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Journal of the American Chemical Society Jun 2024Identifying the active phase with the highest activity, which is long-believed to be a steady state of the catalyst, is the basis of rational design of heterogeneous...
Identifying the active phase with the highest activity, which is long-believed to be a steady state of the catalyst, is the basis of rational design of heterogeneous catalysis. In this work, we performed detailed investigations, successfully capturing the instantaneous structure-activity change in oscillating Pd nanocatalysts during methane oxidation, which reveals an unprecedented oscillatory active state. Combining quantitative environmental transmission electron microscopy and highly sensitive online mass spectrometry, we identified two distinct phases for the reaction: one where the Pd nanoparticles refill with oxygen, and the other, a period of abrupt pumping of oxygen and boosted methane oxidation within about 1 s. It is the rapid reduction process that shows the highest activity for total oxidation of methane, not a PdO or Pd steady state under the conditions applied here (methane:oxygen = 5:1). This observation challenges the traditional understanding of the active phase and requires a completely different strategy for catalyst optimization.
PubMed: 38942067
DOI: 10.1021/jacs.4c02830 -
Plant Physiology and Biochemistry : PPB Jun 2024The root system architecture is an important complex trait in rice. With changing climatic conditions and soil nutrient deficiencies, there is an immediate need to breed...
The root system architecture is an important complex trait in rice. With changing climatic conditions and soil nutrient deficiencies, there is an immediate need to breed nutrient-use-efficient rice varieties with robust root system architectural (RSA) traits. To map the genomic regions associated with crucial component traits of RSA viz. root length and root volume, a biparental F mapping population was developed using TI-128, an Ethyl Methane Sulphonate (EMS) mutant of a mega variety BPT-5204 having high root length (RL) and root volume (RV) with wild type BPT-5204. Extreme bulks having high RL and RV and low RL and RV were the whole genome re-sequenced along with parents. Genetic mapping using the MutMap QTL-Seq approach elucidated two genomic intervals on Chr.12 (3.14-3.74 Mb, 18.11-20.85 Mb), and on Chr.2 (23.18-23.68 Mb) as potential regions associated with both RL and RV. The Kompetitive Allele Specific PCR (KASP) assays for SNPs with delta SNP index near 1 were associated with higher RL and RV in the panel of sixty-two genotypes varying in root length and volume. The KASP_SNPs viz. Chr12_S4 (C→T; Chr12:3243938), located in the 3' UTR region of LOC_Os12g06670 encoding a protein kinase domain-containing protein and Chr2_S6 (C→T; Chr2:23181622) present upstream in the regulator of chromosomal condensation protein LOC_Os2g38350. Validation of these genes using qRT-PCR and in-silico studies using various online tools and databases revealed higher expression in TI-128 as compared to BPT- 5204 at the seedling and panicle initiation stages implying the functional role in enhancing RL and RV.
PubMed: 38941724
DOI: 10.1016/j.plaphy.2024.108836 -
Scientific Reports Jun 2024In order to improve the driving ability of the explosion wave simulation equipment, reduce the erosion effect of condensed explosives on the explosion wave simulation...
In order to improve the driving ability of the explosion wave simulation equipment, reduce the erosion effect of condensed explosives on the explosion wave simulation equipment, improve the safety of the test process, and make better use of the meteorological detonation driving method, it is necessary to optimize the source of the shock wave load in the driving section. Based on the finite volume method of FLACS, a methane detonation driving model corresponding to the test is established to explore the feasibility of using methane as an explosion source to test the structure against explosion shock wave. A methane detonation drive test was carried out to verify the accuracy of the numerical model. Finally, an engineering model for attenuation of shock wave overpressure peak value in pipeline is established by dimensional analysis, and the model coefficient is determined by numerical simulation and test data. The results show that the blast pressure is the highest when the methane volume ratio reaches 9.5 vol% in the methane-air mixture. Simply increasing oxygen content has little effect on the peak overpressure and positive pressure duration of shock wave. In the pure oxygen environment, the detonation effect can be achieved when the volume ratio of methane to oxygen is 1:2, and the incident pressure of the shock wave is proportional to the volume of the gas cloud. When the gas cloud volume is constant, a reasonable selection of methane-oxygen mixture ratio can achieve a better detonation effect, which can effectively increase the peak overpressure of the shock wave in the test section. The research results can provide technical reference for the development of new explosion wave simulation equipment.
