible hydrogen electrode, RHE). In comparison, the C4O4-Cu with an about perfect crystalline structure results in uniformly dispersed Cu-atoms, showing a notable FE of 65.8 % for C2+ products with enhanced capability of C-C coupling. The latter system also shows stable operation over at least 10 h with a high current density of 205.1 mA cm-2 at -1.0 VRHE, i.e., is already at the boarder of practical relevance. This study sheds light on the rational design of Cu-based catalysts for directing the CO2RR reaction pathway.

Unravelling caramelization and Maillard reactions in glucose and glucose + leucine model cakes: Formation and degradation kinetics of volatile markers extracted during baking.

A large number of volatile compounds are formed during the baking of foods by reactions such as caramelization and Maillard reactions. Elucidating the reaction mechanisms may be useful to predict and control food quality. Ten reaction volatile markers were extracted during baking of solid model cakes implemented with known amounts of precursors (glucose with or without leucine) and then quantified by Thermal desorption-Gas chromatography-Mass spectrometry. The kinetic data showed that the level of air convection in the oven had no significant influence on the reaction rates. In contrast, increasing baking temperatures had a nonlinear accelerating impact on the generation of newly formed volatile compounds with a bell-shaped kinetic curve found for most of the markers at 200 °C. The presence of leucine triggered the activation of the Maillard and Strecker routes with a specific and very rapid formation of 3-Methylbutanal and pyrazines. A dynamic model was developed, combining evaporation flow rate and kinetic formation and consumption of reaction markers. It can be used to describe, for two furanic compounds of different volatilities, the vapor concentrations in the oven from the concentrations measured in the model cakes.

Comparative analysis of UV-initiated ARPs for degradation of the emerging substitute of perfluorinated compounds: Does defluorination mean the sole factor?

Due to the increasing attention for the residual of per- and polyfluorinated compounds in environmental water, Sodium p-Perfluorous Nonenoxybenzenesulfonate (OBS) have been considered as an alternative solution for perfluorooctane sulfonic acid (PFOS). However, recent detections of elevated OBS concentrations in oil fields and Frontal polymerization foams have raised environmental concerns leading to the decontamination exploration for this compound. In this study, three advanced reduction processes including UV-Sulfate (UV-SF), UV-Iodide (UV-KI) and UV-Nitrilotriacetic acid (UV-NTA) were selected to evaluate the removal for OBS. Results revealed that hydrated electrons (eaq-) dominated the degradation and defluorination of OBS. Remarkably, the UV-KI exhibited the highest removal rate (0.005 s-1) and defluorination efficiency (35 %) along with the highest concentration of eaq- (K = -4.651). Despite that nucleophilic attack from eaq- on sp2 carbon and H/F exchange were discovered as the general mechanism, high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC/Q-TOF-MS) analysis with density functional theory (DFT) calculations revealed the diversified products and routes. Intermediates with lowest fluorine content for UV-KI were identified, the presence nitrogen-containing intermediates were revealed in the UV-NTA. Notably, the nitrogen-containing intermediates displayed the enhanced toxicity, and the iodine poly-fluorinated intermediates could be a potential-threat compared to the superior defluorination performance for UV-KI.

A comprehensive review of flue gas bio-mitigation: chemolithotrophic interactions with flue gas in bio-reactors as a sustainable possibility for technological advancements.

