Adsorptive removal of herbicides with similar structures from water over nitrogen-enriched carbon, derived from melamine@metal-azolate framework-6.

Based on the recent concern on the pollution of water bodies with herbicides, adsorptive removal of typical herbicides with similar chemical structures, e. g. clofibric acid (CLFA), methylchlorophenoxypropionic acid or mecoprop (MCPP) and 2,4-dichlorophenoxyacetic acid (2,4-D) from water was studied using a porous nitrogen-enriched carbon. To prepare the nitrogen-enriched carbon, pyrolysis of a melamine (MLM) incorporated metal-azolate framework-6 (MLM(x)@MAF6; x = 0-50 M % of the ligand 2-ethylimidazole for MAF6), that was prepared for the first time via an in situ method, was carried out. The MLM(x)@MAF6-derived carbons (MDC6M(x)s) were characterized and used in the removal of CLFA, MCPP and 2,4-D from water. We found that the MDC6M(25), obtained from MLM(25)@MAF6 with 25% MLM (as the optimum precursor composition), showed the highest maximum adsorption capacity (Q0) of 1031 mg/g for CLFA, compared with any reported adsorbents, so far. The physicochemical properties of CLFA, as well as adsorbents and adsorptions under wide pH conditions, were employed to propose a plausible adsorption mechanism including hydrogen bonding. Remarkably, the porous carbon with enriched nitrogen, derived from MAF6 loaded MLM via in situ method, was very competitive in herbicides adsorption because of the contribution of well-dispersed nitrogen sties on the adsorbent. Finally, MDC6M(25) was suggested as a potential adsorbent for the removal of herbcides, including CLFA, MCPP and 2,4-D, from water, which is highly attractive to mitigate the environmental issue, especially, water pollution by various herbicides.

Fullerene Rosette: Two-Dimensional Interactive Nanoarchitectonics and Selective Vapor Sensing.

The simplicity of fullerenes as assembled components provides attractive opportunities for basic understanding in self-assembly research. We applied in situ reactive methods to the self-assembly process of C60 molecules with melamine/ethylenediamine components in solution, resulting in a novel type of fullerene assemblies, micron-sized two-dimensional, amorphous shape-regular objects, fullerene rosettes. ATR−FTIR spectra, XPS, and TGA results suggest that the melamine/ethylenediamine components strongly interact and/or are covalently linked with fullerenes in the fullerene rosettes. The broad peak for layer spacing in the XRD patterns of the fullerene rosettes corresponds roughly to the interdigitated fullerene bilayer or monolayer of modified fullerene molecules. The fullerene rosettes are made from the accumulation of bilayer/monolayer assemblies of hybridized fullerenes in low crystallinity. Prototype sensor systems were fabricated upon immobilization of the fullerene rosettes onto surfaces of a quartz crystal microbalance (QCM), and selective sensing of formic acid was demonstrated as preliminary results for social-demanded toxic material sensing. The QCM sensor with fullerene rosette is categorized as one of the large-response sensors among reported examples. In selectivity to formic acids against basic guests (formic acid/pyridine >30) or aromatic guests (formic acid/toluene >110), the fullerene rosette-based QCM sensor also showed superior performance.

How neutral nitrogen-containing compounds are oxidized in oxidative-denitrogenation of liquid fuel with TiO2@carbon.

Oxidative-denitrogenation (ODN) of indole (IND) and methyl-substituted INDs (methyl-INDs), representative neutral nitrogen-containing compounds (NCCs), was carried out with TiO2@C and H2O2 as heterogeneous catalyst and oxidant, respectively, under ultrasound irradiation. The oxidation of INDs progressed through radical formation, as evidenced by electron spin resonance and radical scavenger experiments. The oxidized position of INDs in the ODN process was checked via characterization of the obtained products. It was observed that the oxidation finally occurred on the carbon rather than on the nitrogen atom of INDs, unlike the oxidation of basic NCCs (e.g., oxidation on the nitrogen atom, as respective N-oxides were formed) and sulfur-containing compounds. To understand the relative reactivity and oxidation position, electron density (ED) on the nitrogen atom of the studied INDs and relative stability of representative intermediates/products were calculated. It could be confirmed that ED on the nitrogen atom of the INDs is very important in the oxidation of INDs since the ODN reactivity of INDs was enhanced with increasing ED on the nitrogen atom of the investigated INDs. Moreover, theoretical analyses of the relative stability of substrate and intermediates/products (especially for IND) can explain the route for the observed final products in ODN. In other words, oxygen on the nitrogen atom, obtained via the first step of oxidation (electrophilic addition of an active oxygen atom on nitrogen), moves to the nearby carbon atom, because of the relative stability of the intermediates and products.

