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1.
Artigo em Inglês | MEDLINE | ID: mdl-38832914

RESUMO

Electrochemical reduction (ECR) of CO2 to C2H4 has a potential key role in realizing the carbon neutral future, which ultimately relies on the availability of an efficient electrocatalyst that can exhibit a high Faradaic efficiency (FE) for C2H4 production and robust, long-term operational stability. Here, for the first time, we report that upon applying reductive potential and electrolyte to the benchmark La2CuO4 catalyst, surface reconstruction occurred, i.e., the appearance of a distinctive phase evolution process over time, which was successfully monitored using ex situ powder XRD and operando Mott-Schottky (M-S) measurements of La2CuO4 samples that were soaked into the electrolyte and subjected to CO2-ECR for different durations. At the end of such a reconstruction process, an outermost layer consisting of lanthanum carbonate, a thin outer layer made of an amorphous Cu+ material formed over the core bulk La2CuO4, as confirmed by various characterization techniques, which resulted in the redistribution of interfacial electrons and subsequent formation of electron-rich and electron-deficient interfaces. This contributed to the enhancement in FE for C2H4, reaching as much as 58.7%. Such surface reconstruction-induced electronic structure tuning gives new explanations for the superior catalytic performance of La2CuO4 perovskite and also provides a new pathway to advance CO2-ECR technology.

2.
Heliyon ; 10(10): e30768, 2024 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-38774313

RESUMO

Malaysia is the second largest producer and exporter of palm oil. Though several works have explored achieving emissions reduction in the palm oil sector, there existing gaps in analysing pathways for achieving net-zero emissions. Moreover, there are limited studies that evaluate the potential of palm oil biomass utilisation pathways based on emissions reduction capabilities, the cost of emissions reduction, and the technology readiness for implementation. Therefore, this study analysed decarbonisation pathways for the upstream and midstream segments of the palm oil sector in Malaysia, encompassing oil palm plantations and palm oil mills. Various sources of greenhouse gas emissions in oil palm plantations and palm oil mills were identified and estimates of emissions were determined as theoretical emissions. The current emissions were established based on the current best practice in the plantation and mill. Several biomass conversion technologies for the recovery of palm-based by-products and conversion into value-added products to decarbonise the palm oil sector and evaluated strategies to attain net-zero status are considered. In this work, the analysis considered both the existing technologies that are adopted by plantations and mills as well as the emerging technologies that have scope for implementation. With the proposed approach, the current emissions level for crude palm oil (CPO) production in Malaysia is estimated as 1121.49 kg CO2-eq/t CPO. In current industry practice, empty fruit bunch (EFB) is underutilised as mills are typically located at rural areas with lack of suitable transportation. Besides, the lack of accessibility to the grid also limits the potential of converting EFB into electricity as supply for national grid. This work examined various pathways for EFB utilisation under different scenarios evaluating their contribution potential towards net-zero target in an energy self-sustained CPO production. As shown in the results, converting EFB to briquettes and pellets are able to achieve the net-zero objective. Furthermore, EFB-biochar and EFB-syngas pathways also exhibit the potential to accomplish the net-zero target. Note that this work also assessed the technologies' readiness levels, identified challenges in implementation, and proposed several recommendations.