Flue gas mitigation technologies aim to reduce the environmental impact of flue gas emissions, particularly from industrial processes and power plants. One approach to mitigate flue gas emissions involves bio-mitigation, which utilizes microorganisms to convert harmful gases into less harmful or inert substances. The review thus explores the bio-mitigation efficiency of chemolithotrophic interactions with flue gas and their potential application in bio-reactors. Chemolithotrophs are microorganisms that can derive energy from inorganic compounds, such as carbon dioxide (CO2), nitrogen oxides (NOx), and sulfur dioxide (SO2), present in the flue gas. These microorganisms utilize specialized enzymatic pathways to oxidize these compounds and produce energy. By harnessing the metabolic capabilities of chemolithotrophs, flue gas emissions can be transformed into value-added products. Bio-reactors provide controlled environments for the growth and activity of chemolithotrophic microorganisms. Depending on the specific application, these can be designed as suspended or immobilized reactor systems. The choice of bio-reactor configuration depends on process efficiency, scalability, and ease of operation. Factors influencing the bio-mitigation efficiency of chemolithotrophic interactions include the concentration and composition of the flue gas, operating conditions (such as temperature, pH, and nutrient availability), and reactor design. Chemolithotrophic interactions with flue gas in bio-reactors offer a potentially efficient approach to mitigating flue gas emissions. Continued research and development in this field are necessary to optimize reactor design, microbial consortia, and operating conditions. Advances in understanding the metabolism and physiology of chemolithotrophic microorganisms will contribute to developing robust and scalable bio-mitigation technologies for flue gas emissions.

Catalytic Mechanism of Fatty Acid Photodecarboxylase: On the Detection and Stability of the Initial Carbonyloxy Radical Intermediate.

In fatty acid photodecarboxylase (FAP), light-induced formation of the primary radical product RCOO⋅ from fatty acid RCOO- occurs in 300 ps, upon which CO2 is released quasi-immediately. Based on the hypothesis that aliphatic RCOO⋅ (spectroscopically uncharacterized because unstable) absorbs in the red similarly to aromatic carbonyloxy radicals such as 2,6-dichlorobenzoyloxy radical (DCB⋅), much longer-lived linear RCOO⋅ has been suggested recently. We performed quantum chemical reaction pathway and spectral calculations. These calculations are in line with the experimental DCB⋅ decarboxylation dynamics and spectral properties and show that in contrast to DCB⋅, aliphatic RCOO⋅ radicals a) decarboxylate with a very low energetic barrier and on the timescale of a few ps and b) exhibit little red absorption. A time-resolved infrared spectroscopy experiment confirms very rapid, ≪300 ps RCOO⋅ decarboxylation in FAP. We argue that this property is required for the observed high quantum yield of hydrocarbons formation by FAP.

Impact of Vacancy Defects on Electrochemical Nitrogen Reduction Reaction Performance of MXenes.

We investigated electrochemical nitrogen reduction reaction (eNRR) on MXenes consisting of the vacancy defects in the functional layer using density functional theory calculations. We considered Mo2C, W2C, Mo2N, and W2N MXenes with F, N, and O functionalization and investigated distal and alternative associative pathways. We analyzed these MXenes for eNRR based on N2 adsorption energy, NH3 desorption energy, NRR selectivity, and electrochemical limiting potential. While we find that most of the considered MXenes surfaces are more favorable for eNRR compared to hydrogen evolution, these surfaces also have strong NH3 binding (>-1.0 eV) and thus will be covered with NH3 during operating conditions. Amongst all considered MXenes, only W2NF2 is found to have a low NH3 desorption energy along with low eNRR overpotential and selectivity towards eNRR. The obtained eNRR overpotential and NH3 desorption energy on W2NF2 are superior to those reported for pristine W2N3 as well as functionalized MXenes.

Cobalt catalyzed ethane dehydrogenation to ethylene with CO2: Relationships between cobalt species and reaction pathways.

