High CH4 Research Articles

Dual‐Site NiO/Bi3O4Br Heterojunction Catalyst for High‐Efficiency CO2‐to‐CH4 Conversion

AbstractSolar light‐driven conversion of CO2 into chemicals with high calorific value is regarded as an upcoming carbon utilization technology for alleviating the energy crisis. This technique faces the challenge of low CO2 conversion and product yield due to charge recombination in the catalyst. In this paper, a dual‐reaction site heterojunction catalyst was designed and fabricated by combining NiO with Bi3O4Br nanosheets, for the separation of CO2 reduction and H2O oxidation semireactions, which effectively promoted electrons and holes separation. The resulting catalyst exhibited a high CH4 production rate (8.12 µmol/g) and selectivity (94.69%). Electron distribution and band structure were investigated to explain the satisfactory catalytic performance. In addition, combining the in‐situ DRIFTS results, a formic acid‐intermediated CO2‐to‐CH4 reaction pathway was proposed. This work aims to pave the way for CH4 production via CO2 photoreduction with high efficiency and selectivity.

Unexpected inhibition roles of methane nanobubbles on hydrate decomposition

Uncontrolled hydrate decomposition poses extraordinary risks, such as submarine landslides during hydrate exploitation, and gas leakage during hydrate storage/transportation. Previous studies suggested inhibitors can effectively prevent hydrate decomposition by adsorbing onto the hydrate surface. However, herein, we find inhibitors have very limited adsorption coverages on hydrate, which cannot fully explain their good performance. In this study, by combining experiments and molecular simulations, a new inhibition mechanism is proposed, in which nanobubbles act as the primary factor in inhibiting hydrate decomposition. Specifically, when PVP (a typical inhibitor) is added into the solution, its hydrophobic groups interact strongly with CH4, thereby increasing CH4 solubility and inducing the formation of CH4 nanobubbles. These nanobubbles are then encapsulated within the hydrate and inhibit hydrate decomposition by the following process: nanobubbles gradually become exposed to the aqueous phase during hydrate decomposition and release CH4 to the region near the nanobubble-hydrate interface. The high local CH4 concentrations near the nanobubble-hydrate interface would promote the formation of microstructures necessary for hydrate nucleation, thereby amplifying the driving force toward nucleation and consequently inhibiting hydrate decomposition. Our proposed “nanobubble inhibition mechanism” can provide a theoretical foundation for developing and applying inhibitors to prevent hydrate decomposition in various industrial applications.

AuAg plasmonic nanoalloys with asymmetric charge distribution on CeO2 nanorods for selective photocatalytic CO2‐to‐CH4 conversion

AbstractConverting CO2 under mild conditions by employing semiconductor photocatalysts is promising to address global environmental issues. However, the current CO2 conversion efficiency is limited by the difficulty activating the thermodynamically stable CO2 molecules. Constructing plasmonic nanoalloy‐based photocatalytic systems with significant localized surface plasmon resonance (LSPR) is full of potential but remains a vast challenge. In this work, AuAg plasmonic nanoalloys were incorporated on CeO2 nanorods (designated as AuAg–CeO2) to achieve selective photoreduction of CO2. The result displays that Ag can serve as a superior electron modifier to promote the electron enrichment of Au, thus producing asymmetric charge distributions to boost the selective conversion of CO2. Furthermore, the improved LSPR effect on AuAg–CeO2 induces the generation of high‐energy hot electrons under irradiation, enhancing the reactivity of electrons for CO2 photoreduction. Due to the aforementioned effects, AuAg–CeO2 exhibits a high CO2‐to‐CH4 performance of 92.6 μmol g−1 through a 3‐h test and a high CH4 selectivity of 94.5%, up to 2.6, 8.7, and 17.1 times higher than the activity of Au–CeO2, pure CeO2, and Ag–CeO2, respectively. This work can provide a new perspective for constructing high‐performance catalysts for photocatalytic CO2 reduction.

Construction of Highly Porous and Robust Hydrogen-Bonded Organic Framework for High-Capacity Clean Energy Gas Storage.