3.
Membranes (Basel) ; 14(5)2024 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-38786950

RESUMO

Water pollution remains a critical concern, one necessitated by rapidly increasing industrialization and urbanization. Among the various strategies for water purification, membrane technology stands out, with polyethersulfone (PES) often being the material of choice due to its robust mechanical properties, thermal stability, and chemical resistance. However, PES-based membranes tend to exhibit low hydrophilicity, leading to reduced flux and poor anti-fouling performance. This study addresses these limitations by incorporating titanium dioxide nanotubes (TiO2NTs) into PES nanofiltration membranes to enhance their hydrophilic properties. The TiO2NTs, characterized through FTIR, XRD, BET, and SEM, were embedded in PES at varying concentrations using a non-solvent induced phase inversion (NIPS) method. The fabricated mixed matrix membranes (MMMs) were subjected to testing for water permeability and solute rejection capabilities. Remarkably, membranes with a 1 wt% TiO2NT loading displayed a significant increase in pure water flux, from 36 to 72 L m2 h-1 bar-1, a 300-fold increase in selectivity compared to the pristine sample, and a dye rejection of 99%. Furthermore, long-term stability tests showed only a slight reduction in permeate flux over a time of 36 h, while dye removal efficiency was maintained, thus confirming the membrane's stability. Anti-fouling tests revealed a 93% flux recovery ratio, indicating excellent resistance to fouling. These results suggest that the inclusion of TiO2 NTs offers a promising avenue for the development of efficient and stable anti-fouling PES-based membranes for water purification.

4.
Chem Commun (Camb) ; 60(39): 5177-5180, 2024 May 09.
Artigo em Inglês | MEDLINE | ID: mdl-38647014

RESUMO

A vertically-stacked MXene/rGO composite membrane with ultrashort transport channels is reported here, which demonstrated outstanding molecular sieving, i.e., H2/CO2 selectivity of up to 83 together with high H2 permeance of 2.7 × 10-7 mol m-2 s-1 Pa-1 at 120 °C, highlighting its applicability for H2/CO2 separation in CO2 capture and sequestration.

5.
Water Res ; 256: 121607, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38640568

RESUMO

This work investigates the physicochemical characteristics of grease-trap wastewater discharged from a large community market. It proposes potential mechanisms of fat, oil, and grease (FOG) solid formation, separation, and accumulation inside grease traps. Sixty-four samples, i.e., the floated scum, suspended solid-liquid wastewater, and settled sludge, were collected from the grease-trap inlet and outlet chambers. A lower pH of 5-6 at 25-29 °C inside the grease trap than those reported under the sewer conditions (pH 6-7) was revealed. A significant difference in solid and dissolved constituents was also discovered between the inlet and outlet chambers, indicating that the baffle wall could affect the separation mechanism. The sludge samples had 1.5 times higher total solids (TS) than the scum samples, i.e., 0.225 vs. 0.149 g g-1 TS, revealing that the sludge amount impacted more significantly the grease trap capacity and operation and maintenance. In contrast, the scum samples had 1.4 times higher volatile solids (VS) than the sludge samples, i.e., 0.134 vs. 0.096 g g-1 VS, matching with the 64.2 vs. 29.7% of carbon content from CHN analysis. About 2/3 of the free fatty acids (FFAs) with palmitic acids were the primary saturated FFAs, while the remaining 1/3 of unsaturated FFAs were found in the solid and liquid samples. Although up to 0.511 g g-1 FOG can be extracted from the scum samples, none from the sludge samples. More diverse minerals/metals other than Na, Cl, and Ca were found in the sludge samples than in the scum samples. Grease-trap FOG solids and open drain samples exhibited similar physicochemical properties to those reported in the literature. Four potential mechanisms (crystallization, emulsification, saponification, and baffling) were presented. This work offers insights into the physicochemical properties of grease-trap wastewater that can help explore its FOG solid formation, separation, and accumulation mechanisms inside a grease trap.


Assuntos
Esgotos , Eliminação de Resíduos Líquidos , Águas Residuárias , Águas Residuárias/química , Esgotos/química
6.
Chemosphere ; 350: 141103, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38184083

