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Solid-liquid extraction was investigated to obtain selected major plant nutrients (P, K, Ca, Mg) from biofuel ash using weak organic acids like salicylic acid, citric acid, and oxalic acid as sacrificial leaching agents. In this study, three organic acids were compared to determine the most effective leaching agent for maximizing the P, K, Ca, and Mg extraction from biofuel ash. The findings indicated that 0.1 M citric acid was the most efficient for plant nutrient recovery, with 81.9% of P recovered after 30 min, 82.4% of Ca, 76.8% of Mg, and 47.3% of K. after 120 min. The highest amount of K, with 59.3% was recovered after 180 min of extraction with 0.1 M oxalic acid. However, recovery of P-80.7% was lower, and much lower recovery of Ca-2.3%, and Mg-68.6% after 180 min of extraction with 0.1 M oxalic acid. The leachates were not contaminated with heavy metals, just 0.47 mg/L of Zn, 7.67 mg/L of Al, and 1.99 mg/L of Fe were detected after 180 min of extraction with 0.1 M oxalic acid. The formation of calcium oxalates after extraction with 0.1 M oxalic acid was seen by SEM-EDS. The findings indicated that to achieve the highest recovery of all beneficial nutrients (P, K, Ca, Mg) different extraction times and different extraction agents are required.
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Biocombustíveis , Ácido Oxálico , Ácido Oxálico/química , Biocombustíveis/análise , Ácido Cítrico/química , Nutrientes/análise , Metais Pesados/análise , Metais Pesados/química , Fósforo/análise , Fósforo/química , Magnésio/química , Magnésio/análise , Ácido Salicílico/química , Cálcio/química , Cálcio/análise , Potássio/análise , Potássio/químicaRESUMO
Interest in energy-to-X and X-to-energy (where X represents green hydrogen, carbon-based fuels, or ammonia) technologies has expanded the field of electrochemical conversion and storage. Solid oxide electrochemical cells (SOCs) are among the most promising technologies for these processes. Their unmatched conversion efficiencies result from favorable thermodynamics and kinetics at elevated operating temperatures (400-900 °C). These solid-state electrochemical systems exhibit flexibility in reversible operation between fuel cell and electrolysis modes and can efficiently utilize a variety of fuels. However, electrocatalytic materials at SOC electrodes remain nonoptimal for facilitating reversible operation and fuel flexibility. In this Review, we explore the diverse range of electrocatalytic materials utilized in oxygen-ion-conducting SOCs (O-SOCs) and proton-conducting SOCs (H-SOCs). We examine their electrochemical activity as a function of composition and structure across different electrochemical reactions to highlight characteristics that lead to optimal catalytic performance. Catalyst deactivation mechanisms under different operating conditions are discussed to assess the bottlenecks in performance. We conclude by providing guidelines for evaluating the electrochemical performance of electrode catalysts in SOCs and for designing effective catalysts to achieve flexibility in fuel usage and mode of operation.
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Boroxine- and borazine-cage analogs to C20, C60, and C70 were calculated and compared in terms of structure, strain indicators, and physical properties relevant to nanoscale applications. The results show C60 and C70 type cages are less strained than the smaller congener, primarily due to minimized bending in the B-arylene-B segments. The smallest cage calculated has a diameter of 2.4 nm, which increases up to 4.9 nm by either variation of the polyhedron (C20 < C60 < C70-type cage) or organic spacer elongation between boron centers. All calculated cages are porous (apertures ranging from 0.6 to 1.9 nm). Molecular electrostatic potential and Hirshfeld population analysis revealed both nucleophilic and electrophilic sites in the interior and exterior cage surfaces. HOMO-LUMO gaps range from 3.98 to 4.89 eV and 5.10-5.18 eV for the boroxine- and borazine-cages, respectively. Our findings provide insights into the design and properties of highly porous boroxine and borazine cages for nanoscience.