Development of highly porous and robust hydrogen-bonded organic frameworks (HOFs) for high-pressure methane and hydrogen storage remains a grand challenge due to the fragile nature of hydrogen bonds. Herein, we report a strategy of constructing the double-walled framework to target highly porous and robust HOF (ZJU-HOF-5a) for extraordinary CH4 and H2 storage. ZJU-HOF-5a features a minimized twofold interpenetration with double-walled structure, in which multiple supramolecular interactions are existed between the interpenetrated walls. This structural configuration can notably enhance the framework robustness while maintaining its high porosity, affording one of the highest gravimetric and volumetric surface areas of 3102 m2 g-1 and 1976 m2 cm-3 among the reported HOFs so far. ZJU-HOF-5a thus exhibits an extremely high volumetric H2 uptake of 43.6 g L-1 at 77 K/100 bar and working capacity of 41.3 g L-1 under combined swing conditions (77 K/100 bar→160 K/5 bar), and also impressive methane storage performance with a 5-100 bar working capacity of 187 (or 159) cm3 (STP) cm-3 at 270 K (or 296 K), outperforming most of the reported porous organic materials. Single-crystal X-ray diffraction studies on CH4-loaded ZJU-HOF-5a reveal that abundant supramolecular binding sites combined with ultrahigh porosities account for its high CH4 storage capacities. Combined with high stability, super-hydrophobicity, and easy recovery, ZJU-HOF-5a is placed among the most promising materials for H2 and CH4 storage applications.

Self-Assembled Controllable Cu-Based Perovskite/Calcium Oxide Hybrids with Strong Interfacial Interactions for Enhanced CH4 Electrosynthesis.

Cu-based perovskite oxide catalysts show promise for CO2 electromethanation, but suffer from unsatisfactory CH4 selectivity and poor stability. Here, we report self-assembled, controllable Cu-based perovskite/calcium oxide hybrids with strongly interacting interfaces for high-performance CH4 electrosynthesis. As proof-of-concept catalysts, the La2CuO4/(CaO)x (x from 0.2 to 1.2) series has tunable CaO phase concentrations and thus controllable interface sizes. The La2CuO4 and CaO components are intimately connected at the interface, leading to strong interfacial interactions mainly manifested by marked electron transfer from Ca2+ to Cu2+. In CH4 electrosynthesis, their activity and selectivity show a volcano-type dependence on the CaO phase concentrations and are positively correlated with the interface sizes. Among them, the La2CuO4/(CaO)0.8 delivers the optimal activity and selectivity for CH4, together with good stability, much better than those of a physical-mixture counterpart and most reported Cu-based perovskite oxides. Moreover, La2CuO4/(CaO)0.8 stands out as one of the most effective Cu-based catalysts for CH4 electrosynthesis, achieving a high CH4 selectivity of 77.6% at 300 mA cm-2. Our experiments and theoretical calculations highlight the significant role of self-assembly-induced strong interfacial interactions in promoting *CO adsorption/hydrogenation, intensifying resistance to structural degradation, and consequently underpinning the achievement of such optimized performance.

Copper Atom Pairs Stabilize *OCCO Dipole Toward Highly Selective CO2 Electroreduction to C2H4

AbstractDeeply electrolytic reduction of carbon dioxide (CO2) to high‐value ethylene (C2H4) is very attractive. However, the sluggish kinetics of C−C coupling seriously results in the low selectivity of CO2 electroreduction to C2H4. Herein, we report a copper‐based polyhedron (Cu2) that features uniformly distributed and atomically precise bi‐Cu units, which can stabilize *OCCO dipole to facilitate the C−C coupling for high selective C2H4 production. The C2H4 faradaic efficiency (FE) reaches 51 % with a current density of 469.4 mA cm−2, much superior to the Cu single site catalyst (Cu SAC) (~0 %). Moreover, the Cu2 catalyst has a higher turnover frequency (TOF, ~520 h−1) compared to Cu nanoparticles (~9.42 h−1) and Cu SAC (~0.87 h−1). In situ characterizations and theoretical calculations revealed that the unique Cu2 structural configuration could optimize the dipole moments and stabilize the *OCCO adsorbate to promote the generation of C2H4.

