Observed changes in China's methane emissions linked to policy drivers.

China is set to actively reduce its methane emissions in the coming decade. A comprehensive evaluation of the current situation can provide a reference point for tracking the country's future progress. Here, using satellite and surface observations, we quantify China's methane emissions during 2010-2017. Including newly available data from a surface network across China greatly improves our ability to constrain emissions at subnational and sectoral levels. Our results show that recent changes in China's methane emissions are linked to energy, agricultural, and environmental policies. We find contrasting methane emission trends in different regions attributed to coal mining, reflecting region-dependent responses to China's energy policy of closing small coal mines (decreases in Southwest) and consolidating large coal mines (increases in North). Coordinated production of coalbed methane and coal in southern Shanxi effectively decreases methane emissions, despite increased coal production there. We also detect unexpected increases from rice cultivation over East and Central China, which is contributed by enhanced rates of crop-residue application, a factor not accounted for in current inventories. Our work identifies policy drivers of recent changes in China's methane emissions, providing input to formulating methane policy toward its climate goal.

Pore-Matched Sponge for Microorganisms Pushes Electron Extraction Limit in Microbial Fuel Cells.

Microbial fuel cells (MFCs) are of great potential for wastewater remediation and chemical energy recovery. Nevertheless, limited by inefficient electron transfer between microorganisms and electrode, the remediation capacity and output power density of MFCs are still far away from the demand of practical application. Herein, a pore-matching strategy is reported to develop uniform electroactive biofilms by inoculating microorganisms inside a pore-matched sponge, which is assembled of core-shell polyaniline@carbon nanotube (PANI@CNT). The maximum power density achieved by the PANI@CNT bioanode is 7549.4 ± 27.6 mW m-2 , which is higher than the excellent MFCs with proton exchange membrane reported to date, while the coulombic efficiency also attains a considerable 91.7 ± 1.2%. The PANI@CNT sponge enriches the exoelectrogen Geobacter significantly, and is proved to play the role of conductive pili in direct electron transfer as it down-regulates the gene encoding pilA. This work exemplifies a practicable strategy to develop excellent bioanode to boost electron extraction in MFCs and provides in-depth insights into the enhancement mechanism.

The critical roles of propanethiol oxidoreductase and sulfide-quinone oxidoreductase in the propanethiol catabolism pathway in Pseudomonas putida S-1.

Propanethiol (PT) is a hazardous pollutant that poses risks to both the environment and human well-being. Pseudomonas putida S-1 has been identified as a microorganism capable of utilizing PT as its sole carbon source. However, the metabolic pathway responsible for PT degradation in P. putida S-1 has remained poorly understood, impeding its optimization and practical application. In this study, we investigated the catabolic network involved in PT desulfurization with P. putida S-1 and identified key gene modules crucial to this process. Notably, propanethiol oxidoreductase (PTO) catalyzes the initial degradation of PT, a pivotal step for P. putida S-1's survival on PT. PTO facilitates the oxidation of PT, resulting H2S, H2O2, and propionaldehyde (PA). Catalase-peroxidase catalyzes the conversion of H2O2 to oxygen and water, while PA undergoes gradual conversion to Succinyl-CoA, which is subsequently utilized in the tricarboxylic acid cycle. H2S is digested in a comprehensive desulfurization network where sulfide-quinone oxidoreductase (SQOR) predominantly converts it to sulfane sulfur. The transcriptome analysis suggests that sulfur can be finally converted to sulfite or sulfate and exported out of the cell. The PT degradation capacity of P. putida S-1 was enhanced by increasing the transcription level of PTO and SQOR genes in vivo.IMPORTANCEThis work investigated the PT catabolism pathway in Pseudomonas putida S-1, a microorganism capable of utilizing PT as the sole carbon source. Critical genes that control the initiation of PT degradation were identified and characterized, such as pto and sqor. By increasing the transcription level of pto and sqor genes in vivo, we have successfully enhanced the PT degradation efficiency and growth rate of P. putida S-1. This work does not only reveal a unique PT degradation pathway but also highlights the potential of enhancing the microbial desulfurization process in the bioremediation of thiol-contaminated environment.

