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Fluoride contamination in groundwater has become a global environmental issue. Magnesium oxide (MgO) has demonstrated effectiveness as an adsorbent in treating fluoride pollution in groundwater. However, its use in powder and fine granular form often results in losses during the adsorption process, posing challenges for post-treatment recovery and potentially causing secondary environmental pollution. In this study, two novel fluoride adsorbents [rice husk (RH) and spent coffee grounds (SCG)-based magnesium oxide (MgO) biochar composites (MgO/RH and MgO/SCG)] were developed to cleanup fluoride-polluted groundwater. During the adsorbent synthesis process, RH and SCG biochar were pyrolyzed at 500 °C and modified by calcination using MgO. Both MgO/RH and MgO/SCG surfaces exhibited abundant pore structures and formed MgO crystal phases. Batch experiments results show that when the MgO/RH and MgO/SCG material dosages were 1 g/L, fluoride removal rates reached 80% and 86% respectively. The isotherms and kinetics of fluoride adsorption with MgO/RH and MgO/SCG followed the Langmuir isotherm equation and pseudo-second-order kinetic model. The maximum fluoride adsorption capacities of MgO/RH and MgO/SCG were 63.47 mg/g and 141.98 mg/g, respectively, indicating these materials used mono-layer adsorption mechanism for fluoride adsorption. The addition of MgO into the pores of porous adsorbent materials effectively increased their reactive sites and enhanced the adsorption performance of carbon materials. Particularly, SCG biochar had a richer pore structure than RH biochar, providing a larger contact surface area, facilitating the effective dispersion and doping of MgO into the pores. Therefore, MgO/SCG composite exhibited excellent fluoride adsorption properties in water, indicating the potential for developing a new type of MgO-modified SCG adsorbent material with green prospects. This composite effectively mitigated fluoride contamination, reducing the fluoride concentration in groundwater. Both RH and SCG are agricultural and food waste by-products, thus offering the opportunity to significantly reduce production, operation, and maintenance costs.
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The metal-organic frameworks (MOFs) attract interest as potential catalysts whose catalytic properties are driven by defects. Several methods have been proposed for the defects-inducing synthesis of MOFs. However, the active species formed on the defective sites remain elusive and uncharacterized, as the spectroscopic fingerprints of these species are hidden by the regular structure signals. In this work, we have performed the synthesis of ZIF-8 MOF with defect-inducing procedures using fully deuterated 2-methylimidazolate ligands to enhance the defective sites' visibility. By combining 1H and 31P MAS NMR spectroscopy and X-ray absorption spectroscopy, we have found evidence for the presence of different structural hydroxyl Zn-OH groups in the ZIF-8 materials. It is demonstrated that the ZIF-8 defect sites are represented by Zn-OH hydroxyl groups with the signals at 0.3 and -0.7 ppm in 1H MAS NMR spectrum. These species are of basic nature and may be responsible for the catalytic activity of the ZIF-8 material.
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MXenes (Mn+1XnTx), a subgroup of 2-dimensional (2D) materials, specifically comprise transition metal carbides, nitrides, and carbonitrides. They exhibit exceptional electrocatalytic and photocatalytic properties, making them well-suited for the detection and removal of pollutants from aqueous environments. Because of their high surface area and remarkable properties, they are being utilized in various applications, including catalysis, sensing, and adsorption, to combat pollution and mitigate its adverse effects. Different characterization techniques like XRD, SEM, TEM, UV-Visible spectroscopy, and Raman spectroscopy have been used for the structural elucidation of 2D MXene. Current responses against applied potential were measured during the electrochemical sensing of the hazardous pollutants in an aqueous system using a variety of electroanalytical techniques, including differential pulse voltammetry, amperometry, square wave anodic stripping voltammetry, etc. In this review, a comprehensive discussion on structural patterns, synthesis, properties of MXene and their application for electrochemical detection of lethal pollutants like hydroquionone, phenol, catechol, mercury and lead, etc. are presented. This review will be helpful to critically understand the methods of synthesis and application of MXenes for the removal of environmental pollutants.