Tungsten Nitride, Well-Dispersed on Porous Carbon: Remarkable Catalyst, Produced without Addition of Ammonia, for the Oxidative Desulfurization of Liquid Fuel.

Polyanilines (pANIs), loaded with phosphotungstic acid (PTA), are pyrolyzed to get WO3 or W2 N (≈6 and ≈7 nm, respectively), which is well-dispersed on pANI-derived porous carbons (pDCs). Depending on the pyrolysis temperature, WO3 /pDC, W2 N/pDC, or W2 N-W/pDCs could be obtained selectively. pANI acts as both the precursor of pDC and the nitrogen source for the nitridation of WO3 into W2 N during the pyrolysis. Importantly, W2 N could be obtained from the pyrolysis without ammonia feeding. The obtained W2 N/pDC is applied as a heterogeneous catalyst for the oxidative desulfurization (ODS) of liquid fuel for the first time, and the results are compared with WO3 /pDC and WO3 /ZrO2 . The W2 N/pDC is very efficient in ODS with remarkable performance compared with WO3 /pDC or WO3 /ZrO2 , which is applied as a representative ODS catalyst. For example, W2 N/pDC shows around 3.4 and 2.7 times of kinetic constant and turnover frequency (based on 5 min of reaction), respectively, compared to that of WO3 /ZrO2 . Moreover, the catalysts could be regenerated in a facile way. Therefore, W2 N/pDC could be produced facilely from pyrolysis (without ammonia feeding) of PTA/pANI, and W2 N, well-dispersed on pDC, can be suggested as a very efficient oxidation catalyst for the desulfurization of liquid fuel.

Hydrophobic Cobalt-Ethylimidazolate Frameworks: Phase-Pure Syntheses and Possible Application in Cleaning of Contaminated Water.

Two highly porous Co-based metal-azolate frameworks (MAFs), MAF-5(Co) and MAF-6(Co), which are isostructural with MAF-5(Zn) and MAF-6(Zn), respectively, were first synthesized in high yield and purity at room temperature. The syntheses compared two mixing methods, slow and fast, using cobalt acetate as the metal ion (Co2+) source and 2-ethylimidazole as the ligand. Triethylamine was applied as an additive/promoter in aqueous/ethanol solutions, and benzene and cyclohexane were used as hydrophobic templates. Phase-pure MAF-5(Co) and MAF-6(Co) were obtained in high yield by optimizing the mixing speed, reactant composition, and solvent/template ratio. It was found that fast mixing of the reactant mixtures was effective for synthesizing MAF(Co) materials. MAF-5(Co) and MAF-6(Co) were found to be very hydrophobic, similar to the MAFs composed of Zn, suggesting possible applications in water purification. MAF-5(Co) and MAF-6(Co) were then applied to adsorb n-octane as a model oil and nonpolar adsorbate from water, and the obtained results were compared to those of related materials, i.e., MAF-4(Co and Zn), MAF-5(Zn), and MAF-6(Zn), as well as with Cu-BTC (Cu-benzenetricarboxylate) and a conventional adsorbent, activated carbon. Surprisingly, despite having low porosity, MAF-5(Co) showed remarkable competitiveness among the typical porous materials for n-octane removal. The results suggest that the framework structure such as cavity and aperture sizes rather than surface area plays a significant role in n-octane removal. Moreover, MAF-5(Co) can easily be regenerated by simple evacuation and reused, and thus it was found to be a potential adsorbent for the removal of spilled oil from water. Additionally, MAFs were applied in the adsorption of diclofenac sodium from water, showing the competitiveness of MAFs in water purification probably because of hydrophobicity.

Metal-Organic Framework on Fullerene (MOFOF) as a Hierarchical Composite by the Integration of Coordination Chemistry and Supramolecular Chemistry.

There is a synergy between coordination chemistry and supramolecular chemistry that has led to the development of innovative hierarchical composites with diverse functionalities. Here, we present a novel approach for the synthesis and characterization of a metal-organic framework on fullerene (MOFOF) composites, achieved through the integration of coordination chemistry and supramolecular chemistry principles. The hierarchical nature of the MOFOF harnesses the inherent properties of metal-organic frameworks and fullerenes. The two-step synthesis procedure involves controlled assembly of fullerenes as tube-like nanostructures (fullerene nanotube: FNT), their surface functionalization, and the on-surface growth of the MOF (in this case, ZIF-67). The method permits the precise tuning of morphology, effective distribution of MOF-on-FNT, and tight compositional control. The materials were comprehensively structurally characterized using electron microscopy, spectroscopic techniques, and other methods to elucidate the unique features and interactions within the MOFOF composites. The main findings reveal that the novel synthesis and characterization of MOFOF composites demonstrate the successful integration of coordination chemistry and supramolecular chemistry for the designing and fabricating of advanced hierarchical composites with tailored properties, including micro- and mesopore channels, interfacial facets, and defect sites. These properties are expected to lead to numerous potential applications such as gas storage and separation, catalysis, sensing, energy storage, and environmental remediation. However, only the capability of acid vapor sensing was tested and is described here.