Enhanced chlorobenzene removal by internal magnetic field through initial cell adhesion and biofilm formation.

Magnetic fields (MF) have been proven efficient in bioaugmentation, and the internal MFs have become competitive because they require no configuration, despite their application in waste gas treatment remaining largely unexplored. In this study, we firstly developed an intensity-regulable bioaugmentation with internal MF for gaseous chlorobenzene (CB) treatment with modified packing in batch bioreactors, and the elimination capacity increased by up to 26%, surpassing that of the external MF. Additionally, the microbial affinity to CB and the packing surface was enhanced, which was correlated with the ninefold increased secreted ratio of proteins/polysaccharides, 43% promoted cell surface hydrophobicity, and half reduced zeta potential. Furthermore, the dehydrogenase content was promoted over 3 times, and CB removal steadily increased with the rising intensity indicating enhanced biofilm activity and reduced CB bioimpedance; this was further supported by kinetic analysis, which resulted in improved cell adhesive ability and biological utilisation of CB. The results introduced a novel concept of adjustable magnetic bioaugmentation and provided technical support for industrial waste gas treatments. KEY POINTS: • Regulable magnetic bioaugmentation was developed to promote 26% chlorobenzene removal • Chlorobenzene mineralisation was enhanced under the magnetic field • Microbial adhesion was promoted through weakening repulsive forces.

Enhancement of bio-S0 recovery and revealing the inhibitory effect on microorganisms under high sulfide loading.

Biodesulfurization is a mature technology, but obtaining biosulfur (S0) that can be easily settled naturally is still a challenge. Increasing the sulfide load is one of the known methods to obtain better settling of S0. However, the inhibitory effect of high levels of sulfide on microbes has also not been well studied. We constructed a high loading sulfide (1.55-10.86 kg S/m3/d) biological removal system. 100% sulfide removal and 0.56-2.53 kg S/m3/d S0 (7.0 ± 0.09-16.4 ± 0.25 µm) recovery were achieved at loads of 1.55-7.75 kg S/m3/d. Under the same load, S0 in the reflux sedimentation tank, which produced larger S0 particles (24.2 ± 0.73-53.8 ± 0.70 µm), increased the natural settling capacity and 45% recovery. For high level sulfide inhibitory effect, we used metagenomics and metatranscriptomics analyses. The increased sulfide load significantly inhibited the expression of flavin cytochrome c sulfide dehydrogenase subunit B (fccB) (Decreased from 615 ± 75 to 30 ± 5 TPM). At this time sulfide quinone reductase (SQR) (324 ± 185-1197 ± 51 TPM) was mainly responsible for sulfide oxidation and S0 production. When the sulfide load reached 2800 mg S/L, the SQR (730 ± 100 TPM) was also suppressed. This resulted in the accumulation of sulfide, causing suppression of carbon sequestration genes (Decreased from 3437 ± 842 to 665 ± 175 TPM). Other inhibitory effects included inhibition of microbial respiration, production of reactive oxygen species, and DNA damage. More sulfide-oxidizing bacteria (SOB) and newly identified potential SOB (99.1%) showed some activity (77.6%) upon sulfide accumulation. The main microorganisms in the sulfide accumulation environment were Thiomicrospiracea and Burkholderiaceae, whose sulfide oxidation capacity and respiration were not significantly inhibited. This study provides a new approach to enhance the natural sedimentation of S0 and describes new microbial mechanisms for the inhibitory effects of sulfide.

Ceramsite made from remediated soil: A risk assessment of its potential role serving as urban street cushion.

To promote the reuse of remediated soil (RS) and facilitate the cleanup of rainwater in sponge city, we investigated the effects of ceramsite made from RS serving as urban street cushion. Ceramsite was prepared by RS or pollution-free soil (PS) and showed no difference in physical properties. Compared with gravel, ceramsite had purification effects on effluents, reducing the content of chemical oxygen demand, total nitrogen, and ammoniacal nitrogen. However, the content of total phosphorus and the concentration of Cr(VI) and arsenic slightly increased in ceramsite groups, inferring potential risk. Microbial community analysis proved that ceramsite promoted microbial growth and increased microbial diversity. A long-term risk assessment indicated that ceramsite was good at fixing heavy metals during leaching process. Taken together, ceramsite prepared from RS could serve as excellent urban street cushion with little potential risk to surroundings.