Risk Assessment of Heavy Metal Accumulation in Cucumber Fruits and Soil in a Greenhouse System with Long-Term Application of Organic Fertilizer and Chemical Fertilizer

Combining organic and chemical fertilizers is a sustainable strategy for vegetable production. However, there is limited research concerning the risks associated with heavy metals (HMs) in greenhouse systems with long-term location application. A three-year investigation, conducted from 2021 to 2023, explored a fifteen-year field experiment with combinations of chemical fertilizer (CH), corn straw (SW) and pig manure (PM). Five treatments were evaluated: excessive fertilization (high CH and PM), conventional fertilization (normal CH), organic–inorganic fertilization (3/4CN + 1/4PN, 2/4CN + 2/4PN and 2/4CN + 1/4PN + 1/4SN). This study evaluated the risks associated with heavy metals (HMs) by analyzing and quantifying their concentrations in soil and cucumber fruits, as well as by calculating the bioconcentration factors (BCFs), the geo-accumulation index (Igeo), and both the non-carcinogenic and carcinogenic risks. The results indicated that excessive fertilization (CF) increased the concentrations of Cu and Zn in fruits, as well as the Igeo values of Cu, Zn, and Cd, and the non-carcinogenic Cu risk, while decreasing the BCFs of Cu and Zn. Organic–inorganic fertilization also elevated the Igeo values of Cu and Zn. Redundancy analyses confirmed a positive correlation between the soil concentrations of Cu and Zn and higher levels of available phosphorus contents (48.4%), alongside a lower pH (4.9%). The concentrations of Cu, Zn, and Cd in both soil and cucumber fruits increased linearly with the duration of application and amount of input. Although the combined application of CH with PM or SW did not significantly elevate the non-carcinogenic or carcinogenic risks associated with most heavy metals, the carcinogenic risks of Cd and As emerged as potential risk factors after 15 years of organic–inorganic fertilization. Utilizing a combination of CH with PM and SW as a fertilizer management strategy can effectively address both the control of heavy metal inputs in the facility and the safety and quality of cucumbers.

Item Response Theory Analysis of the Cultural Humility and Enactment Scale – Supervision

Objective This study aimed to validate the Cultural Humility and Enactment Scale - Supervision (CHES-S). Method The sample included a total of 201 post-masters counselors who were currently engaged in clinical supervision across 11 U.S. states, who were recruited from the state licensing board email lists. Analyses included confirmatory factor analysis (CFA) and item response theory (IRT) analysis based on a multidimensional adaptation of the partial credit model. Results We found evidence to support the three-factor structure of the CHES-S. We also found that the CHES-S can be used to distinguish participants scores from low to high CH, and that the thresholds of each item could capture participants responses in the expected order. Conclusion Evidencing reliability and validity with a sample of post-master’s practitioners engaged in supervision for licensure, the CHES-S can be effectively utilized as a tool to monitor supervisory process and outcome in clinical supervision.

Performance Effects of Different Shutdown Methods on Three Electrode Materials for Electromethanogenesis

AbstractIndustrial applications of microbial electrochemical systems will require regular maintenance shutdowns, involving inspections and component replacements to extend the lifespan of the system. Here, we examined the impact of such shutdowns on the performance of three electrode materials (i. e., platinized titanium, graphite, and nickel) as cathodes in a microbial electrochemical system that would be used for electromethanogenesis in power‐to‐gas applications. We focused on methane (CH4) production from hydrogen (H2) and carbon dioxide (CO2) using Methanothermobacter thermautotrophicus. We showed that the platinized titanium cathode resulted in high volumetric CH4 production rates and Coulombic efficiencies. Using a graphite cathode would be more cost‐effective than using the platinized titanium cathode in microbial electrochemical systems, but showed an inferior performance. The microbial electrochemical system with the nickel cathode showed improvements compared to the graphite cathode. Additionally, this system with a nickel cathode demonstrated the fastest recovery during a shutdown experiment compared to the other two cathodes. Fluctuations in pH and nickel concentrations in the catholyte during power interruptions affected CH4 production recovery in the system with the nickel cathode. This research enhances understanding of the integration of biological and electrochemical processes in microbial electrochemical systems, providing insights into electrode selection and operating strategies for effective and sustainable CH4 production.