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Tailor-made unsaturated coordination of metal ions or organic linkers in zeolitic imidazole frameworks (ZIFs) has great potential in tuning the ZIFs' properties and reactivity for their applications. Taking advantage of the solid-state thermal (SST) method as a facile and eco-friendly synthesis method, the rational coordination of metal ions with imidazole ligands in ZIF-67 through the SST method is investigated. The rational precursor ratio (metal-to-ligand source) under the solvent-free SST method emerges as a perfect strategy to tune the coordinately unsaturated sites within the ZIF-67 frameworks. Different analysis techniques, computational methods (DFT), and catalytic model reactions examine unsaturated coordination in ZIF-67 materials (defect structures). The unsaturated coordination provides unique characteristic properties on materials with excellent catalytic performance. However, the higher reactive properties are negotiated with weaker structural stability on materials. In addition, the post-SST approach is applied to enable rational coordination and modify the pristine ZIF-67 materials. The post-SST method rearranges and modifies coordination in the framework of materials. These findings are crucial to understanding the role of the uncoordinated degree to balance with structural stability based on ZIF-67, which is critical for effective heterogeneous catalysts.
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The synthesis of novel metal-organic coordination polymers (MOCP) with the chemical formula [Mn2L (SCN)2(OH)2]3·CH3OH [L = 1,5-bis(pyridine-4-ylmethylene) carbonohydrazide] {1} was accomplished using two different techniques: solvothermal and sonochemical ultrasonic-assisted. An investigation was carried out to examine the impact of various factors such as reaction time, sonication power, temperature, and reactant concentration on the morphology and size of the crystals. Interestingly, it was found that sonication power and temperature did not affect the crystals' morphology and size. To further analyze the prepared microcrystals of MOCPs, SEM was utilized to examine their surface morphology, and XRD, elemental evaluation composition. The identification of the functional groups present in the prepared Mn-MOCPs was accomplished through the utilization of FT-IR spectroscopy. Subsequently, the calcination of 1 in an air atmosphere at 650 °C led to the formation of Mn3O4 nanoparticles. The geometric and electronic structure of the MOCPs was evaluated using density functional theory (DFT). The utilization of molecular docking methodologies demonstrated that the best cavity of the human androgen receptor possessed an interaction energy of -116.3 kJ mol-1. This energy encompassed a combination of both bonding and non-bonding interactions. The Results showed that steric interaction and electrostatic potential are the main interactions in AR polymer and Mn(II). These interactions in the defined cavity indicated that this polymer could be an effective anti-prostate candidate, because AR is involved in the growth of prostate cancer cells, and these interactions indicated the inhibition of prostate cancer cell growth.
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Polypropylene hybrid polymeric membranes with aramid support have been fabricated using Thermally Induced Phase Separation (TIPS). Different modifying materials, such as metallic nanoparticles and reduced graphene oxide (rGO), improve the properties of these membranes. The nanomaterials and the fabricated membranes have been characterized with FTIR spectrometer, SEM and UV-Vis Spectrophotometer. Following that, the disinfection capabilities of the fabricated hybrid membranes were investigated. The antibacterial capability of the membranes is established through the testing of the membranes against bacterial strains S. aureus and E. coli, whereas the antiviral evaluation of the membranes was made against H9N2 and IBV strains. This research aims to develop advanced hybrid membranes that effectively disinfect water by incorporating novel nanomaterials and optimizing fabrication techniques.
