C1 Compounds Research Articles

Oxygen vacancies–elusive but common catalytic key defects for thermal upgrading of CO2 to CH4, CO and CH3OH

Single carbon products (C1 compounds) are simple but important chemicals in the road towards energy transition. Catalytic conversion of CO2 with H2 (desirably renewable) can be performed over reducible oxides supporting transition metals to obtain products such as CH4, CO and MeOH. Oxygen vacancies (O-vacancies), which are inherent defects of reducible metal oxides, play an enormous role in driving the catalytic performance (activity, selectivity, stability) for the desired reactions. Yet, the assessment of O-defects at realistic conditions is often complex. Only few techniques can provide direct evidence for their existence and influence in CO2 activation. Among them, electron paramagnetic spectroscopy (EPR), Raman spectroscopy, scanning probe microscopies (SPM) and environmental transmission electron microscopy (ETEM) are nowadays the most informative. In most cases, however, the measurements require reaction conditions far away from CO2 valorization applications. Although great efforts have been fruitful in explaining and demonstrating the huge importance of O-vacancies in CO2 catalysis, still ambiguous or erroneous interpretations about structure-function correlations involving O-vacancies are found in literature, especially, when information is not properly gathered, e.g., by O 1s ex-situ X-ray photon spectroscopy (XPS). Moreover, despite the recognized importance of O-vacancies for CO2 valorization, critical literature compilations about their effects in thermal processes are scarce. Herein, we attempt to contribute in closing this gap by integrally encompassing representative investigations on the thermo-catalytic production of CH4, CO and MeOH. Particularly, we emphasize in the proper selection of assessment tools (direct/indirect) to unambiguously establish structure-function relationships to design optimized O-defective catalysts for the targeted compounds.

Entropy-Derived Synthesis of the CuPd Sub-1nm Alloy for CO2-to-acetate Electroreduction.

Bimetallic alloys exhibit remarkable properties in catalysis and energy storage, while their precise synthesis at the subnanoscale remains a formidable challenge due to their immiscible nature in thermodynamics. In this study, we engineer an atomically dispersed CuPd alloy with an average size of 1.5 nm loaded on CuO and phosphomolybdic acid (PMA) coassembly subnanosheets (CuO-PMA SNSs). Driven by the high vibrational entropy, Cu atoms could escape from CuO supports and bond with adjacent Pd single atoms, leading to the in situ formation of CuPd alloys. Furthermore, this strategy can also be utilized for synthesizing the ZnPt alloy with an average size of 1 nm, thereby providing a general pathway for the design of immiscible subnanoalloys. The fully exposed Cu-Pd pairs in CuPd subnanoalloys significantly enhance the adsorption and coverage of surface *CO during the electrochemical reduction of CO2, thereby leading to enhanced stability of ethenone intermediates and facilitating the production of C2 compounds. The resulting CuPd subnanoalloy exhibits a remarkable Faradaic efficiency of 46.5 ± 2.1% for CO2-to-acetate electroreduction and achieves a high acetate productivity of 99 ± 2.8 μmol cm-2 at -0.7 V versus RHE.

Tailoring electrochemical CO2 reduction selectivity over CuSn by modulating surface oxidation state with infrared laser treatment

Infrared laser treatment was used to precisely modify the surface structure of CuSn electrodes, effectively fine-tuning the selectivity of reduction products. With increasing laser power, the metallic Cu and Sn surfaces became more oxidized, and the Sn/Cu composition ratio varied with depth and further changed post-EC reaction. The diversity of reduction products, including C1 (CO, CH4, and formate), C2 (C2H4, ethanol, acetate, acetaldehyde, and glycolaldehyde), and C3 (propanol and isopropanol) compounds, shifted towards a more selective production of C1 (CO and formate) products. These tailored behaviors are attributed to variations in interfacial electronic structures, oxidation states, composition ratios, and the interaction between CO2 and the density of states (Cu, O, and Sn) near the Fermi level. The laser treatment method enables precise tuning of electrode surfaces, modulation of reduction products, and enhancement of selectivity. Moreover, this technique presents a novel approach for electrode design in the field of CO2 reduction, offering new avenues for optimizing catalytic performance.

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.