PubMed: 38942899
DOI: 10.1038/s41598-024-65797-5 -
Science Advances Jun 2024Light-driven oxidative coupling of methane (OCM) for multi-carbon (C) product evolution is a promising approach toward the sustainable production of value-added...
Light-driven oxidative coupling of methane (OCM) for multi-carbon (C) product evolution is a promising approach toward the sustainable production of value-added chemicals, yet remains challenging due to its low intrinsic activity. Here, we demonstrate the integration of bismuth oxide (BiO) and gold (Au) on titanium dioxide (TiO) substrate to achieve a high conversion rate, product selectivity, and catalytic durability toward photocatalytic OCM through rational catalytic site engineering. Mechanistic investigations reveal that the lattice oxygen in BiO is effectively activated as the localized oxidant to promote methane dissociation, while Au governs the methyl transfer to avoid undesirable overoxidation and promote carbon─carbon coupling. The optimal Au/BiO-TiO hybrid delivers a conversion rate of 20.8 millimoles per gram per hour with C product selectivity high to 97% in the flow reactor. More specifically, the veritable participation of lattice oxygen during OCM is chemically looped by introduced dioxygen via the Mars-van Krevelen mechanism, endowing superior catalyst stability.
PubMed: 38941471
DOI: 10.1126/sciadv.ado4390 -
Journal of Chemical Theory and... Jun 2024Frustrated Lewis Pairs (FLP) are an important advance in metal-free catalysis due to their ability to activate a variety of small molecules. Many studies have focused on...
Frustrated Lewis Pairs (FLP) are an important advance in metal-free catalysis due to their ability to activate a variety of small molecules. Many studies have focused on a very limited sample of Lewis acids and bases. Herein, we disclose an automated exploration algorithm using density functional methods, artificial neural networks (ANNs), and a molecule builder that incentivizes the exploration of favorable FLP space for the activation of methane two mechanisms: deprotonation and hydride abstraction. The exploration algorithm creates FLPs with different Lewis acids (LA), Lewis bases (LB), and their substituents (L/L), which proved successful in quickly converging in the favorable chemical space, suggesting chemically sound structures, and generating thousands of potential candidates for methane activating FLPs. By modeling thousands of reactions, an FLP database of methane activation was created, allowing one to data mine properties, , adduct bond length, highest occupied molecular orbital-lowest-unoccupied molecular orbital (HOMO-LUMO) gap, global electrophilicity index, favored Lewis acids/bases/substituents, and substituent steric volume. These properties not only successfully narrow the FLP chemical space but also provide meaningful insight into the chemical nature of competent methane activators. The machine learning discovery strategy disclosed here is general enough to be applicable to many chemical optimization tasks. This study also investigates the efficacy of a Machine-Learned Force Field (MLFF) in predicting the formation energies of Frustrated Lewis Pairs (FLPs). Our model, exhibiting a test error of ±10 kcal/mol, highlighted impressive computational efficiency by enabling the calculation of all possible FLP permutations within our chemical space. The MLFF demonstrated proficiency in predicting energies, providing a significant acceleration compared to quantum mechanics methods. However, challenges emerged in accurately capturing forces, necessitating recourse to classical force fields for reliable structure relaxation. The present study sheds light on the MLFF's potential as a tool for rapid energy predictions, emphasizing the need for further refinement to enhance its accuracy, particularly in force predictions, to expand its utility in chemical simulations.
PubMed: 38941286
DOI: 10.1021/acs.jctc.4c00354 -
MSystems Jun 2024We use metagenome-assembled genomes (MAGs) to understand single-carbon (C1) compound-cycling-particularly methane-cycling-microorganisms in montane riparian floodplain...
Diverse and unconventional methanogens, methanotrophs, and methylotrophs in metagenome-assembled genomes from subsurface sediments of the Slate River floodplain, Crested Butte, CO, USA.
