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A continuous flow methodology for the facile and high-yielding synthesis of the porphyrin-based self-assembled organic cage, P12 L24 is reported, along with the serendipitous discovery of a kinetic product, P9 L18 cage, which has been characterized by MALDI-TOF MS, NMR, and AFM analysis. A theoretical study suggests a tricapped trigonal prismatic geometry for P9 L18 . Unlike P12 L24 , P9 L18 is unstable and readily decomposes into monomers and small oligomers. While the batch synthesis produces only the thermodynamic product P12 L24 , the continuous flow process generates not only the thermodynamic product but also kinetic products, such as P9 L18 , illustrating the advantages of the continuous flow process for the synthesis of self-assembled cages and the exploration of new non-equilibrium assemblies.
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Inverse-electron-demand Diels-Alder reaction (IEDDA) between fullerenes and 1,2,4,5-tetrazine generally requires harsh conditions and long reaction times due to their strong electron-accepting nature. Herein, we report a dramatic enhancement in the reactivity of the fullerenes (C60 /C70 )-tetrazine reaction inside a porous Zn-porphyrinic cage (Zn-PB) under sustainable conditions by installing a tetrazine-based axle (LA) via metal-ligand coordination bond, which modulates the cavity size to facilitate the encapsulation of fullerenes. Upon encapsulation, the close proximity of fullerenes and the tetrazine group of LA dramatically increase their reactivity towards the IEDDA reaction to form fullerene-tetrazine adducts. Furthermore, the C60 -tetrazine adduct is rearranged upon hydration to a bent-shaped C60 -pyrazoline adduct that can be released from the Zn-PB cavity in the presence of excess LA, thus catalyzing the formation of C60 -pyrazoline adduct inside Zn-PB without product inhibition.
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The preparation of sub 3 nm copper nanoparticles (CuNPs) in ethylene glycol (EG) using triethylene tetramine (TETA) as chelating and reducing agents via a rapid microwave (MW) irradiation is reported. The sub 3 nm CuNPs after MW irradiation are clearly seen from the electronic micrographs. The firm chelation of Cu2+ by TETA is illustrated by the dark blue color of Cu2+/TETA/EG solution and the redox reaction is confirmed by the appearance of red color of the mixtures. The optimal mole ratio of TETA/Cu 2+ is found to be 2.5/1 for preparing sub 3 nm CuNPs under the MW irradiation, operated at 800 W for 1 min. The plasmonic absorption λ max demonstrated in UV-vis spectra are found to close to 200 nm for sub 3 nm CuNPs, comparing to 500 â¼ 600 nm for regular, larger CuNPs. The extremely low Tm around 30 °C and the fusion/recrystallization sequence of sub 3 nm CuNPs can be directly measured by their differential scanning calorimetry thermograms.
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In this paper, a cobalt (Co)-chelated polynaphthalene imine (Co-PNIM) was calcined to become an oxygen reduction reaction (ORR) electrocatalyst (Co-N-C) as the cathode catalyst (CC) of an anion exchange membrane fuel cell (AEMFC). The X-ray diffraction pattern of CoNC-1000A900 illustrated that the carbon matrix develops clear C(002) and Co(111) planes after calcination, which was confirmed using high-resolution TEM pictures. Co-N-Cs also demonstrated a significant ORR peak at 0.8 V in a C-V (current vs. voltage) curve and produced an extremely limited reduction current density (5.46 mA cm-2) comparable to commercial Pt/C catalysts (5.26 mA cm-2). The measured halfway potential of Co-N-C (0.82 V) was even higher than that of Pt/C (0.81 V). The maximum power density (Pmax) of the AEM single cell upon applying Co-N-C as the CC was 243 mW cm-2, only slightly lower than that of Pt/C (280 mW cm-2). The Tafel slope of CoNC-1000A900 (33.3 mV dec-1) was lower than that of Pt/C (43.3 mV dec-1). The limited reduction current density only decayed by 7.9% for CoNC-1000A900, compared to 22.7% for Pt/C, after 10,000 redox cycles.
