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1.
J Nanosci Nanotechnol ; 20(2): 752-759, 2020 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-31383070

RESUMO

An Al3+-based metal-organic framework (MOF), CAU-11-COOH, with a V-shaped ligand, DPSDA (3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride), was prepared using the solvothermal method, and was characterized using powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, elemental analysis, thermogravimetric analysis, Brunauer-Emmett-Teller analysis, and CO2 adsorption. The catalytic efficiency of CAU-11-COOH was investigated in the solvent-free cycloaddition of carbon dioxide with epoxides, which yielded five-membered cyclic carbonates under mild reaction conditions. CAU-11-COOH with a co-catalyst, tetrabutylammonium bromide (TBAB), gave higher than 98% yield of epichlorohydrin carbonate at 80 °C without a solvent. A plausible reaction mechanism in which the Lewis acidic metal center, an uncoordinated carboxyl group, and a nucleophilic bromide anion operate synergistically is proposed. The CAU-11-COOH catalysts were found to exhibit high thermal stability and could be reused more than four times without any significant reduction in activity.

2.
Inorg Chem ; 58(17): 11389-11403, 2019 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-31433625

RESUMO

We synthesized two new adenine-based Zn(II)/Cd(II) metal-organic frameworks (MOFs), namely, [Zn2(H2O)(stdb)2(5H-Ade)(9H-Ade)2]n (PNU-21) and [Cd2(Hstdb)(stdb)(8H-Ade)(Ade)]n (PNU-22), containing auxiliary dicarboxylate ligand (stdb = 4,4'-stilbenedicarboxylate). Both MOFs were characterized by multiple analytical techniques such as single-crystal X-ray diffraction (SXRD), powder X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, scanning electron microscopy, as well as temperature program desorption and Brunauer-Emmett-Teller measurements. Both MOFs were structurally robust and possessed unsaturated Lewis acidic metal centers [Zn(II) and Cd(II)] and free basic N atoms of adenine molecules. They were used as heterogeneous catalysts for the fixation of CO2 into five-membered cyclic carbonates. Significant conversion of epichlorohydrin (ECH) was attained at a low CO2 pressure (0.4 MPa) and moderate catalyst (0.6 mol %)/cocatalyst (0.3 mol %) amounts, with over 99% selectivity toward the ECH carbonate. They showed comparable or even higher catalytic activity than other previously reported MOFs. Because of high thermal stability and robust architecture of PNU-21/PNU-22, both catalysts could be reused with simple separation up to five successive cycles without any considerable loss of their catalytic activity. Densely populated acidic and basic sites in both Zn(II)/Cd(II) MOFs facilitated the conversion of ECH to ECH carbonate in high yields. The reaction mechanism of the cycloaddition reaction between ECH and CO2 is described by possible intermediates, transition states, and pathways, from the density functional theory calculation in correlation with the SXRD structure of PNU-21.

3.
ChemSusChem ; 12(5): 1033-1042, 2019 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-30610753

RESUMO

A facile approach for modifying the UiO-66-NH2 metal-organic framework by incorporating imidazolium-based ionic liquids (ILs) to form bifunctional heterogeneous catalysts for the cycloaddition of epoxides to CO2 is reported. Methylimidazolium- and methylbenzimidazolium-based IL units (ILA and ILB, respectively) were introduced into the pore walls of the UiO-66-NH2 framework through a condensation reaction to generate ILA@U6N and ILB@U6N catalysts, respectively. The resultant heterogeneous catalysts, especially ILA@U6N, exhibited excellent CO2 adsorption capability, which makes them effective for cycloaddition reactions producing cyclic carbonates under mild reaction conditions in the absence of any cocatalyst or solvent. The significantly enhanced activity of ILA@U6N is attributed to the synergism between the coordinately unsaturated Lewis acidic Zr4+ centers and Br- ions in the bifunctional heterogeneous catalysts. The size effect of the ILs on coupling between the epoxide and CO2 was also studied for ILA@U6N and ILB@U6N. A periodic DFT study was performed to provide evidence of possible intermediates, transition states, and pathways, as well as to gain deeper insight into the mechanism of the ILA@U6N-catalyzed cycloaddition reaction between epichlorohydrin and CO2 .