RESUMO

This work reports the ion exchange fabrication of maghemite (γ-Fe2O3) modified NaY zeolite (Fe2O3@Y) with bifunction of adsorption and catalysis. The Fe3+ successfully replaced the Na+ in the ß cage of zeolite in the ion exchange process and coordinated with framework oxygens to form magnetic γ-Fe2O3. Therefore, most of the γ-Fe2O3 particles were confined in the ß cages, which resulted in the high dispersal and stability of the catalyst. The Fe2O3@Y could remove methylene blue (MB) model pollutants up to 59.02 and 61.47% through the adsorption and catalysis process, respectively. The hydrogen bond between the OH- ions around the Fe2O3@Y surface and the N and O presented in the MB molecules enabled the chemical adsorption to MB, which accorded with the pseudo-second-order kinetic model. Further, the H+ existed in the solution and the ß cage of zeolite promoted the collapse of micro-nano bubbles (MNBs). Then, the γ-Fe2O3 catalyst would be activated by high temperature and oxidated OH- to produce hydroxyl radicals for pollutant degradation. Thus, pollutant removal was attributed to the combined effects of adsorption and catalysis in the Fe2O3@Y + MNB system. In this work, the Fe2O3@Y was demonstrated as a potentially magnetic adsorbent or MNB catalyst for wastewater treatment.


Assuntos
Poluentes Ambientais , Poluentes Químicos da Água , Zeolitas , Compostos Férricos , Catálise , Adsorção , Poluentes Químicos da Água/análise , Cinética
7.
Int J Biol Macromol ; 257(Pt 1): 128502, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38040139

RESUMO

As a natural raw material to replace synthetic chemicals, cellulose and its derivatives are the most popular choices in the pharmaceutical industry. For drug delivery applications, cellulose is usually used as a cellulose nanocrystal (CNC). CNC-based hydrogels are widely utilized for drug delivery because drug molecules can be encapsulated in their pore-like structures. This study aims to develop CNC hydrogels for the delivery of doripenem antibiotics. CNC was obtained from jackfruit peel extraction, and alginate was used as a network polymer to produce hydrogels. Ionotropic gelation was used in the synthesis of CNC-alginate hydrogel composites. The maximum adsorption of doripenem by CNC was 65.7 mg/g, while the maximum adsorption by CNC-alginate was 98.4 mg/g. One of the most challenging aspects of drug delivery is predicting drug release from a solid matrix using simple and complex mathematical equations. The sigmoidal equation could represent the doripenem release from CNC, while the Ritger-Peppas equation could describe the doripenem release from CNC-Alginate. The biocompatibility testing of CNC and CNC-alginate against a 7F2 cell line indicates that both materials were non-toxic.


Assuntos
Artocarpus , Nanopartículas , Hidrogéis/química , Celulose/química , Doripenem , Alginatos/química , Adsorção , Nanopartículas/química
8.
Front Chem Sci Eng ; : 1-21, 2023 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-37359292

RESUMO

The Association of Southeast Asian Nations is blessed with agricultural resources, and with the growing population, it will continue to prosper, which follows the abundance of agricultural biomass. Lignocellulosic biomass attracted researchers' interest in extracting bio-oil from these wastes. However, the resulting bio-oil has low heating values and undesirable physical properties. Hence, co-pyrolysis with plastic or polymer wastes is adopted to improve the yield and quality of the bio-oil. Furthermore, with the spread of the novel coronavirus, the surge of single-use plastic waste such as disposable medical face mask, can potentially set back the previous plastic waste reduction measures. Therefore, studies of existing technologies and techniques are referred in exploring the potential of disposable medical face mask waste as a candidate for co-pyrolysis with biomass. Process parameters, utilisation of catalysts and technologies are key factors in improving and optimising the process to achieve commercial standard of liquid fuel. Catalytic co-pyrolysis involves a series of complex mechanisms, which cannot be explained using simple iso-conversional models. Hence, advanced conversional models are introduced, followed by the evolutionary models and predictive models, which can solve the non-linear catalytic co-pyrolysis reaction kinetics. The outlook and challenges for the topic are discussed in detail.