A supplementary assessment system of AQI-V for comprehensive management and control of air quality in chemical industrial parks.

Volatile organic compounds (VOCs) are the dominant pollutants in industrial parks. However, they are not generally considered as part of the air quality index (AQI) system, which leads to a biased assessment of pollution in industrial parks. In this study, a supplementary assessment system of AQI-V was established by analyzing VOCs characteristics with vehicle-mounted PTR-TOFMS instrument, correlation analysis and the standards analysis. Three hourly and daily scenarios were considered, and the hierarchical parameter setting was further optimized by field application. The hourly and daily assessments revealed the evaluation factors for the discriminability of different air quality levels, practiced value for regional air quality improvement, and the reservation of general dominant pollutants. Finally, the universality testing in ZPIP successfully recognized most of the peaks, with 54.76%, 38.39% and 6.85% for O3, VOCs and NO2 as the dominant pollutant, and reflected the daily ambient air quality condition, together with the dominant pollutant. The AQI-V system with VOCs sub-index is essential for air quality evaluation in industrial parks, which can further provide scientific support to control the pollution of VOCs and the secondary pollutant, therefore significantly improve the air quality in local industrial parks.

Clinical pharmacology considerations for the approval of belimumab for the treatment of adult patients with active lupus nephritis: A regulatory perspective.

On 16 December 2020, FDA approved Benlysta® (belimumab) for both the intravenous (IV) and subcutaneous (SC) administration routes for the treatment of adult patients with active lupus nephritis (LN) who are receiving standard therapy. This approval represents the first FDA approved treatment of patients with active LN.The approved IV dosing regimen (10 mg/kg dose Q2W for three doses, then 10 mg/kg Q4W thereafter) was based on a randomized double-blind placebo controlled clinical trial in adult patients with LN. For the approval of the SC dosing regimen (400 mg dose QW for four doses, then 200 mg QW thereafter), efficacy was supported solely by pharmacokinetics (PK) modeling and simulation which estimated a matched steady state average concentration and higher trough concentrations for the SC administration route, for bridging to the efficacy of IV belimumab in adults with LN. The safety and immunogenicity profile of the SC administration route has been assessed in the SLE studies.In a population PK analysis, higher proteinuria was associated with greater belimumab clearance and lower belimumab exposure. In an exposure response analysis, the efficacy of belimumab as evaluated by renal response was mainly driven by patients with lower proteinuria at baseline regardless of other baseline characteristics (e.g. baseline renal function, renal biopsy classification), induction therapies, or belimumab exposure levels (within 10 mg/kg dosing regimen), etc. However, post hoc analyses showed that belimumab had activity in LN patients with higher proteinuria at baseline. There is no adequate information to suggest that a higher dose would provide additional benefit for patients with lower exposure (e.g. higher proteinuria).

Direct Measuring Particulate Matters in Smoke Plumes from Chimneys in a Textile Dyeing Industrial Park by a Self-Developed PM Detector on an UAV in Yangtze River Delta of China.

Directly measuring particulate matters (PM) from chimneys in an industrial park is difficult due to it being hard to reach the peak heights. A self-developed PM detector on an unmanned aerial vehicle (UAV) had been deployed to directly measure the PM emissions in smoke plumes from chimneys in a textile dyeing industrial park. Compared with a commercial PM device (LD-5R, SIBATA, Kyoto, Japan), the self-developed detector showed similar performance with a good correlation (R2 varying from 0.911 to 0.951) in simultaneously vertical PM measurements on UAV. The PM emissions from chimneys after different textile treating processes, including pigment printing, dyeing process, and digital printing, were investigated. PM mass concentrations and particle number concentrations (PNC) in different sizes were found to be significantly higher in pigment printing than those in dyeing process and digital printing by 2 or 3 times after electrostatic precipitation. The activated carbon adsorption and electrostatic precipitation were the major PM controlling techniques in the park. The PM mass concentrations and PNC were the highest in the process of dyeing after activated carbon adsorption with the concentrations of PM1 (1000 µg·m-3), PM2.5 (1600 µg·m-3), and PM10 (2000 µg·m-3), respectively. According to the results of PM and PNC, PM2.5 was found to be the dominant particles accounting for 99% of the PM emissions. It may be due to the high temperature in thermo-fixing machine, which is beneficial to the PM2.5 generation. This study revealed PM2.5 was the dominant particles to be reduced in textile dyeing enterprises to mitigate PM pollution.