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α-Hydroxy ketones are a class of vital organic skeletons that generally exist in a variety of natural products and high-value chemicals. However, the traditional synthetic route for their production involves toxic Hg salts and corrosive H2SO4 as catalysts, resulting in harsh conditions and the undesired side reaction of Meyer-Schuster rearrangement. In this study, CO2-promoted hydration of propargylic alcohols was achieved for the synthesis of various α-hydroxy ketones. Notably, this process was catalyzed using an environmentally friendly and cost-effective biomass-based ionic liquids/CuCl system, which effectively eliminated the side reaction. The ionic liquids utilized in this system are derived from natural biomass materials, which exhibited recyclability and catalytic activity under 1 bar of CO2 pressure without volatile organic solvents or additives. Evaluation of the green metrics revealed the superiority of this CuCl/ionic liquid system in terms of environmental sustainability. Further mechanistic investigation attributed the excellent performance to the ionic liquid component, which exhibited multifunctionality in activating substrates, CO2 and the Cu component.
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Alcinos , Líquidos Iônicos , Propanóis , Cetonas , Dióxido de Carbono , Biomassa , CatáliseRESUMO
This study focuses on the mutual interaction of substituents in the nucleophile and substrate - cross interaction constant, ρXY, in the uncatalyzed aminolysis by substituting pyridine with phenyl carbonyl isothiocyanate. The mechanism was found to be a stepwise process with a rate-limiting breakdown of the -NCS leaving group. This stepwise reaction mechanism considers the cross-interaction constant (CIC) with rate-limiting breakdown of tetrahedral intermediate in gas and solvent phases. The corresponding Hammett coefficients are related to the substituents associated with (1) the nucleophiles (X), ρX (-1.93 to -6.54 for the gas phase and 10.5 to 18.9 in the solvent model), and with (2) the substituents associated with the phenyl ring of the substrate (Y), ρY (0.41-3.48 for the gas phase and 1.83 to -10.70 for the solvent model). It also includes the Brønsted coefficient with X, ßX (0.11-1.52 for the gas phase and -2.57 to 3.96 for the solvent model), and CIC values, ρXY (0.69 for the gas phase and 0.87 for the solvent model). In this work, the NBO analysis, reaction potential, reaction electronic flux (REF), dual descriptor, and the structure-energy relationships were considered in interpreting the mechanistic criteria.
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Correlated single-atom catalysts (c-SACs) with tailored intersite metal-metal interactions are superior to conventional catalysts with isolated metal sites. However, precise quantification of the single-atomic interdistance (SAD) in c-SACs is not yet achieved, which is essential for a crucial understanding and remarkable improvement of the correlated metal-site-governed catalytic reaction kinetics. Here, three Ru c-SACs are fabricated with precise SAD using a planar organometallic molecular design and π-π molecule-carbon nanotube confinement. This strategy results in graded SAD from 2.4 to 9.3 Å in the Ru c-SACs, wherein tailoring the Ru SAD into 7.0 Å generates an exceptionally high turnover frequency of 17.92 H2 s-1 and a remarkable mass activity of 100.4 A mg-1 under 50 and 100 mV overpotentials, respectively, which is superior to all the Ru-based catalysts reported previously. Furthermore, density functional theory calculations confirm that Ru SAD has a negative correlation with its d-band center owing to the long-range interactions induced by distinct local atomic geometries, resulting in an appropriate electrostatic potential and the highest catalytic activity on c-SACs with 7.0 Å Ru SAD. The present study promises an attractive methodology for experimentally quantifying the metal SAD to provide valuable insights into the catalytic mechanism of c-SACs.