9.
Data Brief ; 48: 109159, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-37168600

RESUMO

The dataset reported in this article describes the adsorption isotherms of amoxicillin, ampicillin, and doripenem onto bentonite. Batch adsorption experiments were carried out on single antibiotic solutions with various dosage of bentonite across temperatures from 30 to 50 °C. The adsorbent loading dataset was later obtained by measuring the concentration of antibiotic solution at adsorption equilibrium via UV-Vis spectrophotometer. The dataset was also fitted using various isotherm models including Freundlich, Langmuir, Toth, Hill, and Dubinin-Radushkevich models to further analyze the adsorption behavior. On top of that, orthogonal regression was applied to avoid fitting biasness, whereby the fitting results revealed the highest adsorption capacities of 82.259 mg g-1 for amoxicillin, 78.851 mg g-1 for ampicillin, and 93.278 mg g-1 for doripenem using Langmuir model, which gave an accurate representation of the adsorption isotherm dataset that was consistent with the results of Toth and Hill model.

10.
J Colloid Interface Sci ; 644: 533-545, 2023 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-37012113

RESUMO

Metal-organic polymers (MOPs) can enhance the photoelectrochemical (PEC) water oxidation performance of BiVO4 photoanodes, but their PEC mechanisms have yet to be comprehended. In this work, we constructed an active and stable composite photoelectrode by overlaying a uniform MOP on the BiVO4 surface using Fe2+ as the metal ions and 2,5-dihydroxyterephthalic acid (DHTA) as ligand. Such modification on the BiVO4 surface yielded a core-shell structure that could effectively enhance the PEC water oxidation activity of the BiVO4 photoanode. Our intensity-modulated photocurrent spectroscopy analysis revealed that the MOP overlayer could concurrently reduce the surface charge recombination rate constant (ksr) and enhance the charge transfer rate constant (ktr), thus accelerating water oxidation activity. These phenomena can be ascribed to the passivation of the surface that inhibits the recombination of the charge carrier and the MOP catalytic layer that improves the hole transfer. Our rate law analysis also demonstrated that the MOP coverage shifted the reaction order of the BiVO4 photoanode from the third-order to the first-order, resulting in a more favorable rate-determining step where only one hole accumulation is required to overcome water oxidation. This work provides new insights into the reaction mechanism of MOP-modified semiconductor photoanodes.

11.
Small ; 19(18): e2207370, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-36765447

RESUMO

Water pollution caused by the massive use of medicines has caused significant environmental problems. This work first reports the synthesis and characterization of the Cu7 S4 /CuCo2 O4 (CS/CCO) yolk-shell microspheres via hydrothermal and annealing methods, and then investigates their photocatalytic performance in removing organic water pollutants. The 10-CS/CCO composite with yolk-shell microspheres exhibits the highest photodegradation rate of carbamazepine (CBZ), reaching 96.3% within 2 h. The 10-CS/CCO also demonstrates more than two times higher photodegradation rates than the pure (Cu7 S4 ) CS and (CuCo2 O4 ) CCO. This outstanding photocatalytic performance can be attributed to the unique yolk-shell structure and the Z-scheme charge transfer pathway, reducing multiple reflections of the acting light. These factors enhance the light absorption efficiency and efficiently transfer photoexcited charge carriers. In-depth, photocatalytic degradation pathways of CBZ are systematically evaluated via the identification of degradation intermediates with Fukui index calculation. The insights gained from this work can serve as a guideline for developing low-cost and efficient Z-scheme photocatalyst composites with the yolk-shell structure.