Comparative profiling of volatile compounds in white and brown Hypsizygus marmoreus during fruiting body development and postharvest storage

Hypsizygus marmoreus (HM) is a nutritious edible mushroom with high industrial yield and rapid market development. HM has become increasingly popular among customers due to its abundant bioactive compounds, chewy texture and unique aroma. The volatile organic compound (VOC) fingerprints of white and brown HM varieties during fruiting body growth and postharvest storage were established by HS-SPME-GC-MS and HS-GC-IMS. A total of 46 aroma VOC were identified from fresh mature HM. Based on odor activity, 12 VOC have been defined as the characteristic VOC, of which five are prevalent in aquatic products and are the main contributors to HM's unique seafood flavor. The brown variety exhibited higher diversity and abundance of VOC. C8 compounds in brown HM was 5.722 mg/kg, which was 1.99 times higher than that in white HM (2.872 mg/kg). Aromatic compounds such as aldehydes, alcohols, ketones, and terpenes are also more abundant in brown varieties (6.35 mg/kg), which was 1.864 times that of white varieties (3.406 mg/kg). C8 compounds increasingly accumulated in white HM during development, especially intensifying before maturing. After stored at 4 ℃ up to 45 d, the VOC profiles of HM remained less changed despite slight decrease, which helps explain their long shelf-life. The findings of this study shed light on elucidating the VOC that contribute to the unique aroma of HM, as well as tracking the odor changes during industrial production and shelf-life.

Multi-tracer evidence of hydrology and primary production controls on dissolved organic matter composition and stability in the semi-arid aquatic continuum

Autochthonous dissolved organic matter (Auto-DOM) produced by a biological carbon pump using dissolved inorganic carbon (DIC) from carbonate weathering plays an important role in carbon cycling within inland waters. However, little is known regarding how environmental conditions impact the composition and fate of organic matter, especially in surface waters of the semi-arid Loess Plateau, which is enriched in DIC by significant carbonate weathering. To obtain novel insight, we combined hydrochemistry, isotopic composition (δ2H, δ18O, and δ13CDIC), Rayleigh fractionation model, optical spectroscopy (absorbance and fluorescence), and Fourier transform ion cyclotron resonance mass spectrometry measurements to elucidate how primary production and hydrology impact the composition of DOM and the stability of the resulting Auto-DOM throughout the river–reservoir–wetland aquatic continuum of the Bahe River in the carbonate-mineral-rich semi-arid Loess Plateau where carbonate weathering is significant. The Rayleigh fractionation model results indicated that watershed DIC is primarily consumed through aquatic primary production rather than CO2 degassing. Further investigation revealed that primary production and evaporation co-occurred in this watershed. With the enrichment of the stable water isotope δ2H, the relative abundances of the allochthonous compounds decreased and the relative abundances of the autochthonous substances increased, suggesting that the terrestrial signal of riverine DOM decreased while autochthonous production increased along the flow pathway. In addition, associations between optical and molecular characteristics among DOM samples from different water bodies revealed that the stability ratio (Fmax(C2/(C2 + C4))) of Auto-DOM to the ratio of carboxylic-rich alicyclic molecules showed a consistent trend, suggesting that phytoplankton-derived and biomineralized C2 compounds are potentially recalcitrant DOM in inland waters. We conclude that hydrology and primary production affect the source, composition, and, potentially, the stability of DOM in DIC-enriched surface waters of the semi-arid Loess Plateau, which may lead to a more humic-like DOM composition in inland water and export this lower bioavailability DOC to the ocean in the long term.

Analysis and Formation of Polycyclic Aromatic Hydrocarbons in Canned Minced Chicken and Pork during Processing.

Polycyclic aromatic hydrocarbons (PAHs) represent important toxic compounds formed in meat products during processing. This study aims to analyze 22 PAHs by QuEChERS coupled with GC-MS/MS in canned minced chicken and pork during processing. After marinating raw minced chicken and pork separately with a standard flavoring formula used for canning meat in Taiwan, they were subjected to different processing conditions including stir-frying, degassing and sterilizing at 115 °C/60 min (low-temperature-long-time, LTLT) and 125 °C/25 min (high-temperature-short-time, HTST). The quantitation of PAHs in these meat products revealed the formation of only three PAHs including acenaphthylene (AcPy), acenaphthene (AcP) and pyrene (Pyr) in canned minced chicken and pork during processing with no significant difference in total PAHs between the meat types. Analysis of PAH precursors showed the presence of benzaldehyde at the highest level, followed by 2-cyclohexene-1-one and trans,trans-2,4-decadienal in canned minced chicken and pork, suggesting PAH formation through the reaction of benzaldehyde with linoleic acid degradation products and of 2-cyclohexene-1-one with C4 compounds through the Diels-Alder reaction, as well as the reaction of trans,trans-2,4-decadienal with 2-butene. Monounsaturated and polyunsaturated fatty acids were present in the largest proportion in LTLT-sterilized chicken/pork, followed by HTST-sterilized chicken/pork and raw chicken/pork, and their levels did not show a high impact on PAH formation, probably due to an insufficient heating temperature and length of time. A two-factorial analysis suggested that PAH formation was not significantly affected by the sterilization condition or meat type. Principal component analysis corroborated the observed results implying the formation of PAHs in canned minced chicken/pork under different processing conditions with an insignificant difference (p > 0.05) between them, with the individual PAH content following the order of Pyr > AcPy > AcP.

