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1.
J Am Chem Soc ; 146(17): 11887-11896, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38529556

RESUMO

Monitoring the spontaneous reconstruction of the surface of metal oxides under electrocatalytic reaction conditions is critical to identifying the active sites and establishing structure-activity relationships. Here, we report on a self-terminated surface reconstruction of Ruddlesden-Popper lanthanum nickel oxide (La2NiO4+δ) that occurs spontaneously during reaction with alkaline electrolyte species. Using a combination of high-resolution scanning transmission electron microscopy (HR-STEM), surface-sensitive X-ray photoelectron spectroscopy (XPS), and soft X-ray absorption spectroscopy (sXAS), as well as electrochemical techniques, we identify the structure of the reconstructed surface layer as an amorphous (oxy)hydroxide phase that features abundant under-coordinated nickel sites. No further amorphization of the crystalline oxide lattice (beyond the ∼2 nm thick layer formed) was observed during oxygen evolution reaction (OER) cycling experiments. Notably, the formation of the reconstructed surface layer increases the material's oxygen evolution reaction (OER) activity by a factor of 45 when compared to that of the pristine crystalline surface. In contrast, a related perovskite phase, i.e., LaNiO3, did not show noticeable surface reconstruction, and also no increase in its OER activity was observed. This work provides detailed insight into a surface reconstruction behavior dictated by the crystal structure of the parent oxide and highlights the importance of surface dynamics under reaction conditions.

2.
Clin Exp Allergy ; 54(3): 195-206, 2024 03.
Artigo em Inglês | MEDLINE | ID: mdl-38234127

RESUMO

BACKGROUND: IgE antibodies to cross-reactive carbohydrate determinants (CCD) are usually clinically irrelevant but they can be a cause of false positive outcomes of allergen-specific IgE tests in vitro. Their prevalence and levels have been so far cross-sectionally examined among adult allergic patients and much less is known about their origins and relevance in childhood. METHODS: We examined CCD with a cross-sectional approach in 1263 Italian pollen allergic children (Panallergen in Paediatrics, PAN-PED), as well as with a longitudinal approach in 612 German children (Multicenter Allergy Study, MAS), whose cutaneous and IgE sensitization profile to a broad panel of allergen extracts and molecules was already known. The presence and levels of IgE to CCD were examined in the sera of both cohorts using bromelain (MUXF3) as reagent and a novel chemiluminescence detection system, operating in a solid phase of fluorescently labelled and streptavidin-coated paramagnetic microparticles (NOVEOS, HYCOR, USA). RESULTS: IgE to CCD was found in 22% of the Italian pollen allergic children, mainly in association with an IgE response to grass pollen. Children with IgE to CCD had higher total IgE levels and were sensitized to more allergenic molecules of Phleum pratense than those with no IgE to CCD. Among participants of the German MAS birth cohort study, IgE to CCD emerged early in life (even at pre-school age), with IgE sensitization to group 1 and 4 allergen molecules of grasses, and almost invariably persisted over the full observation period. CONCLUSIONS: Our results contribute to dissect the immunological origins, onset, evolution and risk factors of CCD-sIgE response in childhood, and raise the hypothesis that group 1 and/or 4 allergen molecules of grass pollen are major inducers of these antibodies through an antigen-specific, T-B cell cognate interaction.


Assuntos
Hipersensibilidade , Imunoglobulina E , Adulto , Humanos , Criança , Pré-Escolar , Estudos de Coortes , Prevalência , Alérgenos , Carboidratos , Fatores de Risco , Reações Cruzadas
3.
Glob Chang Biol ; 30(4): e17290, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38651789