Airlift two-phase partitioning bioreactor for dichloromethane removal: Silicone rubber stimulated biodegradation and its auto-circulation.

Solid non-aqueous phases (NAPs), such as silicone rubber, have been used extensively to improve the removal of volatile organic compounds (VOCs). However, the removal of VOCs is difficult to be further improved because the poor understanding of the mass transfer and reaction processes. Further, the conventional reactors were either complicated or uneconomical. In view of this, herein, an airlift bioreactor with silicone rubber was designed and investigated for dichloromethane (DCM) treatment. The removal efficiency of Reactor 1 (with silicone rubber) was significantly higher than that of Reactor 2 (without silicone rubber), with corresponding higher chloride ion and CO2 production. It was found that Reactor 1 achieved a much better DCM shock tolerance capability and biomass stability than Reactor 2. Silicone rubber not only enhanced the mass transfer in terms of both gas/liquid and gas/microbial phases, but also decreased the toxicity of DCM to microorganisms. Noteworthily, despite the identical inoculum used, the relative abundance of potential DCM-degrading bacteria in Reactor 1 (91.2%) was much higher than that in Reactor 2 (24.3%) at 216 h. Additionally, the silicone rubber could be automatically circulated in the airlift bioreactor due to the driven effect of the airflow, resulting in a significant reduction of energy consumption.

Does biological rhythm transmit from plants to rhizosphere microbes?

Plant physiological and metabolic processes are modulated by rhythmic gene expression in a large part. Meanwhile, plants are also regulated by rhizosphere microorganisms, which are fed by root exudates and provide beneficial functions to their plant host. Whether the biorhythms in plants would transfer to the rhizosphere microbial community is still uncertain and their intricate connection remains poorly understood. Here, we investigated the role of the Arabidopsis circadian clock in shaping the rhizosphere microbial community using wild-type plants and clock mutants (cca1-1 and toc1-101) with transcriptomic, metabolomic and 16S rRNA gene sequencing analysis throughout a 24-h period. Deficiencies of the central circadian clock led to abnormal diurnal rhythms for thousands of expressed genes and dozens of root exudates. The bacterial community failed to follow obvious patterns in the 24-h period, and there was lack of coordination with plant growth in the clock mutants. Our results suggest that the robust rhythmicity of genes and root exudation due to circadian clock in plants is an important driving force for the positive succession of rhizosphere communities, which will feedback on plant development.

A Novel Dual-Stage Phase Separation Process for CO2 Absorption into a Biphasic Solvent with Low Energy Penalty.

An amine-based biphasic solvent is promising to cut down the energy penalty of CO2 capture. However, the high viscosity of the CO2-enriched solvent retards its industrial application. This work proposed a novel dual-stage phase separation process using a triethylenetetramine and 2-(diethylamino)ethanol blend as a biphasic solvent, which separates a certain proportion of CO2-enriched phase during CO2 absorption to reduce its viscosity. Experimental results showed that the proposed dual-stage phase separation process improved the phase separation behavior and effectively enhanced the absorption rate by 49% at 50 °C, when 50 vol % CO2-enriched phase was separated at 0.3 mol mol-1. Kinetic analysis showed that the absorption rate was mainly controlled by liquid-side mass transfer. The regeneration heat of the dual-stage phase separation process cut down the energy penalty by 33% compared with the monoethanolamine-based process. Compared with the conventional biphasic solvent-based process, the heat duty was further declined by 8%. The 1H nuclear magnetic resonance analysis showed that the dual-stage phase separation process could effectively control the generation of absorption products and intensify the interphase migration of tertiary amines.