4.
ACS Appl Mater Interfaces ; 10(38): 32323-32330, 2018 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-30168328

RESUMO

We report the effect of epoxy adhesion layers with different mechanical or physical property on a magnetoelectric (ME) composite laminate composed of FeBSi alloy (Metglas)/single-crystal Pb(Mg1/3Nb2/3)O3-Pb(Zr,Ti)O3/Metglas to achieve an improved ME conversion performance. Through theoretical simulation, it was revealed that the Young's modulus and the thickness of interfacial adhesives were major parameters that influence the conversion efficiency in ME composites. In the experimental evaluation, we utilized three epoxy materials with a distinct Young's modulus and adjusted the average thickness of the adhesion layers to optimize the ME conversion. The experimental results show that a thin epoxy layer with a high Young's modulus provided the best performance in the inorganic-based ME conversion process. By tailoring the interfacial adhesion property, the ME laminate generated a high conversion coefficient of 328.8 V/(cm Oe), with a mechanical quality factor of 132.0 at the resonance mode. Moreover, we demonstrated a highly sensitive alternating current magnetic field sensor that had a detection resolution below 10 pT. The optimization of the epoxy layers in the ME laminate composite provided significant enhancement of the ME response in a simple manner.

5.
Soft Matter ; 14(6): 1026-1042, 2018 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-29328340

RESUMO

We systematically examined the polymer-mediated interparticle interactions between polymer-grafted nanoparticles (NPs) within chemically identical homopolymer matrices through experimental and computational efforts. In experiments, we prepared thermally stable gold NPs grafted with polystyrene (PS) or poly(methyl methacrylate) (PMMA), and they were mixed with corresponding homopolymers. The nanocomposites are well dispersed when the molecular weight ratio of free to grafted polymers, α, is small. For α above 10, NPs are partially aggregated or clumped within the polymer matrix. Such aggregation of NPs at large α has been understood as an autophobic dewetting behavior of free homopolymers on brushes. In order to theoretically investigate this phenomenon, we calculated two particle interaction using self-consistent field theory (SCFT) with our newly developed numerical scheme, adopting two-dimensional finite volume method (FVM) and multi-coordinate-system (MCS) scheme which makes use of the reflection symmetry between the two NPs. By calculating the polymer density profile and interparticle potential, we identified the effects of several parameters such as brush thickness, particle radius, α, brush chain polydispersity, and chain end mobility. It was found that increasing α is the most efficient method for promoting autophobic dewetting phenomenon, and the attraction keeps increasing up to α = 20. At small α values, high polydispersity in brush may completely nullify the autophobic dewetting, while at intermediate α values, its effect is still significant in that the interparticle attractions are heavily reduced. Our calculation also revealed that the grafting type is not a significant factor affecting the NP aggregation behavior. The simulation result qualitatively agrees with the dispersion/aggregation transition of NPs found in our experiments.

6.
Soft Matter ; 13(33): 5527-5534, 2017 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-28795184

RESUMO

We investigated the domain spacing of an ordered structure formed by polydisperse ARB-type triblock copolymers (triBCPs) with random middle R blocks consisting of A and B monomers. ARB-type triBCPs were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the dispersities of all samples were controlled as narrow as ∼1.2. From the bulk and film morphologies, it was found that the domain swelling increases as the content of middle R blocks increases, which implies that the middle R block even with a small content plays a critical role in dilating the domain spacing. Since the random middle R blocks are energetically neutral, they can be segregated into either A or B blocks. The strong stretching theory (SST) suggests that the dispersities of the resulting constituent blocks are maximized to reduce the elastic energy associated with chain stretching, thereby leading to the dilation of domain spacing.

7.
Soft Matter ; 11(21): 4242-50, 2015 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-25894536

RESUMO

The directed self-assembly (DSA) of block copolymers (BCPs) has emerged as an alternative method to replace or complement conventional photolithography as a result of the approximately 10 nm scale of microdomain ordering, the variety of microstructures that can be obtained and its compatibility with current lithographic processes. In DSA, BCP microdomains are controlled via guide patterns and two main techniques are popular: graphoepitaxy and chemoepitaxy assembly. We have demonstrated a simple and feasible technology for a DSA process by combining graphoepitaxy with "inexpensive" chemoepitaxial assembly to improve the alignment of the lamellar microdomains. For chemoepitaxial assembly, the hexagonal surface patterns from cross-linkable, cylinder-forming BCP were used to guide the graphoepitaxial assembly of the overlying BCP lamellar film. When the guiding patterns were prepared on the hexagonal patterns, it was found that the degree of lamellar alignment was significantly improved compared with the lamellar alignment on the homogeneous neutral layers. Simulation results suggested that the underlying hexagonal pattern can assist the lamellar alignment by reducing the large number of orientation states of the lamellar layers. This strategy is applicable to various nanofabrication processes that require a high degree of fidelity in controlling the nanopatterns over large areas with reduced costs.