Fabrication of Hofmann-type metal-organic framework based mixed-matrix membranes for efficient CH4/N2 separation

The analogous physical and chemical properties of methane (CH4) and nitrogen (N2) pose a great challenge for their separation. Mixed-matrix membranes (MMMs), combining the good separation performance of fillers and easy processability of polymers, are expected to address this challenging task. In this work, one Hofmann-type metal-organic framework (MOF), CoNi-DABCO, featuring abundant oppositely adjacent open metal sites, narrow pore size, and strong binding affinity toward CH4, is introduced into the polymer of polydimethylsiloxane to fabricate MMMs. The presence of CoNi-DABCO in the membranes could enhance the adsorption capacity for CH4, thus facilitating the transport of CH4 molecules through the membranes. Specially, the MMM containing 20 wt% CoNi-DABCO displays a high CH4 permeability of 1285 Barrer and maintains a good CH4/N2 mixed-gas selectivity of 3.7. Furthermore, the MMMs show good pressure resistance (up to 10 bar) and long-term stability for 30 days. This study suggests the potential of Hofmann-type MOF in the development of high-performance membranes for CH4/N2 separation.

Snowflake-like In2S3/Cu2S heterojunction for simultaneous photocatalytic persulfate oxidation of tetracycline hydrochloride and CO2 photoreduction

To achieve tetracycline hydrochloride (TCH) elimination and CO2 photoconversion to CH4 and CO, snowflake-like In2S3/Cu2S heterojunctions were fabricated through the hydrothermal approach. Z-scheme junction generated between In2S3 and Cu2S was likely to separate and migrate the photoactivated e-/h+ pairs, boosting the photocatalytic-persulfate (photo-PS) activity and CO2 photoconversion capacity. The single photo-PS oxidation of TCH and CO2 photoreduction as well as their simultaneous photocatalytic behaviors over snowflake-like In2S3/Cu2S composites were comparatively investigated. For optimal 3-In2S3/Cu2S with a nominal In2S3 content of 5.0 wt%, the removal efficiency of unary photo-PS oxidation system was 99.90 %, CH4 and CO yield rates of single CO2 photoreduction process were respectively 177.67 and 94.42 μmol g-1h−1. In dual photo-PS oxidation and CO2 photoreduction system, the addition of CO2 leaded to the lower photo-PS activity, while the higher CH4 and CO yield rates of 3-In2S3/Cu2S. When added CO2 to dual photocatalytic system, the removal efficiency of TCH, CH4 and CO yield rates reached to 78.38 %, 106.80, and 73.84μmol g-1h−1, which were 0.94, 1.34, and 1.39 folds than those without CO2. This work provided the possibility of simultaneous photo-PS oxidation of pollutants and CO2 photoconversion to C1 compounds.

A microporous fluorinated MOF for efficient separation of C2H2 from C2H2/CO2 and C2H2/C2H4 mixtures

Acetylene (C2H2)-adsorbed physisorbents are promising in addressing significant yet challenging industrial separation processes, such as the purification of C2H2 from carbon dioxide (CO2) and ethylene (C2H4) from C2H2. Herein, we report a fluorinated metal–organic framework (MOF), QDU-MOF-1, featuring micropores full of fluorinated anions, which enables preferential C2H2 adsorption over CO2 and C2H4. QDU-MOF-1 exhibits a high C2H2 adsorption capacity of 141.03 cm3/g at 298 K and 1 bar. Dynamic breakthrough experiments demonstrate a C2H2 capture capacity of 127.76 cm3/g for equimolar C2H2/CO2 mixtures. Strong affinity was revealed by density functional theory calculations between C2H2 and SiF62- in pores through hydrogen bonding, contributing to high C2H2 adsorption capacity. QDU-MOF-1 also shows good air stability and recyclability, making it potential for the C2H2/CO2 and C2H2/C2H4 separation applications. This study underscores the strength of discovering advanced physisorbents for challenging gas separations with low energy footprints.