Mechanisms of Active Substances in a Dielectric Barrier Discharge Reactor: Species Determination, Interaction Analysis, and Contribution to Chlorobenzene Removal.

Several typical active substances (•NO, •NO2, H2O2, O3, •OH, and O2-•), directly or indirectly play dominant roles during dielectric barrier discharge (DBD) reaction. This study measured these active substances and removed them by using radical scavengers, such as catalase, superoxide dismutase, carboxy-PTIO (c-PTIO), tert-butanol (TBA), and MnO2 in different reaction atmospheres (air, N2, and O2). The mechanism for chlorobenzene (CB) removal by plasma in air atmosphere was also investigated. The production of O═NOO-• generated by •NO took around 75% of the total production of O═NOO-•. Removing •NO increased the O3 amount by about 80% likely because of the mutual inhibition between O3 and reactive nitrogen species in or out of the discharge area. The quantitative comparison of •OH and H2O2 revealed that the formation of •OH was 3.06-4.65 times that of H2O2 in these reaction atmospheres. Calculation results showed that approximately 1.61% of H2O was used for O3 generation. Ionization patterns affected the form of solid deposits during the removal of CB in N2 and O2 atmospheres caused by Penning ionization and thermal radiation tendencies, respectively. Correlation analysis results suggested the macroscopic synergistic or inhibitory effects happened among these active substances. A zero-dimensional reaction kinetics model was adopted to analyze the reactions during the formation of active substances in DBD, and the results showed good consistency with experiments. The interactions of each active substance were clarified. Finally, a response surface method model was developed to predict CB removal by the DBD plasma process. Stepwise regression analysis results showed that CB removal was affected by the contents of different active substances in air, N2 atmosphere, and O2 atmosphere, respectively: O2-•, •OH, and O3; H2O2, O═NOO-•, and O3; •OH and O3.

A disease progression model of longitudinal lung function decline in idiopathic pulmonary fibrosis patients.

Pirfenidone and nintedanib are the first two FDA-approved therapies for treatment of idiopathic pulmonary fibrosis (IPF). The clinical programs for pirfenidone and nintedanib included 1132 patients in the placebo arms and 1691 patients in the treatment arms across 6 trials. We developed a disease progression model to characterize the observed variability in lung function decline, measured as percent predicted forced vital capacity (%p-FVC), and its decrease in decline after treatment. The non-linear longitudinal change in %p-FVC was best described by a Weibull function. The median decreased decline in %p-FVC after treatment was estimated to be 1.50% (95% CI [1.12, 1.79]) and 1.96% (95% CI [1.47, 2.36]) at week 26 and week 52, respectively. Smoking status, weight, %p-FVC, %p-DLco and oxygen use at baseline were identified as significant covariates affecting decline in %p-FVC. The decreased decline in %p-FVC were observed among all subgroups of interest, of which the effects were larger at 1 year compared to 6 months. Based on the disease progression model smoking status and oxygen use at baseline may affect the treatment effect size. At week 52, the decreased decline in %p-FVC for current smokers and patients with oxygen use at baseline were 1.56 (90% CI [1.02, 1.99]) and 2.32 (90% CI [1.74, 2.86]), respectively. These prognostic factors may be used to enrich studies with patients who are more likely to respond to treatment, by demonstrating a lesser decline in lung function, and therefore provide the potential to allow for IPF studies with smaller study populations or shorter durations.

Optimization of photocatalytic degradation conditions and toxicity assessment of norfloxacin under visible light by new lamellar structure magnetic ZnO/g-C3N4.