RESUMO

Soil organic nitrogen (N) mineralization not only supports ecosystem productivity but also weakens carbon and N accumulation in soils. Recalcitrant (mainly mineral-associated organic matter) and labile (mainly particulate organic matter) organic materials differ dramatically in nature. Yet, the patterns and drivers of recalcitrant (MNrec) and labile (MNlab) organic N mineralization rates and their consequences on ecosystem N retention are still unclear. By collecting MNrec (299 observations) and MNlab (299 observations) from 57 15N tracing studies, we found that soil pH and total N were the master factors controlling MNrec and MNlab, respectively. This was consistent with the significantly higher rates of MNrec in alkaline soils and of MNlab in natural ecosystems. Interestingly, our analysis revealed that MNrec directly stimulated microbial N immobilization and plant N uptake, while MNlab stimulated the soil gross autotrophic nitrification which discouraged ammonium immobilization and accelerated nitrate production. We also noted that MNrec was more efficient at lower precipitation and higher temperatures due to increased soil pH. In contrast, MNlab was more efficient at higher precipitation and lower temperatures due to increased soil total N. Overall, we suggest that increasing MNrec may lead to a conservative N cycle, improving the ecosystem services and functions, while increasing MNlab may stimulate the potential risk of soil N loss.


Assuntos
Nitrogênio , Microbiologia do Solo , Solo , Solo/química , Nitrogênio/metabolismo , Plantas/metabolismo , Concentração de Íons de Hidrogênio , Nitrificação , Ciclo do Nitrogênio
4.
Chemphyschem ; : e202400270, 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38837531

RESUMO

NMR spectroscopy studies using parahydrogen-induced polarization have previously established the existence of the pairwise hydrogen addition route in the hydrogenation of unsaturated hydrocarbons over heterogeneous catalysts, including those based on rhodium (Rh0). This pathway requires the incorporation of both hydrogen atoms from one hydrogen molecule to the same product molecule. However, the underlying mechanism for such pairwise hydrogen addition must be better understood. The involvement of carbon, either in the form of carbonaceous deposits on the surface of a catalyst or as a metal carbide phase, is known to modify catalytic properties significantly and thus could also affect the pairwise hydrogen addition route. Here, we explored carbon's role by studying the hydrogenation of propene and propyne with parahydrogen on a Rh2C catalyst and comparing the results with those for a Rh0/C catalyst obtained from Rh2C via H2 pretreatment. While the catalysts Rh2C and Rh0/C differ notably in the rate of conversion of parahydrogen to normal hydrogen as well as in terms of hydrogenation activity, our findings suggest that the carbide phase does not play a significant role in the pairwise H2 addition route on rhodium catalysts.

5.
BJU Int ; 133(6): 680-689, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38469686

RESUMO

BACKGROUND: Older men (aged ≥75 years) with high risk, non-metastatic prostate cancer (PCa) are increasingly treated with curative therapy (surgery or radiotherapy). However, it is unclear if curative therapy prolongs life and improves health-related quality of life (HRQoL) in this age group compared to conservative therapy, which has evolved considerably during the last decade. STUDY DESIGN: The Scandinavian Prostate Cancer Group (SPCG) 19/Norwegian Get-Randomized Research Group-Prostate (GRand-P) is a randomised, two-armed, controlled, multicentre, phase III trial carried out at study centres in Norway, Denmark, Finland, and Sweden. ENDPOINTS: The primary endpoints are overall survival and HRQoL (burden of disease scale, European Organisation for the Research and Treatment of Cancer [EORTC] Elderly Cancer patients). Secondary endpoints are PCa-specific survival, metastasis-free survival, role-functioning scale (EORTC quality of life questionnaire 30-item core), urinary irritative/obstructive scale (26-item Expanded Prostate Cancer Index Composite [EPIC-26]), bowel scale (EPIC-26), intervention-free survival, PCa morbidity, use of secondary and tertiary systemic therapies, mean quality-adjusted life-years (QALYs), and mean total healthcare costs. PATIENTS AND METHODS: A total of 980 men (aged ≥75 years) with non-metastatic, high-risk PCa will initially be screened with Geriatric 8 (G8) health status screening tool and Mini-COG© brief cognitive test. Participants identified by G8 as 'fit' or 'frail' will be randomised (ratio 1:1) to either immediate curative therapy (radiotherapy or prostatectomy) or conservative therapy (endocrine therapy or observation). Participants who are unable or unwilling to participate in randomisation will be enrolled in a separate observation group. Randomised patients will be followed for 10 years. TRIAL REGISTRATION: Ethics approval has been granted in Norway (457593), Denmark (H-22051998), Finland (R23043) and Sweden (Dnr 2023-05296-01). The trial is registered on Clinicaltrials.org (NCT05448547).