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In order to yield more Co(II), 2,6-diaminopyridine (DAP) was polymerized with 4,4-methylene diphenyl diisocyanates (MDI) in the presence of Co(II) to obtain a Co-complexed polyurea (Co-PUr). The obtained Co-PUr was calcined to become Co, N-doped carbon (Co-N-C) as the cathode catalyst of an anion exchange membrane fuel cell (AEMFC). High-resolution transmission electron microscopy (HR-TEM) of Co-N-C indicated many Co-Nx (Co covalent bonding with several nitrogen) units in the Co-N-C matrix. X-ray diffraction patterns showed that carbon and cobalt crystallized in the Co-N-C catalysts. The Raman spectra showed that the carbon matrix of Co-N-C became ordered with increased calcination temperature. The surface area (dominated by micropores) of Co-N-Cs also increased with the calcination temperature. The non-precious Co-N-C demonstrated comparable electrochemical properties (oxygen reduction reaction: ORR) to commercial precious Pt/C, such as high on-set and half-wave voltages, high limited reduction current density, and lower Tafel slope. The number of electrons transferred in the cathode was close to four, indicating complete ORR. The max. power density (Pmax) of the single cell with the Co-N-C cathode catalyst demonstrated a high value of 227.7 mWcm-2.
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Aromatic polyimide has good mechanical properties and high-temperature resistance. Based on this, benzimidazole is introduced into the main chain, and its intermolecular (internal) hydrogen bond can increase mechanical and thermal properties and electrolyte wettability. Aromatic dianhydride 4,4'-oxydiphthalic anhydride (ODPA) and benzimidazole-containing diamine 6,6'-bis [2-(4-aminophenyl)benzimidazole] (BAPBI) were synthesized by means of a two-step method. Imidazole polyimide (BI-PI) was used to make a nanofiber membrane separator (NFMS) by electrospinning process, using its high porosity and continuous pore characteristics to reduce the ion diffusion resistance of the NFMS, enhancing the rapid charge and discharge performance. BI-PI has good thermal properties, with a Td5% of 527 °C and a dynamic mechanical analysis Tg of 395 °C. The tensile strength of the NFMS increased from 10.92MPa to 51.15MPa after being hot-pressed. BI-PI has good miscibility with LIB electrolyte, the porosity of the film is 73%, and the electrolyte absorption rate reaches 1454%. That explains the higher ion conductivity (2.02 mS cm-1) of NFMS than commercial one (0.105 mS cm-1). When applied to LIB, it is found that it has high cyclic stability and excellent rate performance at high current density (2 C). BI-PI (120 Ω) has a lower charge transfer resistance than the commercial separator Celgard H1612 (143 Ω).
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A novel cobalt-chelating polyimine (Co-PIM) containing an additional amine group is prepared from the condensation polymerization of diethylene triamine (DETA) and terephthalalehyde (PTAl) by the Schiff reaction. A Co, N-co-doped carbon material (Co-N-C), obtained from two-stage calcination in different gas atmospheres is used as the cathode catalyst of an anion exchange membrane fuel cell (AEMFC). The Co-N-C catalyst demonstrates a CoNx-type single-atom structure seen under high-resolution transmission electron microscopy (HRTEM). The Co-N-C catalysts are characterized by FTIR, XRD, and Raman spectroscopy as well. Their morphologies are also illustrated by SEM and TEM micrographs, respectively. Surface area and pore size distribution are found by BET analysis. Co-N-C catalysts exhibit a remarkable oxygen reduction reaction (ORR) at 0.8 V in the KOH(aq). From the LSV (linear-sweeping voltammetry) curves, the onset potential relative to RHE is 1.19-1.37 V, the half wave potential is 0.73-0.78 V, the Tafel slopes are 76.9-93.6 mV dec-1, and the average number of exchange electrons is 3.81. The limiting reduction current of CoNC-1000A-900 is almost the same as that of commercial 20 wt% Pt-deposited carbon particles (Pt/C), and the max power density (Pmax) of the single cell using CoNC-1000A-900 as the cathode catalyst reaches 361 mW cm-2, which is higher than Pt/C (284 mW cm-2).