Integrated Metabolomics and Proteomics Analysis Provides Insights into the Formation of Volatile Compounds in Three Different Polyembryonic Mango Cultivars.

Understanding volatile compound formation is critical for enhancing the flavor quality of mangoes. Integrated untargeted metabolomics and proteomics were employed to explore volatile compound formation in three different polyembryonic mango cultivars ("Ah Ping," "Rosa," and "Rosigold"). A total of 87 volatile compounds were identified using SPME-GC-MS. Untargeted metabolomics and proteomics resulted in identification of 508 metabolites and 4481 proteins, respectively. Integrative analysis revealed that the volatile compound formation was influenced by fatty acids, amino acids, pentose, and hexose, as well as terpenoid metabolisms. Specifically, upward expression of core enzymes in lipoxygenanse pathway was responsible for the higher levels of some C6 and C9 volatile compounds in "Ah Ping." The differential expression of key enzymes in fatty acid degradation facilitates the varied contents of straight-chain volatile compounds. The upregulation of glutamate decarboxylase and branched-chain amino acid aminotransferase upstream of butanoate metabolism led to the highest levels of butyl esters in "Ah Ping." Furthermore, the different levels of volatile furan and pyran compounds might be attributed to differential expression of critical enzymes in pentose and hexose metabolism. These findings established a metabolic and proteomic map unraveling the biosynthesis of specific volatile compounds and provided insights into understanding the characteristic flavor of mango.

Regulatory mechanism of methyl jasmonate and methyl dihydrojasmonate in enhancing aroma in 'Cabernet Gernischt' via the lipoxygenase pathway.

The present study explored the effects of pre-harvest methyl jasmonates spraying on the volatiles of 'Cabernet Gernischt' grapes through the lipoxygenase pathway. Headspace solid-phase microextraction combined with gas chromatography-mass spectrometry and an enzyme-linked immunosorbent assay were utilized to analyze volatile metabolites and key enzyme activities following methyl jasmonates application. Total RNA extraction and cDNA library construction were followed by transcriptome sequencing. The application of 0.1 mmol L-1 methyl jasmonate and 5 mmol L-1 methyl dihydrojasmonate significantly increased the levels of C6 compounds in 'Cabernet Gernischt' berries, and also enhanced the utilization of unsaturated fatty acids as precursors in the lipoxygenase-hydroperoxides lyase pathway. The up-regulated expression of VvADH1, VvADH2, VvHPL and VvLOX2S genes led to modulations in enzyme activity, thereby enhancing the berries's aromatic profile. There was a significant correlation between linoleic and linolenic acids (i.e. the precursors of the lipoxygenase pathway) and the activities and metabolites of key enzymes. The optimal concentration of methyl jasmonates treatment favorably influences the accumulation of green leaf volatiles in 'Cabernet Gernischt' grape. © 2024 Society of Chemical Industry.

Novel Methods for the Formation of Free Carbyne Radicals in Solution.