Assuntos
Tratamento Conservador , Neoplasias da Próstata , Qualidade de Vida , Idoso , Idoso de 80 Anos ou mais , Humanos , Masculino , Ensaios Clínicos Fase III como Assunto , Prostatectomia , Neoplasias da Próstata/terapia , Neoplasias da Próstata/patologia , Ensaios Clínicos Controlados Aleatórios como Assunto , Estudos Multicêntricos como Assunto
6.
Environ Sci Technol ; 58(14): 6215-6225, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38546713

RESUMO

Globally, agricultural soils account for approximately one-third of anthropogenic emissions of the potent greenhouse gas and stratospheric ozone-depleting substance nitrous oxide (N2O). Emissions of N2O from agricultural soils are affected by a number of global change factors, such as elevated air temperatures and elevated atmospheric carbon dioxide (CO2). Yet, a mechanistic understanding of how these climatic factors affect N2O emissions in agricultural soils remains largely unresolved. Here, we investigate the soil N2O emission pathway using a 15N tracing approach in a nine-year field experiment using a combined temperature and free air carbon dioxide enrichment (T-FACE). We show that the effect of CO2 enrichment completely counteracts warming-induced stimulation of both nitrification- and denitrification-derived N2O emissions. The elevated CO2 induced decrease in pH and labile organic nitrogen (N) masked the stimulation of organic carbon and N by warming. Unexpectedly, both elevated CO2 and warming had little effect on the abundances of the nitrifying and denitrifying genes. Overall, our study confirms the importance of multifactorial experiments to understand N2O emission pathways from agricultural soils under climate change. This better understanding is a prerequisite for more accurate models and the development of effective options to combat climate change.


Assuntos
Gases de Efeito Estufa , Solo , Solo/química , Dióxido de Carbono/análise , Temperatura , Agricultura , Óxido Nitroso/análise
7.
Environ Sci Technol ; 58(6): 2786-2797, 2024 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-38311839

RESUMO

Understanding the underlying mechanisms of soil microbial nitrogen (N) utilization under land use change is critical to evaluating soil N availability or limitation and its environmental consequences. A combination of soil gross N production and ecoenzymatic stoichiometry provides a promising avenue for nutrient limitation assessment in soil microbial metabolism. Gross N production via 15N tracing and ecoenzymatic stoichiometry through the vector and threshold element ratio (Vector-TER) model were quantified to evaluate the soil microbial N limitation in response to land use changes. We used tropical soil samples from a natural forest ecosystem and three managed ecosystems (paddy, rubber, and eucalyptus sites). Soil extracellular enzyme activities were significantly lower in managed ecosystems than in a natural forest. The Vector-TER model results indicated microbial carbon (C) and N limitations in the natural forest soil, and land use change from the natural forest to managed ecosystems increased the soil microbial N limitation. The soil microbial N limitation was positively related to gross N mineralization (GNM) and nitrification (GN) rates. The decrease in microbial biomass C and N as well as hydrolyzable ammonium N in managed ecosystems led to the decrease in N-acquiring enzymes, inhibiting GNM and GN rates and ultimately increasing the microbial N limitation. Soil GNM was also positively correlated with leucine aminopeptidase and ß-N-acetylglucosaminidase. The results highlight that converting tropical natural forests to managed ecosystems can increase the soil microbial N limitation through reducing the soil microbial biomass and gross N production.


Assuntos
Ecossistema , Solo , Nitrogênio/análise , Nitrogênio/metabolismo , Microbiologia do Solo , Florestas , Carbono , Fósforo/metabolismo
8.
Anal Bioanal Chem ; 416(13): 3149-3160, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38563959