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Polyazomethine (PAM) prepared from the polycondensation between p-phenylene diamine (PDA) and p-terephthalaldehyde (PTAl) via Schiff reaction can physically crosslink (complex) with Co ions. Co-complexed PAM (Co-PAM) in the form of gel is calcined to become a Co, N-co-doped carbonaceous matrix (Co-N-C), acting as cathode catalyst of an anion exchange membrane fuel cell (AEMFC). The obtained Co-N-C catalyst demonstrates a single-atom structure with active Co centers seen under the high-resolution transmission electron microscopy (HRTEM). The Co-N-C catalysts are also characterized by XRD, SEM, TEM, XPS, BET, and Raman spectroscopy. The Co-N-C catalysts demonstrate oxygen reduction reaction (ORR) activity in the KOH(aq) by expressing an onset potential of 1.19-1.37 V vs. RHE, a half wave potential of 0.70-0.92 V, a Tafel slope of 61-89 mV/dec., and number of exchange electrons of 2.48-3.79. Significant ORR peaks appear in the current-voltage (CV) polarization curves for the Co-N-C catalysts that experience two-stage calcination higher than 900 °C, followed by double acid leaching (CoNC-1000A-900A). The reduction current of CoNC-1000A-900A is comparable to that of commercial Pt-implanted carbon (Pt/C), and the max power density of the single cell using CoNC-1000A-900A as cathode catalyst reaches 275 mW cm-2.
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A magnesium potassium phosphate hydrate-based flame-retardant coating (MKPC) is formulated by dead-burnt magnesium oxide (magnesia) and potassium dihydrogen phosphate (KH2PO4), behaving as a matrix. Constituents of the MKPC include wollastonite, vermiculite, aluminum fluoride, aluminum trihydroxide, and calcium carbonate. Some of the ingredients inter-react to produce mullite whiskers at high temperatures, despite an acid-base hydration induced reaction between magnesia and KH2PO4. The MKPC's thermal, corrosion-resistant, mechanical, and flame-resistant properties were analyzed using scanning electron microscopy, electrochemical corrosion testing, compression testing, thermogravimetric analysis, and freeze/thaw tests. The results show that with the molar ratio = 4 of magnesia to KH2PO4, MKPC demonstrates lower thermal conductivity (0.19 W/m K), along with better corrosion resistance, stronger compressive strength (10.5 MPa), and higher bonding strength (6.62 kgf/cm2) to the steel substrate. Furthermore, acceptable additives to the formulation could enhance its flame-retardancy and increase its mechanical strength as well. Mullite whisker formed from the interaction of wollastonite, aluminum trihydroxide, and aluminum fluoride acts as an outer ceramic shield that enhances mechanical strength and compactness. In addition, Mg-containing minerals with calcium carbonate treated at high temperatures, transform into magnesium calcium carbonate after releasing CO2. At the optimum composition of MKPC (magnesia/KH2PO4 molar ratio = 4; wollastonite:vermiculite = 20:10 wt.%; aluminum trihydroxide = 10 wt.%; and calcium carbonate = 5 wt.%), coated on a steel substrate, the flame-resistance limit results exhibit below 200 °C on the back surface of the steel substrate after one hour of flaming (ca. 1000 °C) on the other surface, and the flame-resistance rating results demonstrate only 420 °C on the back surface of the steel substrate after three hours of flaming (>1000 °C) on the other surface. Both requirements for the flame-resistance limit and three-hour flame-resistance rating are met with the optimum compositions, indicating that MKPC plays an effective role in establishing flame-retardancy.