12.
Environ Res ; 224: 115550, 2023 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-36841526

RESUMO

Pyrolysis oil from oil palm biomass can be a sustainable alternative to fossil fuels and the precursor for synthesizing petrochemical products due to its carbon-neutral properties and low sulfur and nitrogen content. This work investigated the effect of applying mesoporous acidic catalysts, Ni-Mo/TiO2 and Ni/Al2O3, in a catalytic co-pyrolysis of oil palm trunk (OPT) and polypropylene (PP) from 500 to 700 °C. The obtained oil yields varied between 12.67 and 19.50 wt.% and 12.33-17.17 wt.% for Ni-Mo/TiO2 and Ni/Al2O3, respectively. The hydrocarbon content in oil significantly increased up to 54.07-58.18% and 37.28-68.77% after adding Ni-Mo/TiO2 and Ni/Al2O3, respectively. The phenolic compounds content was substantially reduced to 8.46-20.16% for Ni-Mo/TiO2 and 2.93-14.56% for Ni/Al2O3. Minor reduction in oxygenated compounds was noticed from catalytic co-pyrolysis, though the parametric effects of temperature and catalyst type remain unclear. The enhanced deoxygenation and cracking of phenolic and oxygenated compounds and the PP decomposition resulted in increased hydrocarbon production in oil during catalytic co-pyrolysis. Catalyst addition also promoted the isomerization and oligomerization reactions, enhancing the formation of cyclic relative to aliphatic hydrocarbon.


Assuntos
Polipropilenos , Pirólise , Titânio , Hidrocarbonetos , Catálise , Biomassa , Biocombustíveis , Temperatura Alta
13.
Clean Technol Environ Policy ; : 1-17, 2023 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-36643617

RESUMO

This study aims to propose a new process design, simulation, and techno-economic analysis of an integrated process plant that produces glucose and furfural from palm oil empty fruit bunches (EFB). In this work, an Aspen Plus-based simulation has been established to develop a process flow diagram of co-production of glucose and furfural along with the mass and energy balances. The plant's economics are analyzed by calculating the fixed capital income (FCI), operating costs, and working capital. In contrast, profitability is determined using cumulative cash flow (CCF), net present value (NPV), and internal rate of return (IRR). The findings show that the production capacity of 10 kilotons per year (ktpy) of glucose and 4.96 ktpy of furfural with a purity of 98.21 and 99.54%-weight, respectively, was achieved in this study. The FCI is calculated as United States Dollar (USD) 20.80 million, while the working and operating expenses are calculated as USD 3.74 million and USD 16.93 million, respectively. This project achieves USD 7.65 million NPV with a positive IRR of 14.25% and a return on investment (ROI) of 22.06%. The present work successfully develops a profitable integrated process plant that is established with future upscaling parameters and key cost drivers. The findings provided in this work offer a platform and motivation for future research on integrated plants in the food, environment, and energy nexus with the co-location principle.

14.
Chemosphere ; 303(Pt 1): 134973, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35588882

RESUMO

Construction of Z-scheme heterostructure is an effective strategy to enhance the charge carriers' separation. However, successfully achieving this on the defect heterojunction to improve the photocatalytic activity remains challenging. This work successfully obtained sulfur vacancy in the ZnIn2S4/BiOBr (SZIS/BOB) heterojunction composites with S-O covalent bonding using a hydrothermal method. As a result, they exhibited superior photocatalytic and stability performance. The optimized SZIS/BOB-10 exhibited excellent rhodamine B degradation (95.2%) and chromium (VI) reduction (97.8%) within 100 min under visible light. The enhanced composites with S-vacancies, S-O bond, and internal electric field induced the Z-scheme charge transfer mechanism. We had verified this mechanism based on the surface photovoltage spectra, electron spin response spectra, and density functional theory calculations. This work not only provides valuable insights into designing photocatalysts with a direct Z scheme heterostructure but also delineates a promising strategy for developing efficient photocatalysts to degrade organic pollutants.