8.
ACS Appl Mater Interfaces ; 7(14): 7741-51, 2015 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-25790085

RESUMO

Two new cationic iridium complexes, [Ir(ppy)2(phpzpy)]PF6 (complex 1) and [Ir(dfppy)2(phpzpy)]PF6 (complex 2), bearing a 2-(3-phenyl-1H-pyrazol-1-yl)pyridine (phpzpy) ancillary ligand and either 2-phenylpyridine (Hppy) or 2-(2,4-difluorophenyl)pyridine (Hdfppy) cyclometalating ligands, were synthesized and fully characterized. The photophysical and electrochemical properties of these complexes were investigated by means of UV-visible spectroscopy, emission spectroscopy, and cyclic voltammetry. Density functional theory (DFT) and time dependent DFT (TD-DFT) calculations were performed to simulate and study the photophysical and electrochemical properties of both complexes. Light-emitting electrochemical cells (LECs) were fabricated by incorporating complexes 1 and 2, which respectively exhibit blue-green (488 and 516 nm) and blue (463 and 491 nm) emission colors, achieved through the meticulous design of the ancillary ligand. The luminance and current efficiency measurements recorded for the LEC based on complex 1 were 1246 cd m(-2) and 0.46 cd A(-1), respectively, and were higher than those measured for complex 2 because of the superior balanced carrier injection and recombination properties of the former.

9.
ACS Appl Mater Interfaces ; 6(20): 17416-25, 2014 Oct 22.
Artigo em Inglês | MEDLINE | ID: mdl-25277650

RESUMO

A series of cationic iridium complexes (1-6) were synthesized using alkylated imidazole-based ancillary ligands, and the photophysical and electrochemical properties of these complexes were subsequently evaluated. Light-emitting electrochemical cells (LECs) were fabricated from these complexes, and the effects of the alkyl chain length on the electroluminescent properties of the devices were investigated. The LECs based on these complexes resulted in yellow emission (complexes 1, 3, and 5) and green emission (complexes 2, 4, and 6) with Commission Internationale de L'Eclairage (CIE) coordinates of (0.49, 0.50) and (0.33, 0.59), respectively. Our results indicate that the luminance and efficiency of the LECs can consistently be enhanced by increasing the alkyl chain length of the iridium complexes as a result of suppressed intermolecular interaction and self-quenching. Subsequently, a high luminance of 7309 cd m(-2) and current efficiency of 3.85 cd A(-1) were achieved for the LECs based on complex 5.

10.
Nanoscale Res Lett ; 8(1): 240, 2013 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-23680100

RESUMO

We have investigated the effect of fibrous nanostructured ZnO film as a hole-conducting layer on the performance of polymer photovoltaic cells. By increasing the concentration of zinc acetate dihydrate, the changes of performance characteristics were evaluated. Fibrous nanostructured ZnO film was prepared by sol-gel process and annealed on a hot plate. As the concentration of zinc acetate dihydrate increased, ZnO fibrous nanostructure grew from 300 to 600 nm. The obtained ZnO nanostructured fibrous films have taken the shape of a maze-like structure and were characterized by UV-visible absorption, scanning electron microscopy, and X-ray diffraction techniques. The intensity of absorption bands in the ultraviolet region was increased with increasing precursor concentration. The X-ray diffraction studies show that the ZnO fibrous nanostructures became strongly (002)-oriented with increasing concentration of precursor. The bulk heterojunction photovoltaic cells were fabricated using poly(3-hexylthiophene-2,5-diyl) and indene-C60 bisadduct as active layer, and their electrical properties were investigated. The external quantum efficiency of the fabricated device increased with increasing precursor concentration.