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Cobalt-doped carbon nitride frameworks (CoNC) were prepared from the calcination of Co-chelated aromatic polyimines (APIM) synthesized from stepwise polymerization of p-phenylene diamine (PDA) and o-phthalaldehyde (OPAl) via Schiff base reactions in the presence of cobalt (II) chloride. The Co-chelated APIM (Co-APIM) precursor converted to CoNC after calcination in two-step heating with the second step performed at 100 °C lower than the first one. The CoNCs demonstrated that its Co, N-co-doped carbonaceous framework contained both graphene and carbon nanotube, as characterized by X-ray diffraction pattern, Raman spectra, and TEM micropictures. CoNCs also revealed a significant ORR peak in the current-voltage polarization cycle and a higher O2 reduction current than that of commercial Pt/C in a linear scanning voltage test in O2-saturated KOH(aq). The calculated e-transferred number even reaches 3.94 in KOH(aq) for the CoNC1000A900 cathode catalyst, which has the highest BET surface area of 393.94 m2 g-1. Single cells of anion exchange membrane fuel cells (AEMFCs) are fabricated using different CoNCs as the cathode catalysts, and CoNC1000A900 demonstrates a peak power density of 374.3 compared to the 334.7 mW cm-2 obtained from the single cell using Pt/C as the cathode catalyst.
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Flame-retardant coatings have drawn much attention in recent years. In this study, an inorganic sodium silicate-based intumescent flame-resistance coating with an excellent flameproof properties is developed by mainly utilizing sodium silicate as the ceramizable binder, via hydrolysis and self-condensation reaction. Fly ash, metakaoline, and wollastonite behave as supplement cementing materials. Major formulation encompasses the combination of the ammonium polyphosphate and pentaerythritol as the flame-retardant additives, and aluminum hydroxide or expandable graphite as the intumescence-improving filler agents. Expandable graphite was found to play an important role in the eventual performance of flame-resistance testing. The results showed that solid interaction forces can be formed between metakaoline and sodium silicate, resulting in a similar material to geopolymer with excellent physical properties. After high-temperature flame testing, a densely complex protective layer of carbon-char created on top of the robust silicon dioxide networks offers notable flame resistance. An optimal ratio in this inorganic intumescent coating contains sodium silicate-metakaoline (weight ratio = 9:1)-ammonium polyphosphate and pentaerythritol, aluminum hydroxide (3, 3, 10 wt.%)-expandable graphite (1 wt.%), which can create 4.7 times higher expansion ratio compared with neat sodium silicate matrix. The results of flame testing demonstrate only 387.1 °C and 506.3 °C on the back surface of steel substrate after one and three hours flaming (>1000 °C) on the other surface, respectively, which could meet the requirements according to the level of fire rating.
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Carbon nanofibers functionalized with aminobenzoyl groups (CNF-aminobenzoyl) were prepared via direct Friedel-Crafts acylation in polyphosphoric acid. The functionalization of CNFs was characterized using XPS, FTIR, TGA, and Raman analyses. Hexafluoroisopropylidene-containing polybenzimidazole (6FPBI) composite membranes containing pristine CNFs or CNF-aminobenzoyl were prepared using solvent-assisted dispersion and solvent-casting methods. In this work, the influence of the incorporation of functionalized CNFs on several physicochemical properties of the 6FPBI nanocomposite membranes, including their thermal stability, mechanical strength, and acid doping level, was studied. The results showed that CNF-aminobenzoyl provided better mechanical reinforcement for the nanocomposite membrane, compared to pristine CNF. The SEM observation confirmed the good compatibility between the CNF-aminobenzoyl fillers and the 6FPBI matrix. For the 0.3 wt% CNF-aminobenzoyl/6FPBI composite membrane, the tensile stress was increased by 12% to be 78.9 MPa (as compared to the 6FPBI membrane), the acid doping level was improved to 12.0, and the proton conductivity at 160 °C was measured above 0.2 S cm-1. Furthermore, the fuel cell performance of the membrane electrolyte assembly (MEA) for each nanocomposite membrane was evaluated. The maximum power density at 160 °C was found up to 461 mW cm-2 for the MEA based on the 0.3 wt% CNF-aminobenzoyl/6FPBI composite membrane.