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Phosphorus (P) and Ammonium Nitrogen (N) are essential nutrients for plants and environmental stability. However, their excess in water causes eutrophication, damaging aquatic ecosystems. While adsorption is a promising solution, finding affordable and efficient adsorbents remains a challenge. In this study, magnesium (Mg), iron (Fe), and Mg/Fe doped biochars (BC) adsorbents were synthesized, and evaluated for adsorption of individual P and N and a P + N mixture from a solution and wastewater from a wastewater treatment plant. Compared to other adsorbents, Mg/BC showed excellent performance in adsorbing phosphorus (P) and ammonium nitrogen (N) from aqueous solutions. It demonstrated a large adsorption capacity of 64.65 mg/g and 62.50 mg/g from individual P and N solutions, and 30.3 mg/g and 27.67 mg/g from the P and N mixture solution, respectively. In addition, Mg/BC efficiently removed P and N from real-life wastewater. In the real wastewater, P and N removal efficiencies reached 88.30% and 59.36%, respectively. Kinetics analysis revealed that the pseudo-second-order model accurately described the adsorption of phosphorus (P) and ammonium nitrogen (N) in all solutions. The adsorbent followed the monolayer-Langmuir isotherm for N ions and the multilayer-Freundlich isotherm for P, indicating efficient adsorption processes. Thermodynamic experiments indicated that the adsorption of P and N was not only feasible but also occurred spontaneously in a natural manner. This study revealed that the strategic modification of biochar plays a crucial role in advancing effective wastewater treatment technologies designed for nutrient removal.
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Carvão Vegetal , Magnésio , Nitrogênio , Fosfatos , Águas Residuárias , Poluentes Químicos da Água , Carvão Vegetal/química , Adsorção , Nitrogênio/química , Magnésio/química , Poluentes Químicos da Água/química , Fosfatos/química , Águas Residuárias/química , Cinética , Eliminação de Resíduos Líquidos/métodos , Fósforo/química , Purificação da Água/métodosRESUMO
The utilization of lignin, an abundant and renewable bio-aromatic source, is of significant importance. In this study, lignin oxidation was examined at different temperatures with zirconium oxide (ZrO2)-supported nickel (Ni), cobalt (Co) and bimetallic Ni-Co metal catalysts under different solvents and oxygen pressure. Non-catalytic oxidation reaction produced maximum bio-oil (35.3 wt%), while catalytic oxidation significantly increased the bio-oil yield. The bimetallic catalyst Ni-Co/ZrO2 produced the highest bio-oil yield (67.4 wt%) compared to the monometallic catalyst Ni/ZrO2 (59.3 wt%) and Co/ZrO2 (54.0 wt%). The selectively higher percentage of vanillin, 2-methoxy phenol, acetovanillone, acetosyringone and vanillic acid compounds are found in the catalytic bio-oil. Moreover, it has been observed that the bimetallic Co-Ni/ZrO2 produced a higher amount of vanillin (43.7% and 13.30 wt%) compound. These results demonstrate that the bimetallic Ni-Co/ZrO2 catalyst promotes the selective cleavage of the ether ß-O-4 bond in lignin, leading to a higher yield of phenolic monomer compounds.
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Benzaldeídos , Cobalto , Níquel , Óxidos , Óleos de Plantas , Polifenóis , Zircônio , Lignina , FenóisRESUMO
Plasma-catalytic bireforming of methane was studied and actively optimized using a La0.7Ce0.3NiO3 perovskite catalyst via experimentation in tandem with response surface modeling. Plasma power, inlet flow rate, temperature, CO2/CH4 ratio, and steam concentration were tuned to maximize a variety of process- and sustainability-based metrics. Analysis of the optimal conditions (with respect to different metrics) with and without the catalyst reveals that dry reforming is driven largely via noncatalytic reactions, while steam reforming and water gas shift reactions require the catalyst. The experimental outcome demonstrated that under optimum reaction conditions using the La0.7Ce0.3NiO3 catalyst it is possible to minimize global warming potential (GWP), in terms of inferred CO2 footprint normalized to hydrogen throughput, resulting in maximizing hydrogen yield through steam reforming (and water gas shift reactions) at an SEI of ≈12 eV/molecule. Furthermore, the highest CH4 conversion reached was 87% while the catalyst showed good activity stability in DBD plasma experiments.The actively learned iterative optimization procedure developed in this work allows for a direct juxtaposition of thermal (heat needed to make steam and heat the plasma reactor) and electrical (power requirement for plasma generation) carbon footprints in a highly nonlinear multivariate process. Furthermore, the corresponding GWP was calculated using a conventional electricity mix, wind electricity, and solar electricity, allowing a direct sustainability assessment in catalyst-assisted plasma conversion of carbonaceous feedstock to H2 and CO.