We use metagenome-assembled genomes (MAGs) to understand single-carbon (C1) compound-cycling-particularly methane-cycling-microorganisms in montane riparian floodplain sediments. We generated 1,233 MAGs (>50% completeness and <10% contamination) from 50- to 150-cm depth below the sediment surface capturing the transition between oxic, unsaturated sediments and anoxic, saturated sediments in the Slate River (SR) floodplain (Crested Butte, CO, USA). We recovered genomes of putative methanogens, methanotrophs, and methylotrophs ( = 57). Methanogens, found only in deep, anoxic depths at SR, originate from three different clades (, , and ), each with a different methanogenesis pathway; putative methanotrophic MAGs originate from within the Archaea ( Methanoperedens) in anoxic depths and uncultured bacteria (. Binatia) in oxic depths. Genomes for canonical aerobic methanotrophs were not recovered. Methanoperedens were exceptionally abundant (~1,400× coverage, >50% abundance in the MAG library) in one sample that also contained aceticlastic methanogens, indicating a potential C1/methane-cycling hotspot. . Methylomirabilis MAGs from SR encode pathways for methylotrophy but do not harbor methane monooxygenase or nitrogen reduction genes. Comparative genomic analysis supports that one clade within the . Methylomirabilis genus is not methanotrophic. The genetic potential for methylotrophy was widespread, with over 10% and 19% of SR MAGs encoding a methanol dehydrogenase or substrate-specific methyltransferase, respectively. MAGs from uncultured archaea in the . Gimiplasmatales (UBA10834) contain pathways that may allow for anaerobic methylotrophic acetogenesis. Overall, MAGs from SR floodplain sediments reveal a potential for methane production and consumption in the system and a robust potential for methylotrophy.IMPORTANCEThe cycling of carbon by microorganisms in subsurface environments is of particular relevance in the face of global climate change. Riparian floodplain sediments contain high organic carbon that can be degraded into C1 compounds such as methane, methanol, and methylamines, the fate of which depends on the microbial metabolisms present as well as the hydrological conditions and availability of oxygen. In the present study, we generated over 1,000 MAGs from subsurface sediments from a montane river floodplain and recovered genomes for microorganisms that are capable of producing and consuming methane and other C1 compounds, highlighting a robust potential for C1 cycling in subsurface sediments both with and without oxygen. Archaea from the . Methanoperedens genus were exceptionally abundant in one sample, indicating a potential C1/methane-cycling hotspot in the Slate River floodplain system.
PubMed: 38940520
DOI: 10.1128/msystems.00314-24 -
Environmental Technology Jun 2024Covered anaerobic lagoons (CALs) are Latin America's main livestock waste treatment systems. Mexico has 680 CALs that present low biogas yields (0.05 m m digester d) and...
Covered anaerobic lagoons (CALs) are Latin America's main livestock waste treatment systems. Mexico has 680 CALs that present low biogas yields (0.05 m m digester d) and low COD removal rates (< 60%). This work focused on diagnosing CAL´s low performance in dairy farms by determining and analyzing operational parameters. Seven CALs located in the main dairy basin of Mexico were analyzed. The sampling areas for each CAL were the supernatant, the active zone, settled sludge, and digester inlet and outlet. The variation of the process parameter values corroborated that CALs appeared stratified and not working as expected. The sludge zone, comprising 50-58% of total solids content and 1-15% of total CALs volume, showed an elemental compounds content suitable for organic fertilizer (340, 48, and 5 kg t of C, N, and S, respectively). However, this zone contained, at least, 85% of the slowly hydrolysable material; the methanogenic potential was less than 87 mL CH g VS, and the C/N ratio ranged from 4.9 to 17, outside of the optimal range. The biogas produced did not exceed 60% of methane content and more than 3000 ppm of HS. The sludge zone significantly influences the lagoon's dynamics since it is a nutrient sink. Furthermore, the lack of agitation is the leading cause for the low energy yield and the low removal of organic matter rate. This work provides valuable information to address the operational problems within the CALs improving our understanding that shall allow proposing reactivation alternatives.
PubMed: 38940278
DOI: 10.1080/09593330.2024.2368688 -
The Journal of Physical Chemistry. A Jun 2024Metal oxide clusters with atomic oxygen radical anions are important model systems to study the mechanisms of activating and transforming very stable alkane molecules...