TiO2, ZrO2 and a series of TiO2-ZrO2 (TxZ1, x means the atomic ratio of Ti/Zr = 10, 5, 1, 0.2 and 0.1) composite oxide supports were prepared through co-precipitation, and then 3 wt% Co was loaded through wetness impregnation methods. The obtained 3 wt% Co/TiO2 (3CT), 3 wt% Co/ZrO2 (3CZ) and 3 wt% Co/TxZ1 (3CTxZ1) catalysts were evaluated for the oxidative ethane dehydrogenation reaction with CO2 (CO2-ODHE) as a soft oxidant. 3CT1Z1 catalyst exhibits excellent catalytic properties, with C2H4 yield, C2H6 conversion and CO2 conversion about 24.5 %, 33.8 % and 18.0 % at 650 °C, respectively. X-Ray Diffraction (XRD), in-situ Raman, UV-vis diffuse reflectance spectra (UV-vis DRS), H2 temperature-programmed reduction (H2-TPR), Electron paramagnetic resonance (EPR) and quasi in-situ X-ray Photoelectron Spectroscopy (XPS) have been utilized to thoroughly characterize the investigated catalysts. The results revealed that 3CT1Z1 produced TiZrO4 solid solution with more metal defect sites and oxygen vacancies (Ov), promoting the formation of Co2+-TiZrO4 structure. Furthermore, the presence of Ov and Ti3+can facilitate the high dispersion and stabilization of Co2+, as well as suppressing the severe reduction of Co2+, leading to superior ethane oxidative dehydrogenation activity. Besides, less Co0 is beneficial to ODHE reaction, because of its promotion effects for reverse water gas shift reaction; however, more Co0 results in dry reforming reaction (DRE). This work will shed new lights for the design and preparation of highly efficient catalysts for ethylene production.

Degradation of Butylated Hydroxyanisole by the Combined Use of Peroxymonosulfate and Ferrate(VI): Reaction Kinetics, Mechanism and Toxicity Evaluation.

Butylated hydroxyanisole (BHA), a synthetic phenolic antioxidant (SPA), is now widely present in natural waters. To improve the degradation efficiency of BHA and reduce product toxicity, a combination of peroxymonosulfate (PMS) and Ferrate(VI) (Fe(VI)) was used in this study. We systematically investigated the reaction kinetics, mechanism and product toxicity in the degradation of BHA through the combined use of PMS and Fe(VI). The results showed that PMS and Fe(VI) have synergistic effects on the degradation of BHA. The effects of operational factors, including PMS dosage, pH and coexisting ions (Cl-, SO42-, HCO3-, K+, NH4+ and Mg2+), and different water matrices were investigated through a series of kinetic experiments. When T = 25 °C, the initial pH was 8.0, the initial BHA concentration was 100 µM, the initial concentration ratio of [PMS]0:[Fe(VI)]0:[BHA]0 was 100:1:1 and the degradation rate could reach 92.4% within 30 min. Through liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) identification, it was determined that the oxidation pathway of BHA caused by PMS/Fe(VI) mainly includes hydroxylation, ring-opening and coupling reactions. Density functional theory (DFT) calculations indicated that •OH was most likely to attack BHA and generate hydroxylated products. The comprehensive comparison of product toxicity results showed that the PMS/Fe(VI) system can effectively reduce the environmental risk of a reaction. This study contributes to the development of PMS/Fe(VI) for water treatment applications.

Sandwich Immunosensor Based on Particle Motion: How Do Reactant Concentrations and Reaction Pathways Determine the Time-Dependent Response of the Sensor?

To control and optimize the speed of a molecular biosensor, it is crucial to quantify and understand the mechanisms that underlie the time-dependent response of the sensor. Here, we study how the kinetic properties of a particle-based sandwich immunosensor depend on underlying parameters, such as reactant concentrations and the size of the reaction chamber. The data of the measured sensor responses could be fitted with single-exponential curves, with characteristic response times that depend on the analyte concentration and the binder concentrations on the particle and substrate. By comparing characteristic response times at different incubation configurations, the data clarifies how two distinct reaction pathways play a role in the sandwich immunosensor, namely, analyte binding first to particles and thereafter to the substrate, and analyte binding first to the substrate and thereafter to a particle. For a concrete biosensor design, we found that the biosensor is dominated by the reaction pathway where analyte molecules bind first to the substrate and thereafter to a particle. Within this pathway, the binding of a particle to the substrate-bound analyte dominates the sensor response time. Thus, the probability of a particle interacting with the substrate was identified as the main direction to improve the speed of the biosensor while maintaining good sensitivity. We expect that the developed immunosensor and research methodology can be generally applied to understand the reaction mechanisms and optimize the kinetic properties of sandwich immunosensors with particle labels.