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A parabolic trough collector solar field was designed to supply the heat needed to regenerate the CO2-rich monoethanolamine in a solar-assisted carbon capture system. Process design modeling was performed for 90% of the CO2 removal from 1% of the flue gas produced by a 255 MWe natural gas combined cycle power plant. Calculations with and without 24 h of thermal energy storage by increasing the solar collector size needed and providing a buffer vessel to store hot heat transfer fluid were performed. A dynamic analysis of the solar field using the hourly solar forecast was performed to investigate how heat transfer fluid mass flow changes during January and June to maintain the desired parabolic solar field outlet temperature needed for CO2 reboiler operation. The calculations provided here present an explicit method to calculate relevant solar field design parameters that can be scaled up and used in solar energy-assisted gas capture processes.
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A capacitive micromachined ultrasound transducer (CMUT) was engineered and functionalized with zeolitic imidazolate framework-8 (ZIF-8) dispersed in a photoresist AZ1512HS (AZ) matrix to function as a gravimetric gas sensor. The sensor response was recorded in the presence of nitrogen, argon, carbon dioxide, and methane gases as well as water, acetylene, a propane/butane mixture, n-hexane, gasoline, and diesel vapors. The photoresist matrix alone was found to have a negligible response to all the gases and vapors, except for water vapor. No visible difference in sensor response was detected when switching from nitrogen to methane gas. However, a strong shift in the sensor resonance frequency was observed when exposed to higher hydrocarbons, ranging from 1 kHz for acetylene to 7.5 kHz for gasoline. Even longer-chain hydrocarbons, specifically kerosene and more so diesel, had a significantly reduced sensor frequency shift compared with gasoline. Sensors functionalized with a thin film of AZ+ZIF-8 demonstrated higher sensitivity in their response to a hydrocarbon molecular mass than without functionalization.
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Efficient treatment of nutrient-rich wastewater is of paramount importance for protecting the ecosystem. In this work, an efficient, abundant, and eco-friendly adsorbent was derived from biochar and employed for phosphorus (P) adsorption. The key factors influencing the P removal efficiency of the activated biochar, including P concentration, pH, dosage, temperature, adsorption time, and influence of co-existing ion type, were investigated. Maximum P adsorption percentage (100%) was obtained with 10 mg/L and zinc chloride activated biochar (BC-Zn) compared to the other activated biochars. Results show that by increasing the P concentration from 5 to 200 mg/L, the phosphorus adsorption capacity increases from 0.13 to 10.4 mg/g biochar. Isotherms and kinetic studies further show that the P adsorption follows the Langmuir and quasi-second-order kinetic models. The mechanistic investigation demonstrated that P adsorption occurred by precipitation reaction. Furthermore, P desorption has been studied at different time intervals to understand the P release rate after adsorption.
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Single atom catalysts (SACs) possess unique catalytic properties due to low-coordination and unsaturated active sites. However, the demonstrated performance of SACs is limited by low SAC loading, poor metal-support interactions, and nonstable performance. Herein, we report a macromolecule-assisted SAC synthesis approach that enabled us to demonstrate high-density Co single atoms (10.6 wt % Co SAC) in a pyridinic N-rich graphenic network. The highly porous carbon network (surface area of â¼186 m2 g-1) with increased conjugation and vicinal Co site decoration in Co SACs significantly enhanced the electrocatalytic oxygen evolution reaction (OER) in 1 M KOH (η10 at 351 mV; mass activity of 2209 mA mgCo-1 at 1.65 V) with more than 300 h stability. Operando X-ray absorption near-edge structure demonstrates the formation of electron-deficient Co-O coordination intermediates, accelerating OER kinetics. Density functional theory (DFT) calculations reveal the facile electron transfer from cobalt to oxygen species-accelerated OER.
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This article presents the synthesis, property characterization and catalytic application of CuO-supported disodium titanium phosphate, (CuO@Na2Ti(PO4)2â H2O) for the reduction of industrial pollutant 4-nitrophenol (4-NP). A simple hydrothermal route was developed to synthesize CuO@Na2Ti(PO4)2â H2O catalyst (CuO@Na2TiP) from beach sand ilmenite. The prepared CuO@Na2TiP was characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, and nitrogen adsorption-desorption isotherms. The catalyst 12 wt.% CuO@Na2TiP showed the fastest reduction kinetics for 4-NP.