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Aromatic polyimine (PIM) was prepared through condensation polymerization between p-phenylene diamine and terephthalaldehyde via Schiff reactions. PIM can be physically crosslinked with ferrous ions into gel. The gel-composites, calcined at two consecutive stages, with temperatures ranging from 600 to 1000 °C, became Fe- and N-doped carbonaceous organic frameworks (FeNC), which demonstrated both graphene- and carbon nanotube-like morphologies and behaved as an electron-conducting medium. After the two-stage calcination, one at 1000 °C in N2 and the other at 900 °C in a mixture of N2 and NH3, an FeNC composite (FeNC-1000A900) was obtained, which demonstrated a significant O2 reduction peak in its current-voltage curve in the O2 atmosphere, and thus, qualified as a catalyst for the oxygen reduction reaction. It also produced a higher reduction current than that of commercial Pt/C in a linear scanning voltage test, and the calculated e-transferred number reached 3.85. The max. power density reached 400 mW·cm-2 for the single cell using FeNC-1000A900 as the cathode catalyst, which was superior to other FeNC catalysts that were calcined at lower temperatures. The FeNC demonstrated only 10% loss of the reduction current at 1600 rpm after 1000 redox cycles, as compared to be 25% loss for the commercial Pt/C catalyst in the durability test.
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The hydrophilic initiator potassium persulfate (KPS) was converted into a hydrophobic molecule by complexing with cetyltrimethylammonium bromide (CTAB) at both ends of the molecule (CTAPSu). Inverse emulsion polymerization thus proceeded inside micelles dispersed in the affluent toluene with CTAPSu as the initiator. Polyaniline (PANI) formed inside the micelles and entangled with Fe3O4 nanoparticles already esterified with oleic acid (OA). Iron composites consisted of OA-esterified Fe3O4 nanoparticles covered with PANI after de-emulsification. After calcination at 950 °C in an argon atmosphere, the resultant iron compound was a mixture of α-Fe (ferrite) and Fe3C (cementite), as determined by X-ray diffraction. Eventually, the calcined iron compounds (mixtures) demonstrated superparamagnetic properties with a high saturation magnetization (Ms) of 197 emu/g, which decayed to 160 emu/g after exposure to the atmosphere for four months.
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Oleic acid (OA)-modified Fe3O4 nanoparticles were successfully covered with polyanilines (PANIs) via inverse suspension polymerization in accordance with SEM and TEM micrographs. The obtained nanoparticles were able to develop into a ferrite (α-Fe) and αâ³-Fe16N2 mixture with a superparamagnetic property and high saturated magnetization (SM) of 245 emu g-1 at 950 °C calcination under the protection of carbonization materials (calcined PANI) and other iron-compounds (αâ³-Fe16N2). The SM of the calcined iron-composites slightly decreases to 232 emu g-1 after staying in the open air for 3 months. The calcined mixture composite can be ground into homogeneous powders without the segregation of the iron and carbon phases in the mortar without significantly losing magnetic activities.
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A quaternized polybenzimidazole (PBI) membrane was synthesized by grafting a dimethylimidazolium end-capped side chain onto PBI. The organic-inorganic hybrid membrane of the quaternized PBI was prepared via a silane-induced crosslinking process with triethoxysilylpropyl dimethylimidazolium chloride. The chemical structure and membrane morphology were characterized using NMR, FTIR, TGA, SEM, EDX, AFM, SAXS, and XPS techniques. Compared with the pristine membrane of dimethylimidazolium-functionalized PBI, its hybrid membrane exhibited a lower swelling ratio, higher mechanical strength, and better oxidative stability. However, the morphology of hydrophilic/hydrophobic phase separation, which facilitates the ion transport along hydrophilic channels, only successfully developed in the pristine membrane. As a result, the hydroxide conductivity of the pristine membrane (5.02 × 10-2 S cm-1 at 80 °C) was measured higher than that of the hybrid membrane (2.22 × 10-2 S cm-1 at 80 °C). The hydroxide conductivity and tensile results suggested that both membranes had good alkaline stability in 2M KOH solution at 80 °C. Furthermore, the maximum power densities of the pristine and hybrid membranes of dimethylimidazolium-functionalized PBI reached 241 mW cm-2 and 152 mW cm-2 at 60 °C, respectively. The fuel cell performance result demonstrates that these two membranes are promising as AEMs for fuel cell applications.