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In this study, the magnesium oxide (MgO)-based adsorbents [granulated MgO aggregates (GA-MgO) and surface-modified MgO powder (SM-MgO)] were developed to remediate a fluoride-contaminated groundwater site. Both GA-MgO and SM-MgO had porous, spherical, and crystalline structures. Diameters for GA-MgO and SM-MgO were 1-1.7 mm and 1-10 µm, respectively. The pseudo second-order dynamic adsorption and the Freundlich isotherm could be applied to express the chemical adsorption phenomena. The monolayer adsorption was the dominant mechanism at the initial adsorption period. During the latter part of fluoride adsorption, the multilayer adsorption became the dominant mechanism for fluoride removal from the water phase, which also resulted in the increased adsorption capacity. Higher hydroxide, phosphate, and carbonate concentrations caused a decreased fluoride removal efficiency due to the competition of sorption sites between fluoride and other anions with similar electronic properties. Fluoride removal mechanism using GA-MgO and SM-MgO as the adsorbents was mainly carried out by the chemical adsorption. Reaction paths contained two main processes: (1) formation of magnesium hydroxide after the reaction of MgO with water, and (2) the hydroxyl group of the magnesium hydroxide was replaced by fluoride ions to form magnesium fluoride precipitation. Results from column tests show that up to 61 and 73% of fluoride removal (initial fluoride concentration = 9.3 mg/L) could be obtained after 50 pore volumes of groundwater pumping with GA-MgO and SM-MgO injection, respectively. The GA-MgO system could be applied to contain and remediate fluoride-contaminated groundwater, and SM-MgO could be applied as an immediate fluoride removal alternative to achieve a rapid pollutant removal for emergency responses. Up to 71% of fluoride removal (fluoride concentration = 10.8 mg/L) could be obtained with GA-MgO injection after 30 days of operation. The developed GA-MgO system is a potential and green remediation alternative to contain the fluoride plume significantly.
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Água Subterrânea , Poluentes Químicos da Água , Óxido de Magnésio/química , Fluoretos , Hidróxido de Magnésio , Poluentes Químicos da Água/análise , Adsorção , Água , Cinética , Concentração de Íons de HidrogênioRESUMO
The progressive trend of utilizing bioactive materials constitutes diverse materials exhibiting biocompatibility. The innovative aspect of this research is the tuning of the thermo-mechanical behavior of polyurethane (PU) composites with improved biocompatibility for vibrant applications. Polycaprolactone (CAPA) Mn = 2000 g-mol-1 was used as a macrodiol, along with toluene diisocyanate (TDI) and hexamethylene diisocyanate (HMDI), to develop prepolymer chains, which were terminated with 1,4 butane diol (BD). The matrix was reinforced with various concentrations of chitosan (1-5 wt %). Two series of PU composites (PUT/PUH) based on aromatic and aliphatic diisocyanate were prepared by varying the hard segment (HS) ratio from 5 to 30 (wt %). The Fourier-transformed infrared (FTIR) spectroscopy showed the absence of an NCO peak at 1730 cm-1 in order to confirm polymer chain termination. Thermal gravimetric analysis (TGA) showed optimum weight loss up to 500 °C. Dynamic mechanical analysis (DMA) showed the complex modulus (E*) ≥ 200 MPa. The scanning electron microscope (SEM) proved the ordered structure and uniform distribution of chain extender in PU. The hemolytic activities were recorded up to 15.8 ± 1.5% for the PUH series. The optimum values for the inhibition of biofilm formation were recorded as 46.3 ± 1.8% against E. coli and S. aureus (%), which was supported by phase contrast microscopy.
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Quitosana , Poliuretanos , Poliuretanos/química , Quitosana/química , Escherichia coli , Staphylococcus aureus , BioensaioRESUMO