Biomass Nanoarchitectonics for Supercapacitor Applications.

Nanoarchitectonics integrates nanotechnology with numerous scientific disciplines to create innovative and novel functional materials from nano-units (atoms, molecules, and nanomaterials). The objective of nanoarchitectonics concept is to develop functional materials and systems with rationally architected functional units. This paper explores the progress and potential of this field using biomass nanoarchitectonics for supercapacitor applications as examples of energetic materials and devices. Strategic design of nanoporous carbons that exhibit ultra-high surface area and hierarchically pore architectures comprising micro- and mesopore structure and controlled pore size distributions are of great significance in energy-related applications, including in high-performance supercapacitors, lithium-ion batteries, and fuel cells. Agricultural wastes or natural biomass are lignocellulosic materials and are excellent carbon sources for the preparation of hierarchically porous carbons with an ultra-high surface area that are attractive materials in high-performance supercapacitor applications due to high electrical and ion conduction, extreme porosity, and exceptional chemical and thermal stability. In this review, we will focus on the latest advancements in the fabrication of hierarchical porous carbon materials from different biomass by chemical activation method. Particularly, the importance of biomass-derived ultra-high surface area porous carbons, hierarchical architectures with interconnected pores in high-energy storage, and high-performance supercapacitors applications will be discussed. Finally, the current challenges and outlook for the further improvement of carbon materials derived from biomass or agricultural wastes in the advancements of supercapacitor devices will be discussed.

Adsorptive removal of hazardous organics from water and fuel with functionalized metal-organic frameworks: Contribution of functional groups.

The purification of contaminated water and fuel is very important for our sustainability. Adsorptive removal has attracted significant attention because of possible applications in industry and the rapid development of metal-organic frameworks (MOFs), which can be competitive adsorbents. In this review, the possible/competitive purification of water (contaminated with organics) and fuel (composed of S- and N-Containing compounds) via adsorption using MOFs, especially those with various functional groups (FGs), will be discussed. The contribution of FGs such as -OH, -COOH, -SO3H, -NH2, and -NH3+ to adsorption/purification will be analyzed in detail, not only to understand the plausible adsorption mechanism but also to utilize specific FGs in adsorption. Moreover, methods for introducing FGs onto MOFs will be summarized. Finally, the prospects for both adsorption/removal and emerging fields will be suggested. Studies for practical applications in industry with shaped MOFs from inexpensive route will be important. The solution pH should be considered for the adsorption of aqueous solution. Applications of MOFs in other fields like storage/delivery and enrichment of analytes might be deeply studied.

Well-dispersed Ni or MnO nanoparticles on mesoporous carbons: preparation via carbonization of bimetallic MOF-74s for highly reactive redox catalysts.

A series of metal-organic framework-74s (MOF-74s), composed of two different metallic species (Zn/Ni or Zn/Mn in various compositions), were synthesized, and Ni or MnO-doped carbonaceous materials were first prepared by pyrolysis of the MOFs under an inert environment for catalytic applications. These MOF-derived nanomaterials (MDNMs), obtained by pyrolysis of MOF-74s, were characterized thoroughly to understand their phase, porosity, particle size, dispersion, and composition. With increasing Zn content in the bimetallic MOF-74s, the porosity of the MDNMs increased but the size and content of Ni or MnO in the MDNMs decreased monotonously. One MDNM(75Zn25Mn), prepared from MOF-74(75%Zn/25%Mn), showed noticeably higher activity in the oxidation of benzyl alcohol as compared with not only the MDNM(xZnyMn)s but also MnOx-loaded carbon or loaded γ-alumina (or, MDNM(75Zn25Mn) showed ∼54 times turnover frequency (TOF) to that of MnO/activated carbon). MDNM(75Zn25Mn) was also effective in the oxidative removal of dibenzothiophene from a model fuel. Moreover, MDNM(75Zn25Ni), prepared from MOF-74(75%Zn/25%Ni), had the highest TOF in the reduction of 4-nitrophenol among various MDNM(xZnyNi)s. The highest activity of MDNM(75Zn25Mn) and MDNM(75Zn25Ni), even with the lowest Mn and Ni contents in the respective MDNMs, for oxidation and reduction in several cycles might be due to the well-dispersed MnO (and Ni) and high porosity with mesopores. Therefore, it can be suggested that pyrolysis of mixed-metal MOFs such as MOF-74s can be a facile way to obtain highly effective and recyclable heterogeneous catalysts, with well-dispersed active species in very small sizes, for various organic reactions.