Methylotuvimicrobium alcaliphilum 20Z based ectoine production from various industrial CH4 sources: Cultivation optimization and comprehensive analysis

Methanotroph-based CH4 conversion technology is being widely studied due to its advantages of mild operating conditions and environmental friendliness. In this study, operating strategies were investigated for industrial CH4 sources in order to widely disseminate methanotroph-based CH4 conversion technology using the promising strain, Methylotuvimicrobium alcaliphilum 20Z. The optimal O2/CH4 ratio for extremely different CH4 concentrations was explored based on kinetic-based simulation for biological reaction, and experimentally proven using fermenter-scale experiments. As a result, when high CH4 concentration is used, ectoine production rate can be maximized (33.8 mg/L·h) at an O2/CH4 ratio of 1 while favoring the “production of metabolites”. On the other hand, in the low CH4 concentration case, when changing from the general O2/CH4 ratio of 4 to the optimal O2/CH4 ratio (i.e., 1), although the improvement in ectoine concentration was not noticeable (3.9 to 7.5 mg/L·h), the CH4 conversion rate rapidly decreased (50 to 20 %), suggesting that the focus in the low concentration case should be on “removal of CH4”. In the case of biogas, the rapid pH drop caused by the large amount of CO2 in the feed is offset by a buffer solution, and the concentration of Na+ ions increases during the overall reaction time. Therefore, the production of metaboiltes can be maximized while simultaneously controlling pH and Na+ ion through continuous operation with a high dilution rate (19.8 mg/L·h). Furthermore, major performance indicators for each industrial gas were derived through comprehensive comparative analysis, through which the “dual-functions” of methanotrophs could be emphasized. This study provides a practical and strategic approach for methanotrophs that can flexibly respond to diverse industrial CH4 sources.

Anionic Ionomer: Released Surface-Immobilized Cations and an Established Hydrophobic Microenvironment for Efficient and Durable CO2-to-Ethylene Electrosynthesis at High Current over One Month.

Electrosynthesis of multicarbon products, such as C2H4, from CO2 reduction on copper (Cu) catalysts holds promise for achieving carbon neutrality. However, maintaining a steady high current-level C2H4 electrosynthesis still encounters challenges, arising from unstable alkalinity and carbonate precipitation caused by undesired ion migration at the cathode under a repulsive electric field. To address these issues, we propose a universal "charge release" concept by incorporating tiny amounts of an oppositely charged anionic ionomer (e.g., perfluorinated sulfonic acid, PFSA) into a cationic covalent organic framework on the Cu surface (cCOF/PFSA). This strategy effectively releases the hidden positive charge within the cCOF, enhancing surface immobilization of cations to impede both outward migration of generated OH- and inward migration of cations, inhibiting carbonate precipitation and creating a strong alkaline microenvironment. Meanwhile, the ionomer's hydrophobic chains create a hydrophobic environment within the cCOF, facilitating efficient gas transport. In situ characterizations and theoretical calculations demonstrate that the cCOF/PFSA catalyst establishes a hydrophobic strong alkaline microenvironment, optimizing the adsorption strength and configuration of *CO intermediates to promote the C2H4 formation. The optimized catalyst achieves a 70.5% Faradaic efficiency for C2H4 with a partial current density over 470 mA cm-2. Notably, it delivers a high single-pass carbon efficiency of 96.5% for CO2RR and sustains an exceptional stability over 760 h. When implemented in a large-area MEA electrolyzer and a 5-cell MEA stack, the system achieves an industrial current of 15 A and continuous C2H4 production exceeding 19 mL min-1, marking a significant step toward industrial feasibility in CO2RR-to-C2H4 conversion.

Multifunctional and Ultrastable Co-MOF Effectively Separates Various Different Component Gas Mixtures.

Developing low-cost and multifunctional adsorbents for adsorption separation to obtain high-purity (>99.9%) gases is intriguing yet challenging. Notably, the ongoing trade-off between adsorption capacity and selectivity in separating multicomponent mixed gases still persists as a pressing scientific challenge requiring urgent attention. Herein, the ultrastable TJT-100 exhibits unique structural characteristics including uncoordinated carboxylate oxygen atoms, coordinated water molecules directed toward the pore surface, and sufficient Me2NH2+ cations in channels. TJT-100 exhibits a high adsorption capacity and exceptional separation performance, particularly notable for its high C2H2 capacity of 127.7 cm3/g and remarkable C2H2 selectivity over CO2 (5.4) and CH4 (19.8), which makes it a standout material for various separation applications. In a breakthrough experiment with a C2H2/CO2 mixture (v/v = 50/50), TJT-100 achieved a record-high C2H2 productivity of 69.33 L/kg with a purity of 99.9%. Additionally, TJT-100 demonstrates its effectiveness in separating CO2 from natural gas and flue gas. Its exceptional selectivity for CO2/CH4 (10.7) and CO2/N2 (11.9) results in a high CO2 productivity of 21.23 and 22.93 L/kg with 99.9% purity from CO2/CH4 (v/v = 50/50) and CO2/N2 (v/v = 15/85) mixtures, respectively.