RESUMO

Bats are the second largest mammalian order and are an endangered species group with a strong need for contamination monitoring. To facilitate non-invasive monitoring of the ecological burden in bat populations, a multiresidue method for the simultaneous quantification of 119 analytes including pesticides, persistent organic pollutants (POPs), active pharmaceutical ingredients (APIs), polycyclic aromatic hydrocarbons (PAHs), UV blockers, plasticizers, and other emerging pollutants in bat guano with gas chromatography tandem mass spectrometry (GC-MS/MS) was developed. Sample preparation and clean-up were performed with a modified QuEChERS approach based on DIN EN 15662. The method uses 1.00 g bat guano as sample with acetonitrile and water for liquid-liquid extraction. Phase separation is assisted by citrate-buffered salting out agent. For clean-up of the extract, primary secondary amine (PSA) was combined with graphitized carbon black (GCB). The lower limits of quantification (LLOQ) ranged between 2.5 and 250 µg kg-1. Linearity was shown in a concentration range from the respective LLOQs to 1250 µg kg-1. The median of the mean recovery was 102.4%. Precision was tested at three concentrations. Method and injection precision were adequate with a relative standard deviation (RSD) below 20%. Furthermore, the comparative analysis with LC-MS/MS demonstrated the reliability of the results and provided a valuable extension of the analytical scope. As proof of concept, three guano samples from a German nursery roost of Myotis myotis were analysed. The results show a time-dependent change in contaminant concentration, highlighting the strong need for non-invasive contamination monitoring of whole bat populations.


Assuntos
Quirópteros , Cromatografia Gasosa-Espectrometria de Massas , Limite de Detecção , Espectrometria de Massas em Tandem , Animais , Espectrometria de Massas em Tandem/métodos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Hidrocarbonetos Policíclicos Aromáticos/análise , Reprodutibilidade dos Testes , Extração Líquido-Líquido/métodos , Monitoramento Ambiental/métodos
9.
Phys Chem Chem Phys ; 26(30): 20511-20521, 2024 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-39034776

RESUMO

Chemical looping air separation (CLAS) is a promising process intensification technology for extracting oxygen from air for oxygen enrichment in process streams. Co-doped strontium ferrites (SrFe1-xCoxO3-δ) have been found to have outstanding activities for CLAS processes. In this study, we explore the underlying factors driving the enhancement in oxygen uptake and release performance of perovskite structured SrFe1-xCoxO3-δ oxygen carriers for CLAS. Phase-pure perovskites, with B site substituted by up to 75 mol% Co, were prepared by a sol-gel method and systematically investigated through a wide range of well controlled experimental and computational approaches. While all SrFe1-xCoxO3-δ oxygen carriers showed excellent cyclic stability and structural reversibility over CLAS cycles, increased B site occupancy by Co resulted in monotonic decrease in onset temperature for oxygen release and increase in oxygen carrying capacity. These experimental trends can be fundamentally explained by an increase in the structural tolerance factor, an elevation in transition metal d-band, as well as an increased degree of hybridization between the metal d-band and the O p band. Therefore, these ab initio structural and electronic descriptors are useful design rationales for the hypothesis-driven synthesis of high-performing oxygen carriers for CLAS.

10.
Chimia (Aarau) ; 78(5): 297-303, 2024 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-38822772

RESUMO

Deciphering the structural intricacies of catalysts is essential to advance their atomic-scale engineering. Solid catalysts are complex, with structural features spanning multiple length scales and involving dynamics, which possess challenges in understanding structure-performance relationships. However, advanced operando X-ray characterization techniques, including X-ray absorption spectroscopy (XAS), diffraction (XRD), and pair distribution function analysis (PDF) allow elucidation of structural features under working conditions, discovering transitions from supported nanocrystals to dispersed sites, from solid solutions to supported nanoparticles, or structural changes at the local level. In this mini-review, we discuss case studies exploring the structure of catalysts over different lengths and time scales under different applications, such as CO2 hydrogenation to methanol or the dry reforming of methane, using a combination of operando XAS, XRD and PDF.