Adsorptive removal of aromatic hydrocarbons from water over metal azolate framework-6-derived carbons.

Metal azolate framework-6 (MAF-6) was pyrolyzed at 1000°C to yield MOF-derived carbons (MCs). The obtained MCs were used to eliminate aromatic hydrocarbons, including polyaromatic hydrocarbons (PAHs; e.g., naphthalene (NAP), anthracene (ATC), and pyrene (PRN)) and benzene (BZ) from water via adsorption. The adsorption results over the MCs were compared with that of pristine MAF-6 and commercial activated carbon (AC). MC obtained after 24h (MC-24) exhibited a remarkable adsorption efficiency compared to that of the other MCs (obtained after different durations), MAF-6, and AC. For example, MC-24 led to adsorptions of NAP around 17 and 2.5 times those of pristine MAF-6 and AC, respectively. Or, the maximum adsorption capacities (Q0) of MAF-6, AC and MC-24 for NAP were 14, 104 and 237mg/g, respectively. Moreover, Q0 values of MC-24 for ATC and PRN were also very high of 284 and 307mg/g, respectively. Based on the properties of PAHs and the hydrophobicity of MC-24, hydrophobic interaction was suggested as the main mechanism for the adsorption of PAHs and BZ. In addition, MC-24 can be recycled by washing with acetone with little loss in performance. Therefore, MC-24 is recommended as a competitive adsorbent for aromatic hydrocarbon removal from water.

A remarkable adsorbent for removal of contaminants of emerging concern from water: Porous carbon derived from metal azolate framework-6.

A series of metal-azolate frameworks or MAFs-MAF-4, -5, and -6-were synthesized and pyrolyzed to prepare porous carbons derived from MAFs (CDM-4, -5, -6, respectively). Not only the obtained carbons but also MAFs were characterized and applied for the adsorption of organic contaminants of emerging concern (CECs, including pharmaceuticals and personal care products) such as salicylic acid, clofibric acid, diclofenac sodium, bisphenol-A, and oxybenzone (OXB) from water. CDM-6 was found to be the most remarkable adsorbent among the tested ones (including activated carbon) for all the adsorbates. OXB was taken as a representative adsorbate for detailed adsorption studies as well as understanding the adsorption mechanism. H-bonding (H-acceptor: CDM; H-donor: CECs) was suggested as the principal mechanism for the adsorption of tested adsorbates. Finally, CDMs, especially CDM-6, were suggested as highly efficient and easily recyclable adsorbents for water purification.

Adsorption of benzotriazole and benzimidazole from water over a Co-based metal azolate framework MAF-5(Co).

Benzotriazole (BTA) and benzimidazole (BZI) are regarded as water pollutants because of their extensive uses in industry and appreciable water solubility. The adsorption of both BTA and BZI from water over a newly synthesized metal-organic framework, MAF-5(Co), was investigated and compared with zeolitic imidazole frameworks (ZIFs), such as ZIF-8(Zn) and ZIF-67(Co), as well as commercial activated carbon. MAF-5(Co) had the highest adsorption capacities for both BTA and BZI. The maximum adsorption capacities of MAF-5(Co) for BTA and BZI were 389 and 175mgg-1, respectively. Hydrophobic and π-π interactions between the aromatic adsorbate BTA and MAF-5(Co) were suggested as a plausible mechanism. Based on the zeta potential of MAF-5(Co) and effects of pH on the BTA adsorption, electrostatic interactions between the MAF-5(Co) and BTA species might also affect the adsorption of BTA over MAF-5(Co). MAF-5(Co) can be recycled for adsorptive removal of BTA by simple ethanol washing. Therefore, MAF-5(Co) is suggested as a promising adsorbent for the removal of BTA and BZI from water.

TiO2-Containing Carbon Derived from a Metal-Organic Framework Composite: A Highly Active Catalyst for Oxidative Desulfurization.