Evidence-based surgery for cesarean hysterectomy secondary to placenta accreta spectrum: A systematic review

ObjectiveIn this systematic review, we aim to propose evidence-based management for perioperative care to improve outcomes at the time of planned cesarean hysterectomy for placenta accreta spectrum, a procedure associated with significant maternal and neonatal morbidity. Data SourcesWe conducted a literature search for studies published in MEDLINE (via Ovid), Embase, CINAHL, and Cochrane/CENTRAL up until February 25, 2022. The search included free-text and controlled-vocabulary terms for cesarean section, cesarean delivery, and hysterectomy. Study Eligibility CriteriaWe included randomized controlled trials, prospective cohort, retrospective cohort, and case-control studies published in English that reported on a perioperative intervention in the performance of a planned CH for PAS. Studies must have included a comparator group. Of the 8,907 studies screened in this systematic review, 79 met the inclusion criteria. Study Appraisal and Synthesis MethodsArticles examining each step or intervention of the CH were grouped together and reviewed qualitatively as a group. Evidence levels and recommendations were made by consensus of all authors according to the terminology of the United States Preventive Services Task Force (USPSTF). We synthesized the results of 79 articles, and provided 28 recommendations. ResultsBased on USPSTF criteria, 21.4 % of the recommendations were level B (n = 6), 39.3 % were C (n = 11), 10.7 % were D (n = 3) and 28.6 % were I (n = 8). The interventions with the highest level of recommendation included delivery at a hospital with high cesarean hysterectomy volume, implementation of a standardized hospital protocol, delivery via a planned procedure, neuraxial anesthesia, and transverse skin incision (all level B recommendations by USPSTF criteria). ConclusionsDevelopment of a standardized hospital protocol, delivery at a center with high CH surgical volume, and utilization of neuraxial anesthesia garnered B evidence levels. Recommendations were limited due to the lack of prospective trials. Further research into the technical aspects of this high-risk procedure is warranted.

Landscape patterns of carbon fluxes in natural and disturbed ice-wedge-polygon tundra

ABSTRACT The degradation of ice-rich permafrost ecosystems due to climate change and infrastructure development strongly impacts carbon exchange dynamics in tundra landscapes. This study investigates the effects of surficial geology and infrastructure disturbances from road dust and flooding on vegetation and trace gas fluxes in polygonal ice-wedge tundra in arctic Alaska. We compared CO2 and CH4 fluxes from closed-chamber measurements at common landform elements (polygon centers, troughs, and rims) at a natural site and a disturbed site within the Prudhoe Bay Oil Field. Relationships among environmental parameters, plant species composition, and trace gas fluxes were assessed through nonmetric multidimensional scaling. Map extrapolations showed spatial variations in midsummer landscape-level ecosystem productivity and CH4 efflux at the various geologic landforms. Highest carbon uptake occurred in ice-rich drained thaw lake basins with aquatic, graminoid-dominated polygon troughs. In contrast, wet, featureless areas associated with more recently drained, ice-poor thaw lake basins showed a net carbon loss even during summer. The damming effect of road infrastructure led to deeply flooded, minimally vegetated troughs with low ecosystem respiration and high CH4 fluxes close to the road. This work highlights the importance of the complex interactions among surficial geology, landform elements, vegetation type, and disturbance factors in understanding carbon exchange dynamics in ice-rich permafrost environments.