Degradation of norfloxacin (NFX) by zinc oxide (ZnO)/g-C3N4, a magnetic sheet ZnO with g-C3N4 on its surface was studied. Through a new preparation system method, hydrothermal reaction provides a solid-layered magnetic ZnO material basis, and the simple thermal condensation method was used to transform the urea into g-C3N4 on the magnetic sheet ZnO in a uniform and orderly manner to increase the stability and photocatalytic performance of the material. Compared with previous studies, the pore volume and photocatalytic performance of the material are improved, and became more stable. By studying the degradation effect of basic and photocatalytic materials prepared in different proportions, the kinetic constant of ZGF is 0.01446 (min-1). The response surface methodology (RSM) was used to study the optimization and effect of solution pH (4-12), photocatalyst concentration (0.2-1.8 g/L), and NFX concentration (3-15 mg/L) on the degradation rate of NFX during photocatalytic degradation. The R2 value of the RSM model was 0.9656. The NFX removal rate is higher than 90% when the amount of catalyst is 1.43 g/L, the solution pH is 7.12, and the NFX concentration is less than 8.61 mg/L. After 5 cycles, the degradation rate of magnetic materials decreased to 92.8% of the first time. The capture experiment showed that the photocatalytic machine Toxicities was mainly hole action. The TOC removal rate within 2 h was 30%, a special intermediate toxicity analysis method was adopted according to the characteristics of NFX's inhibitory effect on Escherichia coli community. The toxicity of degraded NFX solution disappeared, and the possibility of non-toxic harm of by-products was verified. LC-Q-TOF method was used to detect and analyze various intermediate products converted from NFX after photocatalytic degradation, and the photocatalytic degradation pathway of NFX was proposed.

Co-pyrolysis of monobasic potassium phosphate and plastic processing sludge: Characteristics and environmental risks of potentially toxic elements.

A high concentration of potentially toxic elements (PTEs) can be frequently observed in the plastic processing sludge (PPS), thereby restricting its environmental applications. The main objective of this study was to investigate the effects of the co-pyrolysis of PPS and KH2PO4 (0, 5, 10 and 20 wt%) on the characteristics and environmental risks associated with the PTEs in PPS and derived chars. General characteristic analysis revealed that the char yield, ash content, pH, and particle size of the chars prepared with KH2PO4 were greater than those of the char prepared without KH2PO4 by 3.13-4.89 wt%, 2.95-4.4 wt%, 0.77-0.93, and 9.64-30.07 µm, respectively. The results of sequential extraction indicated that co-pyrolysis with KH2PO4 could considerably increase the distribution of PTEs in the F4 fraction (non-bioavailable) in PPS by 1.30-65.90% when compared with that obtained via co-pyrolysis with 5 wt% of KH2PO4. The toxic leaching tests indicated that the leaching concentrations of Cr, Ni, Cu, Zn, Cd, and Pb in the char prepared without KH2PO4 decreased to different extents when PPS was subjected to co-pyrolysis with KH2PO4, especially in case of co-pyrolysis with 5 wt% of KH2PO4. The range of decrease was 26.40-88.34%. However, in case of Cu, Zn, and Pb, the leaching concentration of the chars prepared with more than 10 wt% of KH2PO4 increased owing to the decomposition of (Cu Zn)PbVO4(OH) in an acidic environment. The results obtained using Hakanson's equations revealed that the potential ecological risk associated with the PTEs in chars obtained by co-pyrolysis with KH2PO4 decreased, with a minimum decrease of 38.17%. In addition, the risk level associated with PPS reduced from considerable to low after co-pyrolysis with KH2PO4. The observations of this study imply that the co-pyrolysis of PPS with KH2PO4 can be a promising treatment for PTE immobilization.

Pollutant toxicology with respect to microalgae and cyanobacteria.

Microalgae and cyanobacteria are fundamental components of aquatic ecosystems. Pollution in aquatic environment is a worldwide problem. Toxicological research on microalgae and cyanobacteria can help to establish a solid foundation for aquatic ecotoxicological assessments. Algae and cyanobacteria occupy a large proportion of the biomass in aquatic environments; thus, their toxicological responses have been investigated extensively. However, the depth of toxic mechanisms and breadth of toxicological investigations need to be improved. While existing pollutants are being discharged into the environment daily, new ones are also being produced continuously. As a result, the phenomenon of water pollution has become unprecedentedly complex. In this review, we summarize the latest findings on five kinds of aquatic pollutants, namely, metals, nanomaterials, pesticides, pharmaceutical and personal care products (PPCPs), and persistent organic pollutants (POPs). Further, we present information on emerging pollutants such as graphene, microplastics, and ionic liquids. Efforts in studying the toxicological effects of pollutants on microalgae and cyanobacteria must be increased in order to better predict the potential risks posed by these materials to aquatic ecosystems as well as human health.