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The experimentally validated computational models developed herein, for the first time, show that Mn-promotion does not enhance the activity of the surface Na2WO4 catalytic active sites for CH4 heterolytic dissociation during OCM. Contrary to previous understanding, it is demonstrated that Mn-promotion poisons the surface WO4 catalytic active sites resulting in surface WO5 sites with retarded kinetics for C-H scission. On the other hand, dimeric Mn2O5 surface sites, identified and studied via ab initio molecular dynamics and thermodynamics, were found to be more efficient in activating CH4 than the poisoned surface WO5 sites or the original WO4 sites. However, the surface reaction intermediates formed from CH4 activation over the Mn2O5 surface sites are more stable than those formed over the Na2WO4 surface sites. The higher stability of the surface intermediates makes their desorption unfavorable, increasing the likelihood of over-oxidation to CO x , in agreement with the experimental findings in the literature on Mn-promoted catalysts. Consequently, the Mn-promoter does not appear to have an essential positive role in synergistically tuning the structure of the Na2WO4 surface sites towards CH4 activation but can yield MnO x surface sites that activate CH4 faster than Na2WO4 surface sites, but unselectively.
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Unsupervised exploratory data analysis (EDA) is often the first step in understanding complex data sets. While summary statistics are among the most efficient and convenient tools for exploring and describing sets of data, they are often overlooked in EDA. In this paper, we show multiple case studies that compare the performance, including clustering, of a series of summary statistics in EDA. The summary statistics considered here are pattern recognition entropy (PRE), the mean, standard deviation (STD), 1-norm, range, sum of squares (SSQ), and X4, which are compared with principal component analysis (PCA), multivariate curve resolution (MCR), and/or cluster analysis. PRE and the other summary statistics are direct methods for analyzing data-they are not factor-based approaches. To quantify the performance of summary statistics, we use the concept of the "critical pair," which is employed in chromatography. The data analyzed here come from different analytical methods. Hyperspectral images, including one of a biological material, are also analyzed. In general, PRE outperforms the other summary statistics, especially in image analysis, although a suite of summary statistics is useful in exploring complex data sets. While PRE results were generally comparable to those from PCA and MCR, PRE is easier to apply. For example, there is no need to determine the number of factors that describe a data set. Finally, we introduce the concept of divided spectrum-PRE (DS-PRE) as a new EDA method. DS-PRE increases the discrimination power of PRE. We also show that DS-PRE can be used to provide the inputs for the k-nearest neighbor (kNN) algorithm. We recommend PRE and DS-PRE as rapid new tools for unsupervised EDA.
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Algoritmos , Análise por Conglomerados , Entropia , Análise dos Mínimos Quadrados , Análise de Componente PrincipalRESUMO
The complex structure of the catalytic active phase, and surface-gas reaction networks have hindered understanding of the oxidative coupling of methane (OCM) reaction mechanism by supported Na2 WO4 /SiO2 catalysts. The present study demonstrates, with the aid of in situ Raman spectroscopy and chemical probe (H2 -TPR, TAP and steady-state kinetics) experiments, that the long speculated crystalline Na2 WO4 active phase is unstable and melts under OCM reaction conditions, partially transforming to thermally stable surface Na-WOx sites. Kinetic analysis via temporal analysis of products (TAP) and steady-state OCM reaction studies demonstrate that (i) surface Na-WOx sites are responsible for selectively activating CH4 to C2 Hx and over-oxidizing CHy to CO and (ii) molten Na2 WO4 phase is mainly responsible for over-oxidation of CH4 to CO2 and also assists in oxidative dehydrogenation of C2 H6 to C2 H4 . These new insights reveal the nature of catalytic active sites and resolve the OCM reaction mechanism over supported Na2 WO4 /SiO2 catalysts.
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Recovery of nutrients from biomass combustion ash is of great importance for sustainable bioenergy waste use. In this work, granulated fertilizer materials were engineered from biofuel bottom ash, lime kiln dust and water, analysed for their chemical complexity and tested in pot experiments (2017-2018) for their propensity to release nutrients. The results obtained in this work showed that spring barley yield was observed to be the highest for granulated biomass ash with 30% of ash in the granule. The yield increased 3.99 t ha-1 per 100 kg ha-1 potassium oxide (K2O) in 2017 and 1.23 t ha-1 per 100 kg ha-1 K2O in 2018. Straw yield varied between 1.39-5.08 t ha-1/100 kg ha-1 in 2017 and 0.36-1.23 t ha-1/100 kg ha-1 in 2018. Calcium concentration significantly increased in soil. No significant changes in soil mobile phosphorus (P) were obtained as well as for the heavy metal concentrations in soil. This suggests that biofuel ash can be a significant source of certain major nutrients for crops that can also beneficially affect soil pH. The results of this work can provide policy-makers with the information needed to diversify existing and enable new biomass bottom ash utilization routes which currently vary significantly between the countries.