A new metal-organic framework (MOF) composite consisting of Ti- and Zn-based MOFs (ZIF-8(x)@H2N-MIL-125; in brief, ZIF(x)@MOF) was designed and synthesized. The pristine MOF [H2N-MIL-125 (MOF)]- and an MOF-composite [ZIF(30)@MOF]-derived mesoporous carbons consisting of TiO2 nanoparticles were prepared by pyrolysis (named MDC-P and MDC-C, respectively). MDC-C showed a higher surface area, larger pore sizes, and larger mesopore volumes than MDC-P. In addition, the TiO2 nanoparticles on MDC-C have more uniform shapes and sizes and are smaller than those of MDC-P. The obtained MDC-C and MDC-P [together with MOF, ZIF(30)@MOF, pure/nanocrystalline TiO2, and activated carbon] were applied in the oxidative desulfurization reaction of dibenzothiophene in a model fuel. The MDC-C, even with a lower TiO2 content than that of MDC-P, showed an outstanding catalytic performance, especially with a very low catalyst dose (i.e., a very high quantity of dibenzothiophene was converted per unit weight of the catalyst), fast kinetics (∼3 times faster than that for MDC-P), and a low activation energy (lower than that for any reported catalyst) for the oxidation of dibenzothiophene. The large mesopores of MDC-C and the well-dispersed/small TiO2 might be the dominant factors for the superior catalytic conversions. The oxidative desulfurization of other sulfur-containing organic compounds with various electron densities was also studied with MDC-C to understand the mechanism of catalysis. Moreover, the MDC-C catalyst can be reused many times in the oxidative desulfurization reaction after a simple washing with acetone. Finally, composing MOFs and subsequent pyrolysis is suggested as an effective way to prepare a catalyst with well-dispersed active sites, large pores, and high mesoporosity.

Selective Adsorption of n-Alkanes from n-Octane on Metal-Organic Frameworks: Length Selectivity.

The liquid-phase adsorption of n-alkanes (from n-octane (C8) solvent) with different chain lengths was carried out over three metal-organic frameworks (MOFs), viz., metal-azolate framework-6 (MAF-6), copper-benzenetricarboxylate (Cu-BTC), and iron-benzenetricarboxylate (MIL-100(Fe)), and a conventional adsorbent activated carbon (AC). MAF-6 and Cu-BTC were found to have significant selectivity for the adsorption of n-dodecane (C12) and n-heptane (C7), respectively, from C8. Selectivity for C12 on MAF-6 was also observed in competitive adsorption from binary adsorbate systems. To understand the selective adsorption of C12 on MAF-6 more, the adsorption of C12 from C8 over MAF-6 was investigated in detail and compared with that over AC. The obtained selectivities over MAF-6 and Cu-BTC for C12 and C7, respectively, might be explained by the similarity between cavity size of adsorbents and molecular length of n-alkanes. In the case of AC and MIL-100(Fe), no specific adsorption selectivity was observed because the cavity sizes of the two adsorbents are larger than the size of the n-alkanes used in this study. The adsorption capacities (qt) of n-alkanes over AC and MIL-100(Fe) decreased and increased, respectively, as the polarity (or length) of the adsorbates increased, probably because of nonpolar and polar interactions between the adsorbents and n-alkanes. On the basis of the results obtained, it can be concluded that matching the cavity size (of adsorbents) with the molecular length (of n-alknaes) is more important parameter than the MOF's hydrophilicity/hydrophobicity for the selective adsorption/separation of alkanes.

Adsorptive Removal of Pharmaceuticals and Personal Care Products from Water with Functionalized Metal-organic Frameworks: Remarkable Adsorbents with Hydrogen-bonding Abilities.

Adsorption of typical pharmaceuticals and personal care products (PPCPs) (such as naproxen, ibuprofen and oxybenzone) from aqueous solutions was studied by using the highly porous metal-organic framework (MOF) MIL-101 with and without functionalization. Adsorption results showed that MIL-101s with H-donor functional groups such as -OH and -NH2 were very effective for naproxen adsorption, despite a decrease in porosity, probably because of H-bonding between O atoms on naproxen and H atoms on the adsorbent. For this reason, MIL-101 with two functional groups capable of H-bonding (MIL-101-(OH)2) exhibited remarkable adsorption capacity based on adsorbent surface area. The favorable contributions of -OH and -(OH)2 on MIL-101 in the increased adsorption of ibuprofen and oxybenzone (especially based on porosity) confirmed again the importance of H-bonding mechanism. The adsorbent with the highest adsorption capacity, MIL-101-OH, was very competitive when compared with carbonaceous materials, mesoporous materials, and pristine MIL-101. Moreover, the MIL-101-OH could be recycled several times by simply washing with ethanol, suggesting potential application in the adsorptive removal of PPCPs from water.