13.
J Hazard Mater ; 478: 135528, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-39154476

RESUMO

Microplastics (MPs) in agricultural plastic film mulching system changes microbial functions and nutrient dynamics in soils. However, how biodegradable MPs impact the soil gross nitrogen (N) transformations and crop N uptake remain significantly unknown. In this study, we conducted a paired labeling 15N tracer experiment and microbial N-cycling gene analysis to investigate the dynamics and mechanisms of soil gross N transformation processes in soils amended with conventional (polyethylene, PE) and biodegradable (polybutylene adipate co-terephthalate, PBAT) MPs at concentrations of 0 %, 0.5 %, and 2 % (w/w). The biodegradable MPs-amended soils showed higher gross N mineralization rates (0.5-16 times) and plant N uptake rates (16-32 %) than soils without MPs (CK) and with conventional MPs. The MPs (both PE and PBAT) with high concentration (2 %) increased gross N mineralization rates compared to low concentration (0.5 %). Compare to CK, MPs decreased the soil gross nitrification rates, except for PBAT with 2 % concentration; while PE with 0.5 % concentration and PBAT with 2 % concentration increased but PBAT with 0.5 % concentration decreased the gross N immobilization rates significantly. The results indicated that there were both a concentration effect and a material effect of MPs on soil gross N transformations. Biodegradable MPs increased N-cycling gene abundance by 60-103 %; while there was no difference in the abundance of total N-cycling genes between soils without MPs and with conventional MPs. In summary, biodegradable MPs increased N cycling gene abundance by providing enriched nutrient substrates and enhancing microbial biomass, thereby promoting gross N transformation processes and maize N uptake in short-term. These findings provide insights into the potential consequences associated with the exposure of biodegradable MPs, particularly their impact on soil N cycling processes.

14.
JACS Au ; 4(1): 237-252, 2024 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-38274252

RESUMO

Supported, bimetallic catalysts have shown great promise for the selective hydrogenation of CO2 to methanol. In this study, we decipher the catalytically active structure of Ni-Ga-based catalysts. To this end, model Ni-Ga-based catalysts, with varying Ni:Ga ratios, were prepared by a surface organometallic chemistry approach. In situ differential pair distribution function (d-PDF) analysis revealed that catalyst activation in H2 leads to the formation of nanoparticles based on a Ni-Ga face-centered cubic (fcc) alloy along with a small quantity of GaOx. Structure refinements of the d-PDF data enabled us to determine the amount of both alloyed Ga and GaOx species. In situ X-ray absorption spectroscopy experiments confirmed the presence of alloyed Ga and GaOx and indicated that alloying with Ga affects the electronic structure of metallic Ni (viz., Niδ-). Both the Ni:Ga ratio in the alloy and the quantity of GaOx are found to minimize methanation and to determine the methanol formation rate and the resulting methanol selectivity. The highest formation rate and methanol selectivity are found for a Ni-Ga alloy having a Ni:Ga ratio of ∼75:25 along with a small quantity of oxidized Ga species (0.14 molNi-1). Furthermore, operando infrared spectroscopy experiments indicate that GaOx species play a role in the stabilization of formate surface intermediates, which are subsequently further hydrogenated to methoxy species and ultimately to methanol. Notably, operando XAS shows that alloying between Ni and Ga is maintained under reaction conditions and is key to attaining a high methanol selectivity (by minimizing CO and CH4 formation), while oxidized Ga species enhance the methanol formation rate.

15.
J Magn Reson ; 362: 107671, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38614057

RESUMO

Nuclear spin hyperpolarization techniques, such as dynamic nuclear polarization (DNP) and parahydrogen-induced polarization (PHIP), have revolutionized nuclear magnetic resonance and magnetic resonance imaging. In these methods, a readily available source of high spin order, either electron spins in DNP or singlet states in hydrogen for PHIP, is brought into close proximity with nuclear spin targets, enabling efficient transfer of spin order under external quantum control. Despite vast disparities in energy scales and interaction mechanisms between electron spins in DNP and nuclear singlet states in PHIP, a pseudo-spin formalism allows us to establish an intriguing equivalence. As a result, the important low-field polarization transfer regime of PHIP can be mapped onto an analogous system equivalent to pulsed-DNP. This establishes a correspondence between key polarization transfer sequences in PHIP and DNP, facilitating the transfer of sequence development concepts. This promises fresh insights and significant cross-pollination between DNP and PHIP polarization sequence developers.

16.
PNAS Nexus ; 3(5): pgae170, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38745567

RESUMO

Lack of nitrogen limits food production in poor countries while excessive nitrogen use in industrial countries has led to transgression of the planetary boundary. However, the potential of spatial redistribution of nitrogen input for food security when returning to the safe boundary has not been quantified in a robust manner. Using an emulator of a global gridded crop model ensemble, we found that redistribution of current nitrogen input to major cereals among countries can double production in the most food-insecure countries, while increasing global production of these crops by 12% with no notable regional loss or reducing the nitrogen input to the current production by one-third. Redistribution of the input within the boundary increased production by 6-8% compared to the current relative distribution, increasing production in the food-insecure countries by two-thirds. Our findings provide georeferenced guidelines for redistributing nitrogen use to enhance food security while safeguarding the planet.