Reaction Steps in Heterogeneous Photocatalytic Oxidation of Toluene in Gas Phase-A Review.

A review of the current literature shows there is no clear consensus regarding the reaction mechanisms of air-borne aromatic compounds such as toluene by photocatalytic oxidation. Potential oxidation reactions over TiO2 or TiO2-based catalysts under ultraviolet and visible (UV/VIS) illumination are most commonly considered for removal of these pollutants. Along the pathways from a model pollutant, toluene, to final mineralization products (CO2 and H2O), the formation of several intermediates via specific reactions include parallel oxidation reactions and formation of less-reactive intermediates on the TiO2 surface. The latter may occupy active adsorption sites and causes drastic catalyst deactivation in some cases. Major hazardous gas-phase intermediates are benzene and formaldehyde, classified by the International Agency for Research on Cancer (IARC) as Group 1 carcinogenic compounds. Adsorbed intermediates leading to catalyst deactivation are benzaldehyde, benzoic acid, and cresols. The three most typical pathways of toluene photocatalytic oxidation are reviewed: methyl group oxidation, aromatic ring oxidation, and aromatic ring opening.

Temporal Evolution of Morphology, Composition, and Structure in the Formation of Colloidal High-Entropy Intermetallic Nanoparticles.

Morphology-controlled nanoparticles of high entropy intermetallic compounds are quickly becoming high-value targets for catalysis. Their ordered structures with multiple distinct crystallographic sites, coupled with the "cocktail effect" that emerges from randomly mixing a large number of elements, yield catalytic active sites capable of achieving advanced catalytic functions. Despite this growing interest, little is known about the pathways by which high entropy intermetallic nanoparticles form and grow in solution. As a result, controlling their morphology remains challenging. Here, we use the high entropy intermetallic compound (Pd,Rh,Ir,Pt)Sn, which adopts a NiAs-related crystal structure, as a model system for understanding how nanoparticle morphology, composition, and structure evolve during synthesis in solution using a slow-injection reaction. By performing a time-point study, we establish the initial formation of palladium-rich cube-like Pd-Sn seeds onto which the other metals deposit over time, concomitant with continued incorporation of tin. For (Pd,Rh,Ir,Pt)Sn, growth occurs on the corners, resulting in a sample having a mixture of flower-like and cube-like morphologies. We then synthesize and characterize a library of 14 distinct intermetallic nanoparticle systems that comprise all possible binary, ternary, and quaternary constituents of (Pd,Rh,Ir,Pt)Sn. From these studies, we correlated compositions, morphologies, and growth pathways with the constituent elements and their competitive reactivities, ultimately mapping out a framework that rationalizes the key features of the high entropy (Pd,Rh,Ir,Pt)Sn intermetallic nanoparticles based on those of their simpler constituents. We then validated these design guidelines by applying them to the synthesis of a morphologically pure variant of flowerlike (Pd,Rh,Ir,Pt)Sn particles as well as a series of (Pd,Rh,Ir,Pt)Sn particles with tunable morphologies based on control of composition.

Electrochemical Carbon Dioxide Reduction to Ethylene: From Mechanistic Understanding to Catalyst Surface Engineering.