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Triethylenetetramine (TETA) and thiourea complexed Cobalt(II) (Co(II)) ions are used as cathode catalysts for proton exchanged membrane fuel cells (PEMFCs) under the protection of polyaniline (PANI) which can become a conducting medium after calcination. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra clearly reveal the presence of typical carbon nitride and sulfide bonds of the calcined Nitrogen (N)- or Sulfur (S)-doped co-catalysts. Clear (002) and (100) planes of carbon-related X-ray diffraction patterns are found for co-catalysts after calcination, related to the formation of a conducting medium after the calcination of PANI. An increasing intensity ratio of the D to G band of the Raman spectra reveal the doping of N and S elements. More porous surfaces of co-catalysts are found in scanning electronic microscopy (SEM) micropictures when prepared in the presence of both TETA and thiourea (CoNxSyC). Linear sweep voltammetry (LSV) curves show the highest reducing current to be 4 mAcm-2 at 1600 rpm for CoNxSyC, indicating the necessity for both N- and S-doping. The membrane electrode assemblies (MEA) prepared with the cathode made of CoNxSyC produces the highest maximum power density, close to 180 mW cm-2.
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The small sized copper nanoparticles (Cu-NPs), prepared in the presence of triethylene tetramine (TETA) and assisted with microwave irradiation, have an extremely low melting temperature. Melting of the small sizezd Cu-NPs can be triggered by the heat generated from the e-beam irradiation during SEM and TEM image construction. The dispersed Cu atoms around the agglomerated big Cu particles can undergo recrystallization immediately due to the strong driving force of the huge temperature difference to normal melting temperature (Tm = 1085 °C). Some of the Cu-NPs with bigger sizes also recrystallize and agglomerate into dense, big particles. According to X-ray diffraction patterns, these particles can agglomerate into compact, ordered Cu crystals in less than five minutes at 60 °C. The melting and recrystallization related endothermic and exothermic phase transitions of Cu-NPs can be found from differential scanning calorimeter (DSC) thermograms and optical microscopic pictures.
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Calcination reduction reaction is used to prepare Pt/EB (emeraldine base)-XC72 (Vulcan carbon black) composites as the cathode material of a proton exchange membrane fuel cell (PEMFC). The EB-XC72 core-shell composite obtained from directly polymerizing aniline on XC72 particles is able to chelate and capture the Pt-ions before calcination. X-ray diffraction spectra demonstrate Pt particles are successfully obtained on the EB-XC72 when the calcined temperature is higher than 600 °C. Micrographs of TEM and SEM illustrate the affluent, Pt nanoparticles are uniformly distributed on EB-XC72 at 800 °C (Pt/EB-XC72/800). More Pt is deposited on Pt/EB-XC72 composite as temperatures are higher than 600 °C. The Pt/EB-XC72/800 catalyst demonstrates typical type of a cyclic voltammograms (C-V) curve of a Pt-catalyst with clear Pt-H oxidation and Pt-O reduction peaks. The highest number of transferred electrons during ORR approaches 3.88 for Pt/EB-XC72/800. The maximum power density of the single cell based on Pt/EB-XC72/800 reaches 550 mW cm-2.
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To investigate (1) the effects of indoor incense burning upon cognition over 3 years; (2) the associations between indoor incense burning with the brain's structure and functional connectivity of the default mode network (DMN); and (3) the interactions between indoor incense burning and vascular disease markers upon cognitive functions. Community older adults without stroke or dementia were recruited (n = 515). Indoor incense use was self-reported as having burnt incense at home ≥ weekly basis over the past 5 years. Detailed neuropsychological battery was administered at baseline (n = 227) and the Montreal Cognitive Assessment at baseline and year 3 (n = 515). MRI structural measures and functional connectivity of the DMN were recorded at baseline. Demographic and vascular risk factors and levels of outdoor pollutants were treated as covariates. Indoor incense burning was associated with reduced performance across multiple cognitive domains at baseline and year 3 as well as decreased connectivity in the DMN. It interacted with diabetes mellitus, hyperlipidemia and white matter hyperintensities to predict poorer cognitive performance. Indoor incense burning is (1) associated with poorer cognitive performance over 3 years; (2) related to decreased brain connectivity; and (3) it interacts with vascular disease to predispose poor cognitive performance.