Soil and groundwater contamination caused by petroleum hydrocarbons is a severe environmental problem. In this study, a novel electrolyzed catalytic system (ECS) was developed to produce nanobubble-contained electrolyzed catalytic (NEC) water for the remediation of petroleum-hydrocarbon-contaminated soils and groundwater. The developed ECS applied high voltage (220 V) with direct current, and titanium electrodes coated with iridium dioxide were used in the system. The developed ECS prototype contained 21 electrode pairs (with a current density of 20 mA/cm2), which were connected in series to significantly enhance the hydroxyl radical production rate. Iron-copper hybrid oxide catalysts were laid between each electrode pair to improve the radical generation efficiency. The electron paramagnetic resonance (EPR) and Rhodamine B (RhB) methods were applied for the generated radical species and concentration determination. During the operation of the ECS, high concentrations of nanobubbles (nanobubble density = 3.7 × 109 particles/mL) were produced due to the occurrence of the cavitation mechanism. Because of the negative zeta potential and nano-scale characteristics of nanobubbles (mean diameter = 28 nm), the repelling force would prevent the occurrence of bubble aggregations and extend their lifetime in NEC water. The radicals produced after the bursting of the nanobubbles would be beneficial for the increase of the radical concentration and subsequent petroleum hydrocarbon oxidation. The highly oxidized NEC water (oxidation-reduction potential = 887 mV) could be produced with a radical concentration of 9.5 × 10-9 M. In the pilot-scale study, the prototype system was applied to clean up petroleum-hydrocarbon polluted soils at a diesel-oil spill site via an on-site slurry-phase soil washing process. The total petroleum hydrocarbon (TPH)-contaminated soils were excavated and treated with the NEC water in a slurry-phase reactor. Results show that up to 74.4% of TPH (initial concentration = 2846 mg/kg) could be removed from soils after four rounds of NEC water treatment (soil and NEC water ratio for each batch = 10 kg: 40 L and reaction time = 10 min). Within the petroleum-hydrocarbon plume, one remediation well (RW) and two monitor wells (located 1 m and 3 m downgradient of the RW) were installed along the groundwater flow direction. The produced NEC water was injected into the RW and the TPH concentrations in groundwater (initial concentrations = 12.3-15.2 mg/L) were assessed in these three wells. Compared to the control well, TPH concentrations in RW and MW1 dropped to below 0.4 and 2.1 mg/L after 6 m3 of NEC water injection in RW, respectively. Results from the pilot-scale study indicate that the NEC water could effectively remediate TPH-contaminated soils and groundwater without secondary pollution production. The main treatment mechanisms included (1) in situ chemical oxidation via produced radicals, (2) desorption of petroleum hydrocarbons from soil particles due to the dispersion of nanobubbles into soil pores, and (3) enhanced TPH oxidation due to produced radicals and energy after nanobubble bursting.
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Água Subterrânea , Petróleo , Poluentes do Solo , Poluição Ambiental , Hidrocarbonetos , Solo , Poluentes do Solo/análise , Biodegradação Ambiental , Microbiologia do SoloRESUMO
Acoustic-activated polarization at two-dimensional (2D) domains provide supplementary mechanisms for adjustment of empty and occupied orbitals at material heterointerfaces, activating a wide range of physicochemical applications. The piezoelectric nanodomains grown at 2D liquid-metal heterointerfaces represent a new class of polarization-dependent hybrid nanostructures with a highly challenging fabrication process. Here, the controlled growth of selenium-rich piezoelectric nanodomains on the nonpolar 2D surface of liquid Ga-based nanoparticles (NPs) enabled highly efficient and sustainable CO2 conversion. The Ga-based NPs were engulfed in carbon nanotube (CNT) frameworks. The initial hindrance effects of CNT frameworks suppressed the undesirable Ga-Se amalgamation to guarantee the suitable functions of piezocatalyst. Simultaneously, the CNT-Se mesoporous network enhances the transport and interaction of ionic species at heterointerfaces, providing unique selectivity features for CO2 conversion. Driven by acoustic energy, the multiple contributions of Ga-Se polarized heterointerfaces facilitated the piezoelectric switching and therefore increased the CO2 conversion efficiency to the value of 95.8%. The inherent compositional and functional tunability of the Ga-Se nanojunction reveal superior control over the catalyst heterointerfaces and thereby show promising potential for nanoscale applications.