Dynamic Activation of Adsorbed Intermediates via Axial Traction for the Promoted Electrochemical CO2 Reduction.

Regulating the local environment and structure of metal center coordinated by nitrogen ligands (M-N4 ) to accelerate overall reaction dynamics of the electrochemical CO2 reduction reaction (CO2 RR) has attracted extensive attention. Herein, we develop an axial traction strategy to optimize the electronic structure of the M-N4 moiety and construct atomically dispersed nickel sites coordinated with four nitrogen atoms and one axial oxygen atom, which are embedded within the carbon matrix (Ni-N4 -O/C). The Ni-N4 -O/C electrocatalyst exhibited excellent CO2 RR performance with a maximum CO Faradic efficiency (FE) close to 100 % at -0.9 V. The CO FE could be maintained above 90 % in a wide range of potential window from -0.5 to -1.1 V. The superior CO2 RR activity is due to the Ni-N4 -O active moiety composed of a Ni-N4 site with an additional oxygen atom that induces an axial traction effect.

Phase Splitting Agent Regulated Biphasic Solvent for Efficient CO2 Capture with a Low Heat Duty.

A biphasic solvent features high absorption capacity and low heat duty for CO2 capture. Phase separation behavior is essential to cut down energy penalty. Four phase splitting agents with different hydrophobicities, such as 1,3-dimethyl-2-imidazolidinone (DMI), 1-methyl-2-pyrrolidinone (NMP), N,N-dimethylformamide, and sulfolane, were dosed to biphasic solvents, triethylenetetramine and 2-(diethylamino)ethanol. Experimental results revealed that they can tune the phase separation behavior during CO2 absorption. Generally, under the same CO2 loading, the volume ratio of the rich phase increased with their hydrophobicity (log P), which accounts for over 50%. Moreover, their influences on absorption capacity, kinetics, and thermodynamics were also investigated. After dosing NMP, the heat duty was decreased by 22%. Furthermore, a phase splitting agent with a positive log P was more conducive to reducing the heat duty, and one with a negative log P enhanced the absorption rate. With DMI, the absorption rate was 114% higher than that of MEA at rich loading. The 13C NMR analysis showed that the agents were not involved in CO2 absorption and did not affect the reaction mechanism. Furthermore, quantum calculation was used to verify the reaction mechanism, confirming that the phase splitting agent increases the reaction equilibrium constant and makes it proceed more thoroughly.

Novel Biphasic Solvent with Tunable Phase Separation for CO2 Capture: Role of Water Content in Mechanism, Kinetics, and Energy Penalty.

The biphasic solvent-based absorption process has been regarded as a promising alternative to the monoethanolamine (MEA)-based process because of its high absorption capacity, phase separation behavior, and potential for conserving energy for CO2 capture. A trade-off between the absorption capacity and phase separation ratio is critical for developing an advanced biphasic solvent. Typically, water content in the biphasic solvent can be manipulated to tune the phase separation behavior. To explore the relationship between water content and phase separation behavior, an inert organic solvent, 1-methyl-2-pyrrolidinone, was added as a substitute for water in a biphasic solvent, specifically a triethylenetetramine (TETA) and 2-(diethylamino)ethanol (DEEA) blend. Moreover, the water content-kinetics and thermodynamics relationships were also evaluated. Experimental results revealed that reducing the water content was beneficial for phase separation but adverse for adsorption capacity. Kinetic analysis indicated that the water content did not significantly affect the rate of CO2 absorption at a rich loading. Furthermore, the regeneration heat decreased with the water content. The regeneration heat of TETA-DEEA with a water content of 20 wt % was almost 50% less than that of MEA solution. 13C nuclear magnetic resonance analysis revealed that the water content did not affect the reaction mechanism between CO2 and amines.