17.
Nat Commun ; 15(1): 6312, 2024 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-39060235

RESUMO

Azole antifungals inhibit the sterol C14-demethylase (CYP51/Erg11) of the ergosterol biosynthesis pathway. Here we show that the azole-induced synthesis of fungicidal cell wall carbohydrate patches in the pathogenic mold Aspergillus fumigatus strictly correlates with the accumulation of the CYP51 substrate eburicol. A lack of other essential ergosterol biosynthesis enzymes, such as sterol C24-methyltransferase (Erg6A), squalene synthase (Erg9) or squalene epoxidase (Erg1) does not trigger comparable cell wall alterations. Partial repression of Erg6A, which converts lanosterol into eburicol, increases azole resistance. The sterol C5-desaturase (ERG3)-dependent conversion of eburicol into 14-methylergosta-8,24(28)-dien-3ß,6α-diol, the "toxic diol" responsible for the fungistatic activity against yeasts, is not required for the fungicidal effects in A. fumigatus. While ERG3-lacking yeasts are azole resistant, ERG3-lacking A. fumigatus becomes more susceptible. Mutants lacking mitochondrial complex III functionality, which are much less effectively killed, but strongly inhibited in growth by azoles, convert eburicol more efficiently into the supposedly "toxic diol". We propose that the mode of action of azoles against A. fumigatus relies on accumulation of eburicol which exerts fungicidal effects by triggering cell wall carbohydrate patch formation.


Assuntos
Antifúngicos , Aspergillus fumigatus , Azóis , Proteínas Fúngicas , Aspergillus fumigatus/efeitos dos fármacos , Aspergillus fumigatus/metabolismo , Aspergillus fumigatus/genética , Antifúngicos/farmacologia , Proteínas Fúngicas/metabolismo , Proteínas Fúngicas/genética , Azóis/farmacologia , Ergosterol/metabolismo , Ergosterol/biossíntese , Parede Celular/metabolismo , Parede Celular/efeitos dos fármacos , Farmacorresistência Fúngica/genética , Monoterpenos Bicíclicos/farmacologia , Monoterpenos Bicíclicos/metabolismo , Testes de Sensibilidade Microbiana , Esterol 14-Desmetilase/metabolismo , Esterol 14-Desmetilase/genética , Sistema Enzimático do Citocromo P-450/metabolismo , Sistema Enzimático do Citocromo P-450/genética , Oxirredutases/metabolismo , Oxirredutases/genética , Metiltransferases/metabolismo , Metiltransferases/genética , Esqualeno Mono-Oxigenase/metabolismo , Esqualeno Mono-Oxigenase/genética , Lanosterol/análogos & derivados
18.
ACS Catal ; 14(3): 1834-1845, 2024 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-38327645

RESUMO

Transformations of oxygenates (CO2, CO, H2O, etc.) via Mo2C-based catalysts are facilitated by the high oxophilicity of the material; however, this can lead to the formation of oxycarbides and complicate the identification of the (most) active catalyst state and active sites. In this context, the two-dimensional (2D) MXene molybdenum carbide Mo2CTx (Tx are passivating surface groups) contains only surface Mo sites and is therefore a highly suitable model catalyst for structure-activity studies. Here, we report that the catalytic activity of Mo2CTx in Fischer-Tropsch (FT) synthesis increases with a decreasing coverage of surface passivating groups (mostly O*). The in situ removal of Tx species and its consequence on CO conversion is highlighted by the observation of a very pronounced activation of Mo2CTx (pretreated in H2 at 400 °C) under FT conditions. This activation process is ascribed to the in situ reductive defunctionalization of Tx groups reaching a catalyst state that is close to 2D-Mo2C (i.e., a material containing no passivating surface groups). Under steady-state FT conditions, 2D-Mo2C yields higher hydrocarbons (C5+ alkanes) with 55% selectivity. Alkanes up to the kerosine range form, with value of α = 0.87, which is ca. twice higher than the α value reported for 3D-Mo2C catalysts. The steady-state productivity of 2D-Mo2C to C5+ hydrocarbons is ca. 2 orders of magnitude higher relative to a reference ß-Μo2C catalyst that shows no in situ activation under identical FT conditions. The passivating Tx groups of Mo2CTx can be reductively defunctionalized also by using a higher H2 pretreatment temperature of 500 °C. Yet, this approach leads to a removal of carbidic carbon (as methane), resulting in a 2D-Mo2C1-x catalyst that converts CO to CH4 with 61% selectivity in preference to C5+ hydrocarbons that are formed with only 2% selectivity. Density functional theory (DFT) results attribute the observed selectivity of 2D-Mo2C to C5+ alkanes to a higher energy barrier for the hydrogenation of surface alkyl species relative to the energy barriers for C-C coupling. The removal of O* is the rate-determining step in the FT reaction over 2D-Mo2C, and O* is favorably removed in the form of CO2 relative to H2O, consistent with the observation of a high CO2 selectivity (ca. 50%). The absence of other carbon oxygenates is explained by the energetic favoring of the direct over the hydrogen-assisted dissociative adsorption of CO.