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The Salt River is an important urban river in Kaohsiung, Taiwan. In this study, the source identification and risk and toxicity assessment of the heavy-metal-contaminated sediments in the Salt River were investigated. The geo-accumulation index (Igeo), enrichment factor (EF), sediment quality guidelines (SQGs), potential ecological risk index (RI), pollution load index (PLI), and toxic units (TU) were applied to determine effects of heavy metals on microbial diversities and ecosystems. Results from the ecological and environmental risk assessment show that high concentrations of Zn, Cr, and Ni were detected in the midstream area and the sum of toxic units (ΣTUs) in the midstream (7.2-32.0) is higher than in the downstream (14.0-19.7) and upstream (9.2-17.1). It could be because of the continuous inputs of heavy-metal-contained wastewaters from adjacent industrial parks. Results also inferred that the detected heavy metals in the upstream residential and commercial areas were possibly caused by nearby vehicle emissions, non-point source pollution, and domestic wastewater discharges. Results of metagenomic assays show that the sediments contained significant microbial diversities. Metal-tolerant bacterial phyla (Proteobacteria: 24.4%-46.4%, Bacteroidetes: 1.3%-14.8%, and Actinobacteria: 2.3%-11.1%) and pathogenic bacterial phyla (Chlamydiae: 0.5%-37.6% and Chloroflexi: 5.8%-7.2%) with relatively high abundance were detected. Metal-tolerant bacteria would adsorb metals and cause the increased metal concentrations in sediments. Results indicate that the bacterial composition in sediment environments was affected by anthropogenic pollution and human activities and the heavy-metal-polluted ecosystem caused the variations in bacterial communities. PRACTITIONER POINTS: Microbial community in sediments is highly affected by heavy metal pollution. Wastewaters and vehicle traffic contribute to river sediments pollution by heavy metals. Proteobacteria, Bacteroidota, and Actinobacteria are dominant heavy-metal-tolerant bacterial phyla in sediments. Toxicity assessment is required to study risk levels of heavy-metal contained sediments.
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Metais Pesados , Microbiota , Poluentes Químicos da Água , Humanos , Águas Residuárias , Sedimentos Geológicos , Poluentes Químicos da Água/toxicidade , Poluentes Químicos da Água/análise , Monitoramento Ambiental/métodos , Metais Pesados/toxicidade , Metais Pesados/análise , Proteobactérias , Medição de Risco , ChinaRESUMO
Acyl-amide is extensively used as functional group and is a superior contender for the design of MOFs with the guest accessible functional organic sites. A novel acyl-amide-containing tetracarboxylate ligand, bis(3,5-dicarboxy-pheny1)terephthalamide, has been successfully synthesized. The H4L linker has some fascinating attributes as follows: (i) four carboxylate moieties as the coordination sites confirm affluent coordination approaches to figure a diversity of structure; (ii) two acyl-amide groups as the guest interaction sites can engender guest molecules integrated into the MOF networks through H-bonding interfaces and have a possibility to act as functional organic sites for the condensation reaction. A mesoporous MOF ([Cu2(L)(H2O)3]·4DMF·6H2O) has been prepared in order to produce the amide FOS within the MOF, which will work as guest accessible sites. The prepared MOF was characterized by CHN analysis, PXRD, FTIR spectroscopy, and SEM analysis. The MOF showed superior catalytic activity for Knoevenagel condensation. The catalytic system endures a broad variety of the functional groups and presents high to modest yields of aldehydes containing electron withdrawing groups (4-chloro, 4-fluoro, 4-nitro), offering a yield > 98 in less reaction time as compared to aldehydes with electron donationg groups (4-methyl). The amide decorated MOF (LOCOM-1-) as a heterogeneous catalyst can be simply recovered by centrifugation and recycled again without a flagrant loss of its catalytic efficiency.
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A total of 603 samples of selected spices from different seasons (winter and summer) were analyzed for the occurrence of aflatoxin B1 (AFB1), total AFs, and tocopherols. The findings revealed that 120 (38.7%) samples from the summer and 136 (46.4%) samples from the winter season were observed to be infected with AFB1 and a large amount of AFs. The highest means of both AFB1 and total Afs were observed in red pepper, i.e., 15.5 ± 3.90 µg/kg and 22.90 ± 4.10 µg/kg, respectively. The minimum averages of AFB1 and total AFs were observed in cloves of 6.32 ± 1.8 and 8.40 ± 1.60 µg/kg, respectively (from the winter season). The seasonal variations in the levels of the total AFs in selected spices were observed to be nonsignificant (p ≥ 0.05), except for the levels in red pepper and ginger samples, which showed significant differences (p ≤ 0.05). The maximum average of the dietary intake of Afs, 4.80 µg/day/kg, was found in ginger from the winter season in individual females. Furthermore, the findings document that the maximum level of total tocopherol, i.e., 44.8 ± 9.3 mg/100 g, was observed in black pepper from the winter season. A significant difference in the concentration of total tocopherols was observed in selected spices from the summer and the winter seasons (p ≤ 0.05).