Carbyne free radicals RC⋮ (RC) are usually associated with high-energy processes, thus research on their preparation, chemical reactivity, and prevalence under mild conditions is scarce. Recently, it was reported that metallo-complexes containing CR ligands may undergo spontaneous degradation in aqueous solutions to produce free RC radicals. These highly reactive species may react with each other to form the corresponding alkyne and other products. The reaction of 1,1,1 halo-carbo-hydrates with Cr(II) ions also forms RC radicals under mild conditions. Herein, we report two additional synthetic routes that produce free RC radicals under mild conditions. First, the reaction between metallic zinc and acetic anhydride produces 2-butyne and several other C2, C3, and C4 compounds. Isotopic-labeling experiments indicate that the formation of 2-butyne results from an inter-molecular reaction in which two RC moieties from two acetic anhydride molecules combine in solution. In addition, the degradation of the tri-molybdenum complex [Mo3(H3CC≡CCH3)(OAc)(H2O)2Br7], in which a 2-butyne ligand is coordinated to the Mo3 framework in a μ3-η2 (⊥) binding mode in aqueous solution produces several C2, C3, C4 and C5 molecules. This indicates the formation of free CH3C radicals by a homolytic cleavage of the carbon-carbon triple bond.

Redesigning glycolaldehyde synthase for the synthesis of biorefinery feedstock D-xylulose from C1 compounds.

Global climate deterioration intensifies the demand for exploiting efficient CO2 utilization approaches. Converting CO2 to biorefinery feedstock affords an alternative strategy for third-generation biorefineries. However, upcycling CO2 into complex chiral carbohydrates remains a major challenge. Previous attempts at sugar synthesis from CO2 either produce mixtures with poor stereoselectivity or require ATP as a cofactor. Here, by redesigning glycolaldehyde synthase, the authors constructed a synthetic pathway for biorefinery feedstock D-xylulose from CO2 that does not require ATP as a cofactor. The artificial D-xylulose pathway only requires a three-step enzyme cascade reaction to achieve the stereoselective synthesis of D-xylulose at a concentration of 1.2gL-1. Our research opens up an alternative route toward future production of chemicals and fuels from CO2.

Stable Platform for Mevalonate Bioproduction from CO2.

Stable production of value-added products using a microbial chassis is pivotal for determining the industrial suitability of the engineered biocatalyst. Microbial cells often lose the multicopy expression plasmids during long-term cultivations. Owing to the advantages related to titers, yields, and productivities when using a multicopy expression system compared with genomic integrations, plasmid stability is essential for industrially relevant biobased processes. Cupriavidus necator H16, a facultative chemolithoautotrophic bacterium, has been successfully engineered to convert inorganic carbon obtained from CO2 fixation into value-added products. The application of this unique capability in the biotech industry has been hindered by C. necator H16 inability to stably maintain multicopy plasmids. In this study, we designed and tested plasmid addiction systems based on the complementation of essential genes. Among these, implementation of a plasmid addiction tool based on the complementation of mutants lacking RubisCO, which is essential for CO2 fixation, successfully stabilized a multicopy plasmid. Expressing the mevalonate pathway operon (MvaES) using this addiction system resulted in the production of ∼10 g/L mevalonate with carbon yields of ∼25%. The mevalonate titers and yields obtained here using CO2 are the highest achieved to date for the production of C6 compounds from C1 feedstocks.

The Influence of Climatic Conditions Associated with Altitude on the Volatile Composition of Cabernet Sauvignon Wines from Argentina, Spain and Portugal

In addition to winemaking techniques, wine’s quality and typicity are linked to the place where the grapes are grown. Climate, soil and the cultivar are major drivers of the terroir’s expression. Moreover, climate change is affecting the distribution of grapevine varieties in different wine-growing regions because changes in climatic conditions over the past years is affecting grape production. This study investigated the influence of some terroir parameters on the volatile composition of Cabernet Sauvignon wines. Eight wines from vineyards sited in Argentina, Spain and Portugal with altitudes between 2400 and 77 m above sea level (a.s.l.) with different soils and climatic conditions were selected. The results suggested that the vineyard’s place significantly modified the volatile composition of Cabernet Sauvignon wines because all chemical groups of volatiles quantified were affected. Volatile acids, C6 compounds, aldehydes, esters and terpenes showed the highest concentrations at 2400 m a.s.l., where the highest thermal amplitude was observed. In Portugal, where the vineyard studies were sited at lower altitudes (77 m a.s.l.) and under warm climatic conditions, high concentrations of alcohols and lactones were observed. Alcohols also showed high concentrations in wines from vineyards sited at 413 and 155 m a.s.l. (Spain). Principal component analysis showed the positive correlation of Cabernet Sauvignon wines located at higher altitudes with terpenes. On the contrary, wines from grapes grown at lower altitude conditions exhibited a correlation with alcohols and lactones.