Assuntos
Cromo , Água , Bismuto , Software
15.
Membranes (Basel) ; 12(2)2022 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-35207112

RESUMO

Catalytic dehydrogenation coupling of methane (DCM) represents an effective way to convert natural gas to more useful C2 products (C2H6, C2H4). In this work, BaCe0.85Tb0.05Co0.1O3-δ (BCTCo) perovskite hollow fiber membranes were fabricated by the combined phase inversion and sintering method. SrCe0.95Yb0.05O3-δ (SCYb) perovskite oxide was loaded as a catalyst onto the inner hollow fiber membrane surface, which promoted the CH4 conversion and the C2 hydrocarbon selectivity during the DCM reaction. The introduction of steam into the methane feed gas mixture elevated the C2 selectivity and yield due to the alleviation of coke deposition. Switching N2 to air as the sweep gas further increased the C2 selectivity and yield. However, the conversion of methane was limited by both the low permeability of the membrane and the insufficient catalytic activity of the catalyst, leading to low C2 yield.

16.
Angew Chem Int Ed Engl ; 61(6): e202110429, 2022 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-34612568

RESUMO

Piezocatalysis, a newly emerging catalysis technology that relies on the piezopotential and piezoelectric properties of the catalysts, is attracting unprecedented research enthusiasm for applications in energy conversion, organic synthesis, and environmental remediation. Despite the rapid development in the past three years, the mechanism of piezocatalysis is still under debate. A fundamental understanding of the working principles of this technology should enable the future design and optimization of piezocatalysts. Herein, we provide an overview of the two popular theories used to explain the observed piezocatalysis: energy band theory and screening charge effect. A comprehensive discussion and clarification of the differences, relevance, evidence, and contradiction of the two mechanisms are provided. Finally, challenges and perspectives for future mechanistic studies are highlighted. Hopefully, this Review can help readers gain a better understanding of piezocatalysis and enable its application in their own research.

17.
Polymers (Basel) ; 13(13)2021 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-34201884

RESUMO

The 'Back-to-nature' concept has currently been adopted intensively in various industries, especially the pharmaceutical industry. In the past few decades, the overuse of synthetic chemicals has caused severe damage to the environment and ecosystem. One class of natural materials developed to substitute artificial chemicals in the pharmaceutical industries is the natural polymers, including cellulose and its derivatives. The development of nanocelluloses as nanocarriers in drug delivery systems has reached an advanced stage. Cellulose nanofiber (CNF), nanocrystal cellulose (NCC), and bacterial nanocellulose (BC) are the most common nanocellulose used as nanocarriers in drug delivery systems. Modification and functionalization using various processes and chemicals have been carried out to increase the adsorption and drug delivery performance of nanocellulose. Nanocellulose may be attached to the drug by physical interaction or chemical functionalization for covalent drug binding. Current development of nanocarrier formulations such as surfactant nanocellulose, ultra-lightweight porous materials, hydrogel, polyelectrolytes, and inorganic hybridizations has advanced to enable the construction of stimuli-responsive and specific recognition characteristics. Thus, an opportunity has emerged to develop a new generation of nanocellulose-based carriers that can modulate the drug conveyance for diverse drug characteristics. This review provides insights into selecting appropriate nanocellulose-based hybrid materials and the available modification routes to achieve satisfactory carrier performance and briefly discusses the essential criteria to achieve high-quality nanocellulose.

18.
ACS Appl Mater Interfaces ; 13(17): 20105-20113, 2021 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-33886260

RESUMO

Hydrocarbon-fueled solid oxide fuel cells (SOFCs) that can operate in the intermediate temperature range of 500-700 °C represent an attractive SOFC device for combined heat and power applications in the industrial market. One of the ways to realize such a device relies upon exploiting an in situ steam reforming process in the anode catalyzed by an anti-carbon coking catalyst. Here, we report a new Ni and Ru bimetal-doped perovskite catalyst, Ba(Zr0.1Ce0.7Y0.1Yb0.1)0.9Ni0.05Ru0.05O3-δ (BZCYYbNRu), with enhanced catalytic hydrogen production activity on n-butane (C4H10), which can resist carbon coking over extended operation durations. Ru in the perovskite lattice inhibits Ni precipitation from perovskite, and the high water adsorption capacity of proton conducting perovskite improves the coking resistance of BZCYYbNRu. When BZCYYbNRu is used as a steam reforming catalyst layer on a Ni-YSZ-supported anode, the single fuel cell not only achieves a higher power density of 1113 mW cm-2 at 700 °C under a 10 mL min-1 C4H10 continuous feed stream at a steam to carbon (H2O/C) ratio of 0.5 but also shows a much better operational stability for 100 h at 600 °C compared with those reported in the literature.