Metal oxide clusters with atomic oxygen radical anions are important model systems to study the mechanisms of activating and transforming very stable alkane molecules under ambient conditions. It is extremely challenging to characterize the activation and conversion of methane, the most stable alkane molecule, by metal oxide cluster anions due to the low reactivity of the anionic species. In this study, using a ship-lock type reactor that could be run at relatively high pressure conditions to provide a high number of collisions in ion-molecule reactions, the rate constants of the reactions between (MoO)O ( = 1-21) cluster anions and the light alkanes (C-C) were measured under thermal collision conditions. The relationships among the reaction rates of different alkanes were obtained to establish a model to predict the low rate constants with methane from the high rate constants with C-C alkanes. The model was tested by using available experimental results in literature. This study provides a new method to estimate the relatively low reactivity of atomic oxygen radical anions with methane on metal oxide clusters.
PubMed: 38937133
DOI: 10.1021/acs.jpca.4c01163 -
Waste Management (New York, N.Y.) Jun 2024Passive methane oxidation biosystems (PMOBs) are developed as an innovative and cost-effective solution to reduce methane (CH) emissions from municipal solid waste...
Passive methane oxidation biosystems (PMOBs) are developed as an innovative and cost-effective solution to reduce methane (CH) emissions from municipal solid waste landfills. A PMOB consists of a methane oxidation layer (MOL) and an underlying gas distribution layer (GDL). The length of unrestricted gas migration (LUGM) has been recently proposed as the design criterion for PMOBs where the LUGM is calculated as the horizontal length along the MOL-GDL interface with the volumetric gas content (θ) exceeding the threshold volumetric gas content (θ). This paper examined water and gas migration within three PMOBs with different MOL-GDL interfaces subject to precipitation and evaporation using verified numerical models. The results show that the use of a single-phase flow model underestimates the LUGM values of the PMOB for heavy precipitation events, and a two-phase flow model should be used to calculate both the LUGM and the total gas mass flow rate into the MOL when designing PMOBs. Both zig-zag and trapezoidal MOL-GDL interfaces can redistribute the gas mass flow rate at the MOL-GDL interface, while the trapezoidal MOL-GDL interface slightly outperforms the zig-zag MOL-GDL interface for enhancing the total gas mass flow rate into the MOL when comparing with the planar MOL-GDL interface. The zig-zag and trapezoidal MOL-GDL interfaces allow gas migration in the upper part of each PMOB segment even when the lower part of each PMOB segment was filled with water, and thus have a potential to minimize hotspot formation.
PubMed: 38936305
DOI: 10.1016/j.wasman.2024.06.018 -
Journal of Environmental Management Jun 2024In this paper, a novel methodology and extended hybrid model for the real time control, prediction and reduction of direct emissions of greenhouse gases (GHGs) from...
In this paper, a novel methodology and extended hybrid model for the real time control, prediction and reduction of direct emissions of greenhouse gases (GHGs) from wastewater treatment plants (WWTPs) is proposed to overcome the lack of long-term data availability in several full-scale case studies. A mechanistic model (MCM) and a machine learning (ML) model are combined to real time control, predict the emissions of nitrous oxide (NO) and carbon dioxide (CO) as well as effluent quality (COD - chemical oxygen demand, NH-N - ammonia, NO-N - nitrate) in activated sludge method. For methane (CH), using the MCM model, predictions are performed on the input data (VFA, CODs for aerobic and anaerobic compartments) to the MLM model. Additionally, scenarios were analyzed to assess and reduce the GHGs emissions related to the biological processes. A real WWTP, with a population equivalent (PE) of 125,000, was studied for the validation of the hybrid model. A global sensitivity analysis (GSA) of the MCM and a ML model were implemented to assess GHGs emission mechanisms the biological reactor. Finally, an early warning tool for the prediction of GHGs errors was implemented to assess the accuracy and the reliability of the proposed algorithm. The results could support the wastewater treatment plant operators to evaluate possible mitigation scenarios (MS) that can reduce direct GHG emissions from WWTPs by up to 21%, while maintaining the final quality standard of the treated effluent.
PubMed: 38936025
DOI: 10.1016/j.jenvman.2024.121502