11.
Nanoscale Res Lett ; 7(1): 5, 2012 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-22221320

RESUMO

We have investigated the effect of pentacene-doped poly(3,4-ethylenedioxythiophene:poly(4-styrenesulfonate) [PEDOT:PSS] films as a hole-conducting layer on the performance of polymer photovoltaic cells. By increasing the amount of pentacene and the annealing temperature of pentacene-doped PEDOT:PSS layer, the changes of performance characteristics were evaluated. Pentacene-doped PEDOT:PSS thin films were prepared by dissolving pentacene in 1-methyl-2-pyrrolidinone solvent and mixing with PEDOT:PSS. As the amount of pentacene in the PEDOT:PSS solution was increased, UV-visible transmittance also increased dramatically. By increasing the amount of pentacene in PEDOT:PSS films, dramatic decreases in both the work function and surface resistance were observed. However, the work function and surface resistance began to sharply increase above the doping amount of pentacene at 7.7 and 9.9 mg, respectively. As the annealing temperature was increased, the surface roughness of pentacene-doped PEDOT:PSS films also increased, leading to the formation of PEDOT:PSS aggregates. The films of pentacene-doped PEDOT:PSS were characterized by AFM, SEM, UV-visible transmittance, surface analyzer, surface resistance, and photovoltaic response analysis.

12.
Nanoscale Res Lett ; 7(1): 56, 2012 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-22221558

RESUMO

We have investigated the performance characteristics of bulk-heterojunction polymer solar cells based on poly(3-hexylthiophene-2,5-diyl) and [6,6]-phenyl C61 butyric acid methyl ester by adding 1,8-octanedithiol as a processing agent in an active layer. The effects of the additive, 1,8-octanedithiol, on the device performance parameter characteristics have been discussed. The current density-voltage measurements, UV-Vis absorption spectra, X-ray diffraction spectra, and scanning probe microscope images have been used to discuss the performance characteristics of polymer solar cells.

13.
Colloids Surf B Biointerfaces ; 38(3-4): 155-60, 2004 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-15542318

RESUMO

As functional metal complexes, copper phthalocyanine (CuPc) and Cobalt (II) meso-tetraphenylporphyrin (CoTPP) were chosen to prepare metal complex/polymer hybrid thin films which were prepared by metal complex sublimation and reactive monomer evaporation onto the glass substrate in the bell jar reactor in vacuum conditions. The polarized transmission micrograph images show that the film deposited at 80 degrees C contains uniformly dispersed tiny grains and the film deposited at 30 degrees C is amorphous and homogeneous. As the deposition rate increases, the crystalline clusters were found and were dispersed uniformly. Those crystalline clusters are not to be developed by recrystallization process. Deposited metal complex/acrylate hybrid thin films were in situ photopolymerized. The kinetics of photopolymerization was investigated by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The thickness of the films was about 200 nm. The reactive monomer acts as a solvent to avoid the recrystallization of metal complexes and to have two-compositional continuous phase. The percent of metal complex can be adjusted up to 60% by controlling the metal complex sublimation rate. A good achievement in the uniformity and continuity of the film matrix has been made and the recrystallization of metal complex in the hybrid films has not been observed.


Assuntos
Acrilatos/química , Metais/química , Porfirinas/química , Cristalização , Cinética , Fotoquímica , Espectroscopia de Infravermelho com Transformada de Fourier
14.
Colloids Surf B Biointerfaces ; 38(3-4): 161-5, 2004 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-15542319

RESUMO

Cobalt(II) meso-tetraphenylporphyrin (CoTPP)/acrylate hybrid thin films were prepared by CoTPP sublimation and reactive monomer evaporation onto the glass substrate in vacuum conditions. Deposited CoTPP/acrylate thin films were in situ photopolymerized. The oxygen-uptake behaviors of CoTPP/acrylate films were investigated by means of sorption measurements, monitored by gravimetric means, and analyzed using dual mode sorption model. The loading percent of CoTPP in the film was adjusted up to 60% by controlling the CoTPP sublimation rate. The thickness of the CoTPP/acrylate hybrid film was about 200 nm and oxygen-uptake data obtained from the sorption measurements indicated that CoTPP molecules in the CoTPP/acrylate hybrid films were able to bind oxygen molecules reversibly.


Assuntos
Acrilatos/química , Metais/química , Oxigênio/química , Porfirinas/química , Ligantes , Fotoquímica
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