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Biocombustíveis , Poluentes do Solo , Biomassa , Cinza de Carvão , Fertilizantes , Nutrientes , Solo , Poluentes do Solo/análiseRESUMO
This review focuses on recent fundamental insights about methane dehydroaromatization (MDA) to benzene over ZSM-5-supported transition metal oxide-based catalysts (MOx/ZSM-5, where M = V, Cr, Mo, W, Re, Fe). Benzene is an important organic intermediate, used for the synthesis of chemicals like ethylbenzene, cumene, cyclohexane, nitrobenzene and alkylbenzene. Current production of benzene is primarily from crude oil processing, but due to the abundant availability of natural gas, there is much recent interest in developing direct processes to convert CH4 to liquid chemicals. Among the various gas-to-liquid methods, the thermodynamically-limited Methane DehydroAromatization (MDA) to benzene under non-oxidative conditions appears very promising as it circumvents deep oxidation of CH4 to CO2 and does not require the use of a co-reactant. The findings from the MDA catalysis literature is critically analyzed with emphasis on in situ and operando spectroscopic characterization to understand the molecular level details regarding the catalytic sites before and during the MDA reaction. Specifically, this review discusses the anchoring sites of the supported MOx species on the ZSM-5 support, molecular structures of the initial dispersed surface MOx sites, nature of the active sites during MDA, reaction mechanisms, rate-determining step, kinetics and catalyst activity of the MDA reaction. Finally, suggestions are given regarding future experimental investigations to fill the information gaps currently found in the literature.
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Salt cocrystals with components that assemble by hydrogen bonds and aromatic anion-molecule stacks (π--π stacks) are reported. U-shaped bipyridines and an isocoumarin carboxylic acid self-assemble to form 5-, 6-, and 10-component aggregates with components in double and quadruple face-to-face stacks. DFT calculations support the π--π stacks to help stabilize the salt cocrystals.
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Using the mechanosynthesis of the calcium urea phosphate fertilizer cocrystal as a model, we provide a quantitative investigation of chemical autocatalysis in a mechanochemical reaction. The application of in situ Raman spectroscopy and synchrotron X-ray powder diffraction to monitor the reaction of urea phosphate and either calcium hydroxide or carbonate enabled the first quantitative and in situ study of a mechanochemical system in which one of the products of a chemical reaction (water) mediates the rate of transformation and underpins positive feedback kinetics. The herein observed autocatalysis by water generated in the reaction enables reaction acceleration at amounts that are up to 3 orders of magnitude smaller than in a typical liquid-assisted mechanochemical reaction.
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A gravimetric gas detection device based on surface functionalized Capacitive Micromachined Ultrasound Transducers (CMUTs) was designed, fabricated and tested for detection of carbon dioxide (CO2) and sulfur dioxide (SO2) mixtures in nitrogen. The created measurement setup of continuous data collection, integrated with an in-situ Fourier Transform Infrared (FT-IR) spectroscopy, allows for better understanding of the mechanisms and molecular interactions with the sensing layer (methylated poly(ethylene)imine) and its need of surface functionalization for multiple gas detection. During experimentation with CO2 gases, weak molecular interactions were observed in spectroscopy data. Linear sensor response to frequency shift was observed with CO2 concentrations ranging from 0.16 vol % to 1 vol %. Moreover, the Raman and FT-IR spectroscopy data showed much stronger SO2 and the polymer interactions, molecules were bound by stronger forces and irreversibly changed the polymer film properties. However, the sensor change in resonance frequency in the tested region of 1 vol % to 5 vol % SO2 showed a linear response. This effect changed not only the device resonance frequency but also affected the magnitude of electroacoustic impedance which was used for differentiating the gas mixture of CO2, SO2, in dry N2.
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2D atomic crystals have been widely explored, usually owing to their numerous shapes, of which the typical hexagon has drawn the most interest. However, the relationship between shape and properties has not been fully probed, owing to the lack of a proper system. Here, we demonstrate for the first time the shape-dependent surface oxidation of 2D Mo2C crystals, where the elongated flakes are preferentially oxidized under ambient conditions when compared with regular ones, showing higher chemical activity. The gradual surface oxidation of elongated Mo2C crystals as a function of time is clearly observable. Structural determinations reveal that a discrepancy in the arrangement of Mo and C atoms between elongated and regular crystals accounts for the selective oxidation behavior. The identification of the shape-dependent surface oxidization of Mo2C crystals provides significant possibilities for tuning the properties of 2D materials via shape-control.