Influence of the La/Ce ratio on La-Ce oxides promoted by Sr in the methane oxidative coupling reaction

The high methane availability and its significant role as a greenhouse gas have led the scientific community to pursue methods for its use. This paper proposes the usage of the oxidative coupling of methane (OCM) as a promising path to transform methane directly into value-added hydrocarbons, mostly ethylene, which serves as a crucial compound in the petrochemical sector. An efficient OCM catalyst should contain substantial basicity and oxygen vacancies for providing surface electrophilic oxygen species, such as superoxides and peroxides, instrumental for boosting selectivity towards C2 products. Mixed lanthanum-cerium oxide (La-Ce) catalysts have emerged as strong candidates in OCM due to their high thermal stability, oxygen mobility, and high alkalinity. In this study, they were prepared through a surfactant-assisted hydrothermal method with different La/Ce ratios for fine-tuning their basic properties and promoting oxygen mobility on the surface of the catalysts. Samples followed a volcano-shaped relationship between C2 yield and La content, with optimal performance at a La/Ce molar ratio of 2.1, attributed to the interplay between the high amount of basic sites and oxygen vacancies, increasing the presence of superoxide species over lattice oxygen. Moreover, the Sr-promoted catalyst showed high density of strong basic sites while preserving the reactive oxygen species, achieving 20 % CH4 conversion, with 57 % C2 compounds selectivity at 750 °C and GHSV of 18.000 mL.gcat−1.h−1.

Bioactive prenylated c6–c3 derivatives from the roots of Illicium brevistylum

Three new prenylated C6–C3 compounds (1–3), together with two known prenylated C6–C3 compounds (4–5) and one known C6–C3 derivative (6), were isolated from the roots of Illicium brevistylum A. C. Smith. The structures of 1–3 were elucidated by spectroscopic methods including 1D and 2D NMR, HRESIMS, CD experiments and ECD calculations. The structure of illibrefunone A (1) was confirmed by single-crystal X-ray diffraction analysis. All compounds were evaluated in terms of their anti-inflammatory potential on nitric oxide (NO) generation in lipopolysaccharide-stimulated murine RAW264.7 macrophages and murine BV2 microglial cells, antiviral activity against Coxsackievirus B3 (CVB3) and influenza virus A/Hanfang/359/95 (H3N2). Compounds 3 and 4 exhibited potent inhibitory effects on the production of NO in RAW 264.7 cells with IC50 values of 20.57 and 12.87 μM respectively, which were greater than those of dexamethasone (positive control). Compounds 1 and 4–6 exhibited weak activity against Coxsackievirus B3, with IC50 values ranging from 25.87 to 33.33 μM.

Mannitol as a Growth Substrate for Facultative Methylotroph Methylobrevis pamukkalensis PK2.

Biochemistry of carbon assimilation in aerobic methylotrophs growing on reduced C1 compounds has been intensively studied due to the vital role of these microorganisms in nature. The biochemical pathways of carbon assimilation in methylotrophs growing on multi-carbon substrates are insufficiently explored. Here we elucidated the metabolic route of mannitol assimilation in the alphaproteobacterial facultative methylotroph Methylobrevis pamukkalensis PK2. Two key enzymes of mannitol metabolism, mannitol-2-dehydrogenase (MTD) and fructokinase (FruK), were obtained as His-tagged proteins by cloning and expression of mtd and fruK genes in Escherichia coli and characterized. Genomic analysis revealed that further transformation of fructose-6-phosphate proceeds via the Entner-Doudoroff pathway. During growth on mannitol + methanol mixture, the strain PK2 consumed both substrates simultaneously demonstrating independence of C1 and C6 metabolic pathways. Genome screening showed that genes for mannitol utilization enzymes are present in other alphaproteobacterial methylotrophs predominantly capable of living in association with plants. The capability to utilize a variety of carbohydrates (sorbitol, glucose, fructose, arabinose and xylose) suggests a broad adaptability of the strain PK2 to live in environments where availability of carbon substrate dynamically changes.