19.
ACS Omega ; 5(44): 28673-28683, 2020 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-33195920

RESUMO

Oil palm trunk (OPT) represents one of the five main oil palm biomass wastes with high carbon content that can be economically converted to a large surface area, porous activated carbon (AC) adsorbent to treat palm oil mill effluent wastewater in Indonesia and Malaysia. In the first portion of this work, the design of the experiment was used to determine the optimum set of synthesis parameters required to maximize the iodine number of AC [i.e., Brunauer-Emmett-Teller (BET) specific surface area indicator] prepared from OPT via chemical activation route using H3PO4. The iodine numbers of AC and AC yield were probed as the impregnation ratio, the activation time, and the activation temperature were varied in the range of 0.28-3.47, 5.68-69.32 min, and 379-521 °C, respectively. An impregnation ratio of 2.29, an activation time of 6 min, and an activation temperature of 450 °C were identified as the optimum set of synthesis parameters. In the second portion of the work, the AC synthesized using the optimum parameters were then characterized and tested as an adsorbent for tannin. N2 sorption results revealed that the AC exhibits type IV isotherm, that is, contains micropores and mesopores and displays a relatively high BET specific surface area of 1657 m2 g-1. Adsorption equilibria isotherms for tannin adsorption onto the AC were collected at three different pH of 2, 4, and 6 and were nonlinearly fitted using Langmuir and Freundlich isotherm models, where the Langmuir isotherm gave better fitting than Freundlich. The higher adsorption capacity at lower pH can be explained in terms of the absence of electrostatic repulsion interaction between the AC surface and the tannic acid species as suggested by the point of zero charges (pHpzc) of 4.8 and an increasing ionization of tannic acid with pH rise between 4 and 7. Adsorption kinetics data were also obtained at four different pH of 2, 4, 6, and 8 where the nonlinear pseudo-first-order model best fitted the kinetic at pH of 2 and the nonlinear pseudo-second-order model represented the kinetic best at the remaining higher pH, which suggests that tannin adsorption onto AC occurred by physisorption at pH of 2 and by chemisorption at pH of 4, 6, and 8.

20.
Small ; 16(14): e1906276, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32130789

RESUMO

Direct conversion of syngas to dimethyl ether (DME) through the intermediate of methanol allows more efficient DME production in a simpler reactor design relative to the conventional indirect route. Although Cu/ZnO-based multicomponent catalysts are highly active for methanol synthesis in this process, the sintering issue of Cu during the prolonged reaction generally deteriorates their performance. In this work, Cu/ZnO catalysts in a novel octahedron structure are prepared by a two-step pyrolysis of Zn-doped Cu-BTC metal-organic framework (MOF) in N2 and air. The catalyst CZ-350/A, hybrid of MOF-derived Cu/ZnO sample CZ-350 and γ-Al2 O3 for methanol dehydration, displays the best activity for DME formation (7.74% CO conversion and 70.05% DME selectivity) with the lowest deterioration rate over 40 h continuous reaction. Such performance is superior to its counterpart CZ-CP/A made via the conventional coprecipitation method. This is mainly due to the confinement of Cu nanoparticles within the octahedron matrix hindering their migration and aggregation. Besides, partial reduction of ZnO in the activated CZ-350 prompts the formation of Cu+ -O-Zn, further facilitating the DME production with the highest selectivity compared to literature results. The results clearly indicate that Cu and ZnO distribution in the catalyst architecture plays an important role in DME formation.

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