19.
Sci Total Environ ; 915: 170020, 2024 Mar 10.
Artigo em Inglês | MEDLINE | ID: mdl-38224895

RESUMO

Stover mulching in no-tillage farming has been widely proposed as an optimized agricultural management practice to increase soil carbon storage and improve fertilizer nitrogen (N) use efficiency in current agroecosystems. However, the regulation of soil internal gross N transformation dynamics on NO3--N leaching potential in response to long-term conservation tillage practices is still lacking. Here, based on a combination of 15N-tracing incubation and in situ monitoring experiments, we investigated the effect of 9-year no-tillage and maize stover mulching on the vertical migration of fertilizer-derived NO3--N into a deeper soil profile and the associated gross NO3--N transformation dynamics in the Mollisol of Northeast China. The net positive NO3--N production rates (varied from 3.14 to 6.22 mg N kg-1 d-1) were observed across all management practices in the studied Mollisol, indicating a relatively high NO3--N leaching potential in the cropland of Northeast China, which was further confirmed by an average of 7.4 % fertilizer-derived NO3--N being vertically transferred to the 80-100 cm soil layer after a complete maize growing period. Compared with traditional ridge tillage, long-term stover mulching in no-tillage farming significantly reduced total NO3--N production by decreasing autotrophic nitrification while simultaneously enhancing total NO3--N consumption by stimulating nitrate reduction and microbial NO3--N immobilization, revealing a markedly reduction of net NO3--N production in the no-tillage agroecosystem. Therefore, converting traditional ridge tillage toward no-tillage with maize stover mulching can effectively decrease fertilizer-derived NO3--N leaching amounts and thus formulate targeted mitigation strategies for sustainable agriculture in Mollisols of Northeast China.

20.
Nat Ecol Evol ; 8(7): 1270-1284, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38849504

RESUMO

Microbial inoculation involves transplanting microorganisms from their natural habitat to new plants or soils to improve plant performance, and it is being increasingly used in agriculture and ecological restoration. However, microbial inoculants can invade and alter the composition of native microbial communities; thus, a comprehensive analysis is urgently needed to understand the overall impact of microbial inoculants on the biomass, diversity, structure and network complexity of native communities. Here we provide a meta-analysis of 335 studies revealing a positive effect of microbial inoculants on soil microbial biomass. This positive effect was weakened by environmental stress and enhanced by the use of fertilizers and native inoculants. Although microbial inoculants did not alter microbial diversity, they induced major changes in the structure and bacterial composition of soil microbial communities, reducing the complexity of bacterial networks and increasing network stability. Finally, higher initial levels of soil nutrients amplified the positive impact of microbial inoculants on fungal biomass, actinobacterial biomass, microbial biomass carbon and microbial biomass nitrogen. Together, our results highlight the positive effects of microbial inoculants on soil microbial biomass, emphasizing the benefits of native inoculants and the important regulatory roles of soil nutrient levels and environmental stress.


Assuntos
Biomassa , Microbiota , Microbiologia do Solo , Bactérias/classificação , Biodiversidade , Inoculantes Agrícolas/fisiologia , Solo/química , Fungos/fisiologia
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