Electrochemical Synthesis of Isoquinoline Sulfone Compounds and Study of their Inhibition of Acetolactate Synthase Enzyme Activity

AbstractBoth of sulfone compounds and isoqunoline derivatives are important compounds. In this paper, Isoquinoline C1 and C3 Sulfone compounds have been synthesized by electrochemical means using isoquinoline N‐Oxides and some sodium benzenesulfinate as reactants, inexpensive and easily available sodium iodide as electrolytes, and a mixture of acetonitrile, water and acetic acid as reaction solvents. By using the method, a series of isoquinoline sulfone compounds have been synthesized in high yields. The reaction does not need oxidants and catalysts, and the reaction conditions are mild, environmentally friendly, efficient and suitable. In addition, we also carried out ALS enzyme inhibition experiments on the synthesized isoquinoline sulfone compounds, six of the isoquinoline sulfone compounds synthesized herein were found to inhibit ALS enzyme at a high rate, four of them inhibited ALS enzyme at a rate comparable to that of the commercialized herbicides Halosulfuron and Broadstrike, and the other two compounds also inhibited ALS enzyme at a rate higher than that of Halosulfuron and Broadstrike. Therefore, it is possible to find lead compounds with good herbicidal activity potential from these 6 compounds.

Innovative study and analysis on MAX phase (Ti3AlC2) A-layer atom solid solution with potential A site doped elements

“Ti3AlC2, a member of the Mn+1AXn ceramic phases, demonstrates outstanding oxidation resistance, high specific stiffness, excellent corrosion resistance, and thermal conductivity. This research delves into the A-site solid-solution treatment of Ti3AlC2, with a specific focus on 18 elements derived from the main and subgroups of the periodic table. These elements, such as Pb, As, Si, S, Sb, P, Ir, Ge, Sn, Fe, Au, Co, Cu, Ni, In, Zn, and Ga, are all considered potential candidates for the A site.The enthalpies of formation of the Ti3(Al0.5A0.5)C2 compounds were determined to be negative, suggesting that these compounds can be synthesized through exothermic reactions. This finding highlights the improved formation capability when a specific A atom substitutes for an Al atom. Notably, Ti3(Al0.5Ir0.5)C2 exhibited the highest formation efficiency, as evidenced by its significantly higher absolute value of heat of formation compared to the other compounds.The electronic structures of all the compounds indicated that the energy bands became broader and showed improved electrical conductivity when the active element replaced the Al atomic position. In particular, the substitution of Al atomic positions in Ti3AlC2 with main group elements such as Si, Ge, and As, as well as B group elements such as Fe, Co, and Ir, leads to the formation of stronger bonds between Ti atoms, thereby creating a more stable structure.The substitution of Al atoms with Si, Ge, As, Fe, Co, and Ir atoms in Ti3(Al0.5A0.5)C2 was found to improve the resistance of the material to compressive deformation. This substitution also resulted in a decrease in the hardness of the Ti3AlC2 ceramic material but enhanced its ductility.

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 (n = 57). Methanogens, found only in deep, anoxic depths at SR, originate from three different clades (Methanoregulaceae, Methanotrichaceae, and Methanomassiliicoccales), each with a different methanogenesis pathway; putative methanotrophic MAGs originate from within the Archaea (Candidatus Methanoperedens) in anoxic depths and uncultured bacteria (Ca. Binatia) in oxic depths. Genomes for canonical aerobic methanotrophs were not recovered. Ca. 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. Ca. 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 Ca. 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 Thermoplasmata archaea in the Ca. 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 Ca. Methanoperedens genus were exceptionally abundant in one sample, indicating a potential C1/methane-cycling hotspot in the Slate River floodplain system.

Improving the roughness of copper working electrode through electroless deposition for carbon dioxide reduction reaction

Electrocatalytic CO2 conversion into usable fuels (CO, CH4, C2H4, and HCOOH) is a promising approach to mitigate the greenhouse effect and the energy deficit. Herein, we employ the wet etching process to significantly enhance the surface roughness of the copper foil, followed by deposition of Cu particles on the surface-etched copper foil (Cu NPs/Cu foil) for electrochemical CO2 reduction. FESEM and AFM results confirms the morphology and roughness changes. Introducing glycine to the electrolyte increase the Faraday efficiency (FE) of the resulting products. Upon adding 5 × 10−5 mM glycine significantly improves the FEs 10.1 % CO, 8.7 % CH4, 11.7 % C2H4, and 44.5 % HCOOH, with 75.0 % as C1 and C2 compounds. Concurrently, hydrogen production decreases to 20.2 % at a potential of –1.4 V utilizing roughened Cu NPs/Cu foil as a catalyst. These results shed light on the factors contributing to increased hydrocarbons and formic acid production with enhanced surface roughness of Cu foil.