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Aflatoxinas , Capsicum , Aflatoxina B1/análise , Aflatoxinas/análise , Cromatografia Líquida de Alta Pressão , Contaminação de Alimentos/análise , Medição de Risco , Estações do Ano , Especiarias/análise , TocoferóisRESUMO
Water oxidation has become very popular due to its prime role in water splitting and metal-air batteries. Thus, the development of efficient, abundant, and economical catalysts, as well as electrode design, is very demanding today. In this review, we have discussed the principles of electrocatalytic water oxidation reaction (WOR), the electrocatalyst and electrode design strategies for the most efficient results, and recent advancement in the oxygen evolution reaction (OER) catalyst design. Finally, we have discussed the use of OER in the Oxygen Maker (OM) design with the example of OM REDOX by Solaire Initiative Private Ltd. The review clearly summarizes the future directions and applications for sustainable energy utilization with the help of water splitting and the way forward to develop better cell designs with electrodes and catalysts for practical applications. We hope this review will offer a basic understanding of the OER process and WOR in general along with the standard parameters to evaluate the performance and encourage more WOR-based profound innovations to make their way from the lab to the market following the example of OM REDOX.
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The performance of most polymer membranes suffers from the trade-off relationship between permeability and selectivity [...].
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For large-scale applications, dye-sensitized solar cells (DSSCs) require the replacement of the scarce platinum (Pt)-based counter electrode (CE) with efficient and cheap alternatives. In this respect, low-cost perovskite oxides (ABO3) have been introduced as promising additives to composite-based CEs in Pt-free DSSCs. Herein, we synthesized composites from La0.9Ce0.1NiO3 (L) perovskite oxide and functionalized-multiwall-carbon-nanotubes wrapped in selenides derived from metal-organic-frameworks (f-MWCNT-ZnSe-CoSe2, "F"). L and F were then mixed with carbon black (CB) in different mass ratios to prepare L@CB, F@CB, and L@F@CB composites. The electrochemical analysis revealed that the L@F@CB composite with a mass ratio of 1.5:3:1.5 exhibits better electrocatalytic activity than Pt. In addition, the related DSSC reached a better PCE of 7.49% compared to its Pt-based counterpart (7.09%). This improved performance is the result of the increase in the oxygen vacancy by L due to the replacement of La with Ce in its structure, leading to more active sites in the L@F@CB composites. Moreover, the F@CB composite favors the contribution to the high electrical conductivity of the hybrid carbon nanotube-carbon black, which also offers good stability to the L@F@CB CE by not showing any obvious change in morphology and peak-to-peak separation even after 100 cyclic voltammetry cycles. Consequently, the corresponding L@F@CB-based device achieved enhanced stability. Our work demonstrates that L@F@CB composites with a low cost are excellent alternatives to Pt CE in DSSCs.
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In this work, a Cs2 CO3 -promoted synthetic approach was identified for (hetero)aryl ether synthesis via the C-O coupling of various (hetero)aryl chlorides and alcohols/phenol. To our delight, the reactions could be carried out under transition-metal-free and solvent-free conditions. Moreover, analytical-grade reagents and air atmosphere were readily tolerated. To showcase the practical usefulness of the present protocol, the assembly of a bioactive molecule was facilely realized and the gram-scale production of selected ether products was also efficiently accomplished. In addition, density functional theory (DFT) studies, along with a few mechanistic experiments, were conducted to elucidate a proposed reaction pathway and rationalize the pivotal role of Cs2 CO3 in promoting this process. Hopefully, this work could provide useful information for researchers who are engaging in C-O cross-coupling reactions.