Impacts of O2:CH4 ratios and CH4 concentrations on the denitrification and CH4 oxidations of a novel AME-AD system

Aerobic methane (CH4) oxidation coupled to denitrification (AME-D) is a promising process for the denitrification of low C/N wastewater. Compared with anaerobic denitrifying bacteria, aerobic denitrifying bacteria may enable AME-D have high denitrification ability under aerobic conditions. This study constructed a novel aerobic methane oxidation coupled to aerobic denitrification (AME-AD) system using the typical aerobic denitrifying bacteria Paracoccus pantotrophus ATCC35512 and the typical aerobic methane oxidizing bacteria Methylosinus trichosporium OB3b. The denitrification and CH4 oxidations of AME-AD with different O2:CH4 ratios (0:1, 0.25:1, 0.5:1, 0.75:1, 1:1 and 1.25:1) and CH4 concentrations (0, 14000, 28000, 42000, 56000 and 70000 mg m−3) were investigated in batch experiments. Higher O2:CH4 ratios can significantly improve the denitrification and CH4 oxidations of the AME-AD (P < 0.05). The treatment with an O2:CH4 ratio of 1.25:1 had the highest denitrification rate (0.036 mg h−1) and highest CH4 oxidation rate (0.20 mg h−1). The CH4 concentration in the headspace was positively correlated with the AME-AD denitrification rate. The calculated CH4/NO3−(mol/mol) in most treatments ranged from 5.76 to 6.84. In addition, excessively high O2 and CH4 concentrations can lead to increased nitrous oxide (N2O) production in AME-AD. The N2O production rate was up to 1.00 μg h−1 when the O2:CH4 was 1.25:1. These results can provide data support for the application of AME-AD for low-C/N wastewater treatment and greenhouse gas emission reduction.

Designing metal organic framework/ionic liquid composite materials to enhance CH₄/N₂ selectivity via computational and experimental approaches

In this work, we propose a computational and experimental approach to systematically select pyridine-based ionic liquids (IL) and examine their impact on the pore structure of CH4/N2 adsorption materials. Our objective is to design novel MIL-53(Al)@IL composites, with MIL-53(Al) as the parent metal organic framework (MOF), for efficient CH4/N2 separation. The optimal addition of pyridine-based ionic liquids resulted in the MIL-53(Al)@BH-3 (N-butylpyridinium hydrogen sulfate abbreviated as BH-3) composite, which features an ultramicropore structure and a large specific surface area of 1204 cm2 g−1. The MIL-53(Al)@BH-3 composite achieved a high CH4 capacity of 28.21 cm³(STP) g−1 and a selectivity of 7.7 at 298K and 1 bar in pure-component equilibrium adsorption. In breakthrough experiments, CH4 breakthrough occurred significantly later than N2 (approximately 2 min). Therefore, the strategy of manufacturing porous MIL-53(Al)@BH-3 composites effectively enhances the overall adsorption performance for CH4/N2 separation.

A mixed polynuclear clusters-based Y-MOF with an unprecedented (12, 12, 18)-c topology: highly efficient propylene/ethylene separation and iodine adsorption

The design and synthesis of highly stable metal–organic frameworks (MOFs) bearing unpredictable polynuclear clusters and new topologies are important for the development of novel and complicated MOFs. Herein, the polynuclear rare-earth (RE) clusters with more coordination modes and the small V-shaped ligand (2,5-thiophenedicarboxylic acid) were chosen, and subsequently JLU-MOF132 with three different yttrium clusters (two independent Y6 and one Y9 clusters) and a novel (12, 12, 18)-connected topology was successfully synthesized. Notably, JLU-MOF132 exhibits high porosity, excellent thermal, acid-base, and solvent stabilities. JLU-MOF132 shows considerable potential in methanol-to-olefins (MTO) products (C3H6 and C2H4) separation. The high ideal adsorbed solution theory C3H6/C2H4 selectivities (9.2, 10.6, and 15.1) and the breakthrough experiments results, including the high C2H4 purity (>99.9 %) and productivities (26.1, 73.1, and 101.0 L·kg-1), demonstrate its practical purification capability. Semi-empirical tight binding (xTB) quantum chemical calculations explain the mechanisms that differentiate C2H4 and C3H6 adsorption in JLU-MOF132. In addition, JLU-MOF132 also displays outstanding radioactive iodine adsorption performance, with an iodine uptake of 750 mg·g-1 in vapor and 153 mg·g-1 in cyclohexane solutions. Briefly, this work not only demonstrates the viability of employing the V-shaped ligand to increase the structural diversity of highly stable MOFs, but also enhances the application potential of MOFs in the fields of the MTO products separation and radioactive iodine adsorption.