Electrochemical carbon dioxide reduction reaction (CO2RR) provides a promising way to convert CO2 to chemicals. The multicarbon (C2+) products, especially ethylene, are of great interest due to their versatile industrial applications. However, selectively reducing CO2 to ethylene is still challenging as the additional energy required for the C-C coupling step results in large overpotential and many competing products. Nonetheless, mechanistic understanding of the key steps and preferred reaction pathways/conditions, as well as rational design of novel catalysts for ethylene production have been regarded as promising approaches to achieving the highly efficient and selective CO2RR. In this review, we first illustrate the key steps for CO2RR to ethylene (e.g., CO2 adsorption/activation, formation of *CO intermediate, C-C coupling step), offering mechanistic understanding of CO2RR conversion to ethylene. Then the alternative reaction pathways and conditions for the formation of ethylene and competitive products (C1 and other C2+ products) are investigated, guiding the further design and development of preferred conditions for ethylene generation. Engineering strategies of Cu-based catalysts for CO2RR-ethylene are further summarized, and the correlations of reaction mechanism/pathways, engineering strategies and selectivity are elaborated. Finally, major challenges and perspectives in the research area of CO2RR are proposed for future development and practical applications.

Enhanced biomethane production with a low carbon footprint via anaerobic co-digestion of swine wastewater with rice husk.

An electricity-assisted anaerobic co-digestion (EAAD) process was developed and compared with conventional anaerobic co-digestion (AD) using piggery wastewater and rice husk as feedstocks. Various methodologies, including kinetic models, microbial community analyses, life-cycle carbon footprints, and preliminary economic analysis, were integrated to comprehensively evaluate the performance of the two processes. The results demonstrated that EAAD exhibited a positive improvement of 2.6 % to 14.5 % in biogas production compared to AD. The suitable wastewater-to-husk ratio for EAAD was found to be 3:1, which corresponded to a carbon-to­nitrogen ratio of approximately 14. This ratio demonstrated positive co-digestion effects and electrical enhancements in the process. According to the modified Gompertz kinetics, the biogas production rate in EAAD ranged from 1.87 to 5.23 mL/g-VS/d, significantly higher than the range of 1.19 to 3.74 mL/g-VS/d observed in AD. The study also investigated the contributions of acetoclastic and hydrogenotrophic methanogens to biomethane formation, revealing that acetoclastic methanogens accounted for 56.6 % ± 0.6 % of the methane production, while hydrogenotrophic methanogens contributed to 43.4 % ± 0.6 %. No significant difference in the methanogenic reaction pathways was observed between AD and EAAD, indicating that the introduction of an external electric field did not alter the predominant pathways (p > 0.05, two-sample t-test). Furthermore, retrofitting existing AD plants with EAAD units can reduce the carbon intensity of piggery wastewater treatment by 17.6 % to 21.7 %. The preliminary economic analysis indicated a benefit-cost ratio of 1.33 for EAAD, confirming the feasibility of implementing EAAD for wastewater treatment while simultaneously producing bioenergy. Overall, this study provides valuable insights into upgrading the performance of existing AD plants by introducing an external electric field. It demonstrates that EAAD can achieve higher and cost-effective biogas production with a lower life-cycle carbon footprint, thus enhancing the sustainability and efficiency of the biogas production process.

Advanced oxidation and a metrological strategy based on CLC-MS for the removal of pharmaceuticals from pore & surface water.

In this work, it is studied the photolysis, electrolysis, and photo-electrolysis of a mixture of pharmaceutics (sulfadiazine, naproxen, diclofenac, ketoprofen and ibuprofen) contained in two very different types of real water matrices (obtained from surface and porewater reservoirs), trying to clarify the role of the matrix on the degradation of the pollutants. To do this, a new metrological approach was also developed for screening of pharmaceuticals in waters by capillary liquid chromatography mass spectrometry (CLC-MS). This allows the detection at concentrations lower than 10 ng mL-1. Results obtained in the degradation tests demonstrate that inorganic composition of the water matrix directly influences on the efficiency of the drugs removal by the different EAOPs and better degradation results were obtained for experiments carried out with surface water. The most recalcitrant drug studied was ibuprofen for all processes evaluated, while diclofenac and ketoprofen were found to be the easiest drugs for being degraded. Photo-electrolysis was found to be more efficient than photolysis and electrolysis, and the increase in the current density was found to attain a slight improvement in the removal although with an associated huge increase in the energy consumption. The main reaction pathways for each drug and technology were also proposed.